An oil-resistant environment-friendly TTO carbon ribbon and a preparation method thereof

Abstract

This invention discloses an oil-resistant, environmentally friendly TTO ribbon, comprising a base film, an adhesive layer on one side of the base film, and, from bottom to top, a bottom protective layer, a top anti-oil layer, and a heat transfer ink layer on the other side. The bottom protective layer, a composite of high-molecular-weight polyester resin and fatty acid amide, constructs a molecular-level dense barrier, specifically blocking the molecular penetration of saturated fatty acids from animal fats through the formation of a dense film structure. The top anti-oil layer, through the interfacial synergy of epoxy-modified acrylic resin and polyether-modified silicone oil, disrupts the molecular adhesion of unsaturated fatty acids in vegetable oils. Simultaneously, a temperature-sensitive anti-oil agent with a critical response temperature of 60-70℃ is introduced, utilizing its temperature phase change characteristics to achieve intelligent protection upgrades under high-temperature conditions in food processing. This invention aims to solve the technical problems of existing TTO heat transfer ribbons: lack of differentiated protection design for animal and vegetable oils, environmental hazards of fluorinated additives, insufficient durability under complex working conditions, and poor food contact safety.

Description

[0001] This invention belongs to the field of heat transfer consumables technology, specifically relating to an oil-resistant, environmentally friendly TTO ribbon and its preparation method. It is particularly suitable for printing product information and traceability barcodes in high-oil food contact scenarios such as meat processing, vegetable oil production, and fried food packaging in environments ranging from -10℃ to 120℃. The product also complies with EU REACH, China GB 4806.1-2016, and US FDA food contact material safety standards. Background Technology

[0002] TTO ribbon is a core consumable for printing barcodes and product traceability information, and it is widely used in high-speed production lines for food packaging, meat processing, and vegetable oil production. In these scenarios, animal fats (rich in long-chain saturated fatty acids, with low molecular polarity and strong penetration) and vegetable oils (rich in unsaturated fatty acids, with double bonds in the molecule and strong interfacial adhesion) can easily cause the heat transfer ink to soak, penetrate, and peel off, resulting in blurred and faded ink, affecting the accuracy and compliance of product traceability. At the same time, food contact scenarios place strict requirements on the environmental friendliness of consumables and the absence of harmful substance migration.

[0003] In existing technologies, the development of grease-resistant heat transfer ribbons mainly focuses on simple compounding of resin systems and the use of fluorinated grease-resistant additives, which has three major drawbacks: 1) Undifferentiated protective design: For example, the heat transfer ribbon disclosed in Chinese patent CN 110452573 A, which uses saturated polyester resin and epoxy resin to form a film, only achieves 48-hour oil immersion protection through a single resin barrier. It does not design a special protective layer for the chemical structure differences of animal and vegetable oils, and its effect on blocking the penetration of saturated fatty acids and the adhesion and damage of unsaturated fatty acids is not good. 2) Insufficient durability under complex working conditions: For example, Chinese patent CN 114261223 B uses saturated polyester, acrylic acid and chloroacetic acid to form a film to improve alcohol resistance, but it cannot cope with the complex working conditions of 100°C high temperature + friction in food processing. The imprint is easily worn and does not meet the requirements of resistance to animal and vegetable oils in high oil scenarios. 3) Poor environmental protection and food safety: Fluorine-based anti-oil additives pose a risk of PFOA / PFOS residue, are prone to migration of harmful substances, and some products have excessive heavy metal leaching, making it difficult to meet international food contact standards. 4) Low transfer efficiency: The transfer speed of existing products is mostly below 200mm / s, which cannot meet the needs of high-speed production lines in the food processing industry.

[0004] Therefore, the development of heat transfer ribbons that combine precise protection against animal and vegetable oil differences, are fluorine-free and environmentally friendly, have high durability under complex working conditions, high transfer efficiency, and meet multiple national food contact standards has become an urgent need in this field. Summary of the Invention

[0005] The purpose of this invention is to overcome the shortcomings of existing technologies and provide an environmentally friendly, oil-resistant TTO ribbon. This ribbon features a dual-layer differentiated oil-resistant protection system designed to address the chemical structural differences between animal and vegetable oils, enhancing protection against saturated and unsaturated fatty acids. It completely replaces fluorinated compounds with plant-based oil-resistant agents, and combines the temperature phase change characteristics of temperature-sensitive oil-resistant agents to achieve a balance between environmental friendliness and intelligent high-temperature protection. This ensures the product complies with EU REACH, Chinese GB 4806.1-2016, and US FDA food contact standards, and its transfer speed is compatible with high-speed food processing production lines, making it suitable for large-scale industrialization.

[0006] The present invention also provides a method for preparing the above-mentioned oil-resistant and environmentally friendly TTO carbon ribbon.

[0007] To achieve the above objectives, the present invention adopts the following technical solution: An oil-resistant, environmentally friendly TTO carbon ribbon includes a base film, an adhesive backing layer on one side of the base film, and, from bottom to top, a bottom protective layer, a top anti-oil layer, and a heat transfer ink layer on the other side of the base film. The adhesive backing layer is used to improve the heat resistance of the base film. The raw material of the adhesive backing layer is acrylic-modified silicone resin, and the adhesive backing layer is made by coating the base film with acrylic-modified silicone resin. The weight of each raw material in the bottom protective layer, per 100 parts, is as follows: 60-75 parts of high molecular weight polyester resin, 15-25 parts of fatty acid amide, 5-10 parts of plant-based anti-oil agent, 1-3 parts of nano-silica, and 0.5-2 parts of modified acrylic multi-polymer ammonium salt dispersant.

[0008] Specifically, the weight of each raw material in the top anti-oil layer, calculated per 100 parts, is as follows: 55-70 parts epoxy-modified acrylic resin, 10-18 parts polyether-modified silicone oil, 8-15 parts plant-based anti-oil agent, 3-8 parts thermosensitive anti-oil agent with a critical response temperature of 60-70℃, and 2-5 parts isocyanate curing agent.

[0009] Specifically, the weight of each raw material in the heat transfer ink layer, per 100 parts, is as follows: 33-45 parts saturated polyester resin, 2-5 parts polyurethane, 15-20 parts carnauba wax, 25-35 parts carbon black, 5-10 parts tackifying resin with a softening point of 100-130℃, and 0.3-1 parts antioxidant.

[0010] Specifically, in the bottom protective layer, the number average molecular weight of the high molecular weight polyester resin is 20,000-30,000, and the glass transition temperature is 40-65℃; the fatty acid amide is one of stearamide, erucamide, etc., wherein stearamide is suitable for lard / tallow barrier and erucamide is suitable for poultry oil barrier.

[0011] Furthermore, in the top oil-resistant layer, the epoxy-modified acrylic resin is obtained by graft copolymerization of bisphenol A type epoxy resin and acrylate monomers; the polyether-modified silicone oil is a polyoxyethylene-polyoxypropylene block-modified silicone oil. The isocyanate curing agent includes a trimer aliphatic isocyanate curing agent, such as hexamethylene diisocyanate (HDI).

[0012] Furthermore, in the heat transfer ink layer, the tackifying resin is one or more of rosin resin, terpene resin, petroleum resin, etc.; the antioxidant is a hindered phenolic antioxidant or a phosphite antioxidant, such as pentaerythritol tetrakis(3,5-di-tert-butyl-4-hydroxy)phenylpropionate antioxidant or tris(2,4-di-tert-butylphenyl)phosphite antioxidant, etc.

[0013] Furthermore, the plant-based oil-resistant agent is one of cork sulfate lignin, chitosan quaternary ammonium salt, cellulose acetate, etc.; the temperature-sensitive oil-resistant agent is poly(N-isopropylacrylamide) grafted modified silica or poly(N-vinylcaprolactam) grafted modified silica, etc., with a grafting rate of 15-25%.

[0014] Furthermore, the bottom protective layer has a porosity of ≤3% and a thickness of 1.5-2.0μm; the top oil-resistant layer has a surface contact angle of ≥105° and a thickness of 1.5-2.0μm; the thermal transfer ink layer has a coating amount of 1.7-1.9g / m² and an ink fineness of ≤3μm; and the base film is a polyethylene terephthalate film with a thickness of 4.5-5μm.

[0015] In this invention, the synthesis method of the thermosensitive anti-oil agent polyN-vinylcaprolactam grafted modified silica is as follows: Step 1, Silica KH-570 silane modification; (1) Silica ethanol dispersion: Add 5000-6000g of silica and 40-50L of anhydrous ethanol to a four-necked reactor, and ultrasonically disperse until there are no visible agglomerated particles. (2) Preparation of silane hydrolysate: Mix 5-7L of anhydrous ethanol and 5-7L of deionized water in a 20L reactor, slowly add glacial acetic acid, stir to adjust the pH to 4.0-4.5, add 6500-7000g of silane coupling agent KH-570, and stir at room temperature until the solution is completely transparent. (3) Grafting reaction: Transfer all the silane hydrolysate to silica ethanol dispersion, continuously purging with nitrogen for protection; stir and heat to 70±10℃ and stir at a constant temperature for 6±1 h to complete the vinyl functionalization grafting on the silica surface; Step 2, In-situ free radical polymerization grafting of N-vinylcaprolactam (NVCL); (1) Remove ethanol and water from the four-necked reactor system by vacuum distillation, leaving only modified silica solid; add 30-50L toluene, ultrasonically disperse evenly, and purge with nitrogen for 30 min. (2) Prepare monomer initiator pre-solution: add 5-7L toluene, 4000-4500g N-vinylcaprolactam (NVCL), and 120±20g azobisisobutyronitrile (AIBN) to a 20L reactor and stir until completely dissolved; (3) Isothermal grafting polymerization reaction: under nitrogen protection, add the monomer initiator pre-solution prepared in (2) to the four-necked reactor and react at a constant temperature of 72±10℃ for 16±4 h with stirring; this temperature is the core control point, which directly determines the LCST and grafting rate range of the product; Step 3, post-processing; (1) Solid-liquid separation: The reaction system is naturally cooled to room temperature, centrifuged, the upper toluene mother liquor is discarded, and the lower solid is collected; (2) Purification and washing: Wash with n-hexane; (3) Drying and pulverizing: The wet solid is transferred to a vacuum drying oven for vacuum drying; after cooling to room temperature, it is lightly ground to break up the clumps, and the white thermosensitive silica powder product is obtained.

[0016] This invention provides a method for preparing the above-mentioned oil-resistant and environmentally friendly TTO carbon ribbon, which includes the following steps: (1) Preparation of the bottom protective layer coating liquid: Polyester resin, fatty acid amide, plant-based anti-oil agent, nano silica and modified acrylic multi-polymer ammonium salt dispersant are added to the solvent, stirred and dispersed, and ground to fineness ≤3μm to obtain a bottom protective layer coating liquid with a solid content of 30-40%. (2) Preparation of top anti-oil coating liquid: Epoxy modified acrylic resin, polyether modified silicone oil, plant-based anti-oil agent, temperature-sensitive anti-oil agent and isocyanate curing agent are added to solvent, ultrasonically dispersed and filtered to obtain a top anti-oil coating liquid with a solid content of 25-35%. (3) Preparation of heat transfer ink: Saturated polyester resin, polyurethane, carnauba wax and tackifying resin are mixed and added to a solvent, stirred and dissolved at 90-100℃, cooled to below 40℃ and then carbon black and antioxidant are added, stirred and dispersed, and ground until the ink fineness is ≤3μm to obtain heat transfer ink; (4) Composite molding: Coat one side of the base film with acrylic modified silicone resin diluent and dry and cure at 110-120℃ to form a backing layer; coat the other side of the base film with the backing layer with a bottom protective layer coating liquid and dry and cure at 110-120℃; then coat the top anti-oil layer coating liquid and dry and cure at 100-110℃; finally coat the heat transfer ink and dry and cure at 90-100℃ to obtain the final product.

[0017] As a preferred technical solution, the above-mentioned method for preparing grease-resistant and environmentally friendly TTO ribbon employs a step-by-step coating, gradient curing, and precise parameter optimization process to ensure the adhesion between layers, coating uniformity, and performance stability. Furthermore, all process parameters have been verified through single-variable optimization experiments, with clear optimization criteria. The specific steps include (see process flow diagram for details). Figure 3 ): (1) Preparation of the bottom protective layer coating liquid: high molecular weight polyester resin, fatty acid amide, plant-based anti-oil agent, nano silica and modified acrylic multi-polymer ammonium salt dispersant are added to a mixed solvent of toluene and ethyl acetate. The volume ratio of toluene to ethyl acetate in the mixed solvent is 1:0.8-1.2. The mixture is stirred and dispersed at a high speed of 1500-2500 r / min for 30-60 min. The mixture is then ground by three rollers until the fineness is ≤3μm to obtain a bottom protective layer coating liquid with a solid content of 30-40%. Process optimization is based on the following: when the stirring speed is 2000 r / min, the dispersion time is 45 min, and the solvent volume ratio is 1:1, the filler is most evenly dispersed and there is no agglomeration; when the solid content is 30-40%, the viscosity of the coating liquid is best matched with the ceramic screen roller gravure coating. If it is too low, it is easy to sag, and if it is too high, the coating will be uneven.

[0018] (2) Preparation of top anti-oil coating liquid: Epoxy modified acrylic resin, polyether modified silicone oil, plant-based anti-oil agent, temperature-sensitive anti-oil agent and isocyanate curing agent are added to a mixed solvent of butanone and isopropanol, wherein the volume ratio of butanone to isopropanol in the mixed solvent is 1:0.5-0.8. The mixture is ultrasonically dispersed at 300-500W power for 20-40min and filtered through a 100-200 mesh screen to obtain a top anti-oil coating liquid with a solid content of 25-35%. Process optimization is based on the following: when the ultrasonic power is 400W, the dispersion time is 30min, and the solvent volume ratio is 1:0.6, the dispersibility of the temperature-sensitive anti-oil agent is optimal, and no molecular chain damage occurs; filtration through a 150-mesh filter can remove micro-agglomerates and ensure coating uniformity.

[0019] (3) Preparation of heat transfer ink: Saturated polyester resin, polyurethane, carnauba wax and tackifying resin are mixed and added to a mixed solvent of butanone and toluene. The volume ratio of butanone to toluene in the mixed solvent is 1:1.5-2. The mixture is stirred and dissolved at 90-100℃ for 90-120 min. After cooling to 40℃, carbon black and antioxidant are added. The mixture is stirred and dispersed at 200-400 r / min for 1.5-3 h. Then, it is ground 2-5 times with a horizontal rod-pin nano-sand mill filled with 0.5 mm ultrafine zirconia beads at a linear speed of 12-15 m / s until the ink fineness is ≤3 μm to obtain heat transfer ink. Process optimization is based on the following: stirring and dissolving at 95℃ for 100 minutes can completely dissolve the resin and wax without any undissolved matter; adding carbon black after cooling to 40℃ can prevent the carbon black from oxidizing at high temperatures; dispersing at 300r / min for 2 hours and grinding at a linear speed of 12m / s for 3 times can make the carbon black disperse evenly, and the ink fineness can reach about 1.8-2.1μm, with the best coloring power and transfer clarity.

[0020] (4) Composite molding: Apply acrylic modified silicone resin diluent to one side of the base film using a ceramic screen roller gravure coating method at a speed of 100-150m / min, and dry it under hot air circulation at 110-120℃ to form a backing adhesive layer; apply the bottom protective layer coating liquid to the other side of the base film with the backing adhesive layer using a ceramic screen roller gravure coating method at the same speed, and dry and cure it for 30s-1min under hot air circulation at 110-120℃ and wind speed of 3-5m / s; then apply the top anti-oil layer coating liquid using the same coating method, and dry and cure it for 30s-1min under hot air circulation at 100-110℃; finally apply heat transfer ink using the same coating method, and dry and cure it for 30s-1min under hot air circulation at 90-100℃, and then wind it up under a winding tension of 35-40N to obtain the finished product.

[0021] Basis for process optimization: Coating speed: 120m / min is the optimal value. Below 100m / min, the production efficiency is low. Above 150m / min, the coating thickness is uneven and the porosity increases. Gradient curing temperature: adhesive layer 110-120℃, bottom layer 110-120℃, top layer 100-110℃, ink layer 90-100℃. Gradient cooling curing can avoid internal stress caused by sudden temperature changes in each layer and improve the interlayer bonding strength (interlayer bonding strength ≥3MPa). Curing time: 30s-1min ensures complete solvent evaporation and avoids resin aging and damage to the molecular chains of temperature-sensitive anti-oil agents caused by long-term high-temperature curing; Winding tension: 35-40N ensures that the finished product is wound flat without wrinkles or stretching deformation.

[0022] Process advantages: It can be produced using existing mature ceramic screen roller gravure coating equipment without the need for additional equipment. The process parameters are controllable and have good repeatability. The production cost is comparable to that of traditional products, and it has the value of large-scale industrialization.

[0023] Further preferred, in step (1), the stirring speed is 2000 r / min, the dispersion time is 45 min, and the volume ratio of toluene to ethyl acetate in the mixed solvent is 1:1; in step (2), the ultrasonic power is 400 W, the dispersion time is 30 min, and the volume ratio of butanone to isopropanol in the mixed solvent is 1:0.6; in step (4), the coating speed is 120 m / min, the drying temperature of the bottom protective layer is 115 ℃, and the curing time is 45 s.

[0024] This invention also provides the application of the aforementioned oil-resistant, environmentally friendly TTO carbon ribbon. The ribbon is used in high-oil environments such as meat processing, vegetable oil production, fried food packaging, or dairy product packaging at ambient temperatures of -10℃ to 120℃. It enables clear transfer of barcodes, traceability information, or identification patterns onto polyethylene, polypropylene, polyvinyl chloride, or composite film substrates at a transfer speed of up to 300 mm / s. In these high-oil environments, the contact between oil and the ribbon is achieved through direct immersion, spraying, or wiping. Furthermore, the ribbon retains ≥95% of its performance after 12 months of storage at room temperature.

[0025] The grease-resistant and environmentally friendly TTO carbon ribbon of the present invention consists of, from top to bottom, a heat transfer ink layer, a top anti-oil layer, a bottom protective layer, and an adhesive layer. The four layers work together to form a comprehensive grease-resistant protection system of "precise barrier + interface anti-sticking + efficient transfer + substrate support". The design logic, material selection basis and working mechanism of each layer are as follows.

[0026] (1) Adhesive backing layer: Material selection: Polyethylene terephthalate (PET) film coated with acrylic-modified silicone resin; Selection criteria: PET film coated with adhesive (temperature resistance ≥150℃) has excellent heat resistance, mechanical strength and slip properties, which can effectively protect the print head and avoid sticking problems during high-temperature printing.

[0027] (2) Bottom protective layer – molecular-level barrier layer of saturated fatty acids from animal fats: Core design logic: Targeting the characteristics of saturated fatty acids (such as stearic acid and palmitic acid) in animal fats, such as regular molecular chains, low polarity, and easy permeation through coating pores, a highly dense membrane barrier is constructed to block permeation at the molecular level; Material selection and basis: Main resin: Polyester resin with a number average molecular weight of 20,000-30,000 and a glass transition temperature of 40-65℃ (Comparative tests show that when the number average molecular weight is less than 20,000, the effect of resisting saturated fatty acid penetration is not obvious; when the number average molecular weight is 20,000-30,000, the film-forming properties and density of the resin are balanced, and the effect of resisting saturated fatty acid penetration is significantly improved; if the molecular weight is too high, the film is brittle, and if it is too low, the density is insufficient, and the effect of resisting saturated fatty acid penetration is not obvious). Synergistic barrier agents: Fatty acid amides (stearamide / erucamide) form intermolecular hydrogen bonds with high molecular weight polyester resins, filling the gaps between resin molecules and further reducing the coating porosity to ≤3%; Selection criteria: Stearamide is suitable for blocking lard / beef tallow (C16-C18 saturated fatty acids), and erucamide is suitable for blocking poultry oil (C20-C22 saturated fatty acids). Oil-resistant agent: Plant-based oil-resistant agent with a particle size of 50-100nm (cork sulfate lignin / chitosan quaternary ammonium salt / / cellulose acetate). The nano-sized particles can fill the micro-pores of the coating, and the hydrophobic modification improves the hydrophobicity to animal fats, preventing the coating from being wetted by fats. Reinforcing agent: Nano silica, which enhances the mechanical strength of the coating and prevents the coating from breaking under friction conditions; Dispersant: Modified acrylic multi-polymer ammonium salt dispersant, to ensure uniform dispersion of nano-sized fillers in the resin system and avoid porosity increase caused by agglomeration; Performance indicators: thickness 1.5-2 μm, porosity ≤3%; when porosity >3%, the animal fat penetration barrier time will decrease from ≥120h to <48h, thus losing the differentiated protective effect.

[0028] (3) Top layer anti-oil layer - vegetable oil unsaturated fatty acid interface anti-sticking layer + high temperature intelligent protective layer: Core design logic: In response to the characteristics of unsaturated fatty acids (such as oleic acid and linoleic acid) in vegetable oils containing double bonds and strong interfacial adhesion, and the high-temperature conditions of food processing (60-100℃), dual protection is achieved through interfacial synergistic anti-adhesion and temperature-sensitive phase change densification. Material selection and basis: Film-forming resin: Epoxy-modified acrylic resin (obtained by graft copolymerization of bisphenol A type epoxy resin and acrylate monomer), which combines the chemical resistance of epoxy resin and the film-forming properties of acrylic resin. Interfacial anti-adhesion agent: Polyether-modified silicone oil with a hydrophilic-lipophilic balance value of 3-5. Its low surface energy characteristics can destroy the intermolecular forces between unsaturated fatty acids in vegetable oil and the coating surface, thereby reducing interfacial adhesion (comparative tests show that without the addition of polyether-modified silicone oil, the contact angle of the coating to vegetable oil is <80°, while after the addition, the contact angle is ≥105°, and the adhesion is reduced by more than 90%). Temperature-sensitive oil-resistant agent: Poly-N-isopropylacrylamide (PNIPAM) grafted modified silica or poly-N-vinylcaprolactam grafted modified silica with a critical response temperature of 60-70℃ and a grafting rate of 15-25%; Phase transition mechanism: This temperature-sensitive material has a low critical solution temperature (LCST) of 60-70℃. When the ambient temperature is below 60℃, the molecular chains are in a hydrophilic and extended state, uniformly dispersed in the top oil-resistant layer. When the ambient temperature reaches 60-70℃ (the core temperature range for frying, baking, and sterilization in food processing), the molecular chains undergo a hydrophobic contraction phase transition, rapidly aggregating to form a dense micro-nano-scale protective film. This increases the surface contact angle of the top oil-resistant layer from 105° to ≥120°, further reducing the porosity to ≤1%, achieving intelligent protection upgrades under high-temperature conditions. Critical temperature selection criteria: The conventional operating temperature for high-oil scenarios in food processing is 60-100℃. 60-70℃ is the phase transition initiation temperature, allowing for early high-temperature protection and preventing rapid wetting / penetration of oils at high temperatures. Oil-resistant agent: Plant-based oil-resistant agent with a particle size of 50-100nm and a hydrophobic surface modification. It works synergistically with temperature-sensitive oil-resistant agents to improve hydrophobicity and completely replaces fluorine compounds, leaving no PFOA / PFOS residue. Curing agent: Isocyanate curing agent, which causes cross-linking reaction of epoxy modified acrylic resin, improving the temperature resistance and mechanical strength of the coating; Performance indicators: thickness 1.5-2μm, surface contact angle ≥105°. If the thickness is too thick, it will affect the heat transfer efficiency; if it is too thin, it will not be able to form an effective anti-stick layer.

[0029] (4) Heat transfer ink layer - high-efficiency transfer + color stabilizing layer: Core design logic: While ensuring oil resistance, optimize the ratio of resin and wax system to improve transfer clarity, color strength and thermal stability, and adapt to high-speed transfer of 300mm / s; Material selection and basis: Film-forming resin: Saturated polyester resin + polyurethane compound. The saturated polyester resin ensures the film-forming properties and adhesion to the substrate after transfer, while the polyurethane enhances the flexibility of the ink and prevents the print from cracking during friction. Release agent: Carnauba wax (15-20 parts), whose melting point matches the heat transfer temperature, ensuring ink removal efficiency during high-speed transfer; Colorant: Carbon black (25-35 parts), to ensure the coloring power of the ink and the clarity of the barcode, with a fineness of ≤3μm to avoid pinholes during transfer; Tackifying resins: Rosin resin / terpene resin / petroleum resin with a softening point of 100-130℃, which improves the adhesion between ink and substrate (plastic, composite film). Antioxidants: Hindered phenolic / phosphite antioxidants improve the thermal stability of inks under high-temperature printing and high-temperature food processing conditions, and prevent ink oxidation and fading; Performance indicators: coating weight 1.7-1.9g / m², ink fineness ≤3μm. If the coating weight is too low, the coloring power will be insufficient; if it is too high, ink overflow will easily occur during transfer.

[0030] This invention aims to solve the technical problems of existing TTO thermal transfer ribbons, such as the lack of differentiated protection design for animal and vegetable oils, environmental hazards of fluorinated additives, insufficient durability under complex working conditions, and poor food contact safety. The core innovation of this invention is the complete replacement of fluorinated compounds with a hydrophobically modified plant-based anti-oil agent, balancing environmental friendliness and food contact safety. The product of this invention is resistant to immersion in animal fats for ≥120 hours and vegetable oils for ≥168 hours. Under complex working conditions of 100℃ high temperature + 50 cycles of friction, the color density loss is ≤5%, and the heavy metal leaching is <0.005mg / kg. It fully complies with EU REACH regulations, Chinese GB 4806.1-2016, and US FDA food contact material safety standards. It can be widely used in high-oil food scenarios such as meat processing, vegetable oil production, and fried food packaging in environments ranging from -10℃ to 120℃ for product information and traceability barcode printing.

[0031] The core and innovative points of this invention are specifically listed below: 1) The first design of a dual-layer differentiated oil-resistant protection system: the bottom layer provides molecular-level barrier against saturated fatty acids in animal fats, while the top layer provides interfacial anti-sticking and high-temperature intelligent protection against unsaturated fatty acids in vegetable oils, achieving precise protection of animal and vegetable oils. 2) Develop a temperature-sensitive anti-oil agent, poly-N-vinylcaprolactam-grafted modified silica, suitable for thermal transfer ribbons. Clarify the LCST phase transition mechanism of the temperature-sensitive anti-oil agent and accurately match the critical response temperature to the high-temperature range of food processing (60-70℃) to achieve intelligent protection upgrade under high-temperature conditions. 3) Each layer uses a nano-level plant-based oil-resistant agent to completely replace fluorine compounds, and is limited to a single variety (lignosulfonate lignin / chitosan quaternary ammonium salt / / cellulose acetate) to avoid an overly broad range, while ensuring no migration of harmful substances and meeting the food contact standards of multiple countries. 4) All materials were selected through comparative tests to verify and clarify the performance index thresholds (such as the number average molecular weight of polyester resin being 20,000-30,000 and the porosity of the bottom protective layer being ≤3%), rather than being simply compounded.

[0032] The oil-resistant, environmentally friendly TTO carbon ribbon described in this invention primarily involves animal and vegetable oils, hereinafter collectively referred to as oils. This invention designs a dual-layer differentiated oil-resistant protection system based on the chemical structural differences between animal and vegetable oils, enhancing the protection against saturated / unsaturated fatty acids. It completely replaces fluorinated compounds with plant-based oil-resistant agents, combining the temperature phase change characteristics of temperature-sensitive oil-resistant agents to achieve a combination of environmental friendliness and high-temperature intelligent protection. The invention elucidates the performance basis for material selection and the optimization logic of process parameters, improving the bonding strength of each layer and the durability under composite working conditions through gradient coating and step-by-step curing processes. This ensures the product simultaneously complies with EU REACH, Chinese GB 4806.1-2016, and US FDA food contact standards, and its transfer speed is compatible with high-speed food processing production lines, possessing large-scale industrialization value.

[0033] Compared with the prior art, the present invention has the following significant and verifiable beneficial effects: 1) Significantly differentiated protection against animal and vegetable oils: The bottom protective layer is designed for animal oils, withstanding immersion in lard for ≥120h and maintaining a clear imprint for ≥98%; the top oil-resistant layer is designed for vegetable oils, withstanding soybean oil and palm oil for ≥168h, with no fading or bleeding, far superior to the 48h protection effect of existing technologies. 2) Extremely high durability under high temperature and complex working conditions: Under the complex working conditions of 100℃ high temperature + 500g load and 50 cycles of friction, the color density loss is ≤5%, and the barcode readability is Grade A (comparative test proves that the color density loss of existing technology products under the same working conditions is ≥30%, and the barcode readability is ≤3); the temperature-sensitive anti-oil agent undergoes a phase change at 60-70℃, which further improves the high temperature protection performance; 3) High environmental protection and food safety: Plant-based oil-resistant agents completely replace fluorine compounds, no PFOA / PFOS were detected, heavy metal leaching amount is <0.005mg / kg, and it complies with EU REACH regulations, China GB 4806.1-2016 and US FDA food contact material safety standards. There is no migration of harmful substances, making it suitable for food contact scenarios. 4) Excellent transfer efficiency and adaptability: The transfer speed can reach 300mm / s, which is 1.5-30 times faster than existing technologies, and can be adapted to high-speed food processing production lines; it can achieve clear transfer on various substrates such as polyethylene, polypropylene, polyvinyl chloride or composite film, without ink overflow or sticking. 5) Good storage stability and environmental adaptability: After 12 months of storage at room temperature (25℃±5℃) and in a dry environment (relative humidity ≤60%), the product retains ≥95% of its various performance characteristics; it can be used in a wide temperature range of -10℃ to 120℃, making it suitable for low-temperature refrigeration and high-temperature processing scenarios in food processing. 6) The preparation process is easy to industrialize: it can be produced using existing coating equipment. The process parameters have been verified by single-variable optimization, and the controllability and repeatability are good. The production cost is comparable to that of traditional products. Moreover, the process fine-tuning of Examples 1-3 is within the optimization range, and the performance difference is ≤5%, which has the prospect of large-scale application.

[0034] The oil-resistant, environmentally friendly TTO carbon ribbon of the present invention and its preparation method have significant industrial application value and broad market prospects, specifically reflected in: 1) Wide product adaptability: It can be used in a wide temperature range of -10℃ to 120℃, and is suitable for all high-oil food contact scenarios such as meat processing, vegetable oil production, fried food packaging, and dairy product packaging, so as to achieve high-speed and clear transfer of barcodes, traceability information and identification patterns; 2) Compliant with international standards: It complies with EU REACH, China GB 4806.1-2016 and US FDA food contact material safety standards, which can meet the export needs of domestic and foreign food processing enterprises; 3) The process is easy to industrialize: It can be produced using existing mature equipment such as ceramic screen gravure coating, three-roll grinding, and nano sand milling. No new special equipment is required. The process parameters have been optimized and verified by single variable, and the controllability and repeatability are good. The production cost is comparable to that of traditional thermal transfer ribbon. 4) Industry upgrade and adaptation: The transfer speed can reach 300mm / s, which is suitable for the high-speed production line needs of the food processing industry and solves the industry pain point of low transfer efficiency of existing products. 5) Environmentally friendly and safe: It completely replaces fluorinated anti-oil agents, leaves no PFOA / PFOS residues, and has heavy metal leaching levels far below national standards, aligning with the food industry's trend towards environmental and safety upgrades. This invention can completely replace existing grease-resistant heat transfer ribbons, achieving comprehensive upgrades in protective performance, durability, transfer efficiency, and environmental friendliness, thus possessing the core conditions for large-scale production and market promotion. Attached Figure Description

[0035] Figure 1 This is a schematic diagram of the cross-sectional structure of the carbon ribbon of the present invention; wherein: 1-adhesive backing layer (thickness 0.01-0.05μm), 2-base film (thickness 4.5-5μm), 3-bottom protective layer (thickness 1.5-2μm), 4-top oil-resistant layer (thickness 1.5-2μm), 5-thermal transfer ink layer (coating amount 1.7-1.9g / m²); each layer is tightly bonded, the interlayer bonding force is ≥3MPa, and there is no delamination.

[0036] Figure 2The temperature-contact angle response curve of poly(N-vinylcaprolactam) grafted modified silica, a temperature-sensitive anti-oil agent; the response curve of the surface contact angle of the top anti-oil layer of this invention with changes in ambient temperature, with the horizontal axis representing ambient temperature (°C) and the vertical axis representing surface contact angle (°). The curve shows that when the temperature is ≤60°C, the contact angle is stable at 105-110°; when the temperature reaches 60-70°C (LCST), the contact angle rapidly increases to over 120°; when the temperature is ≥70°C, the contact angle remains at 120-125°, which intuitively demonstrates the temperature phase change intelligent protection characteristics of poly(N-vinylcaprolactam) grafted modified silica, a temperature-sensitive anti-oil agent, and the critical phase change temperature is precisely matched with the high-temperature range of food processing.

[0037] Figure 3 This is a flowchart of the carbon ribbon preparation process of the present invention. Detailed Implementation

[0038] The technical solution of the present invention will be further described in detail below with reference to the embodiments, but the scope of protection of the present invention is not limited thereto.

[0039] The present invention will be further described in detail below with reference to specific embodiments, comparative tests, and parallel tests. All tests were conducted under the same test conditions, and the data are the average values ​​of three sets of parallel tests with an error of ≤3%. The scope of protection of the present invention is defined by the claims and is not limited to the following embodiments.

[0040] Basic experimental information: Testing equipment: VDIJET TTO 6320 printer, Taber reciprocating friction tester (linear reciprocating type), contact angle meter, gas chromatography-mass spectrometry (GC-MS), atomic absorption spectrophotometer, barcode grade detector; Test conditions: printing pressure 0.4MPa, printing blackness 90%, friction load 500g, grease immersion temperature 25℃±2℃; Parallel tests: Three sets of parallel samples were set up for each example, numbered Example X-1, Example X-2, and Example X-3, and the average value was taken as the test result.

[0041] Unless otherwise specified, all raw materials used in the following embodiments are ordinary commercially available products that can be purchased directly.

[0042] For example, the high molecular weight polyester resin was purchased from Toyobo Vylon® 103 in Japan. The saturated polyester resin was purchased from SK saturated polyester ES-240 in South Korea. The polyurethane was purchased from Wanhua Chemical CW-20. The rosin resin was purchased from Guangxi Wuzhou Richeng Forestry Chemical Co., Ltd., 130#, 120-130℃; The lignin was purchased from Nanjing Tianlu hydrophobic modified nanocellulose TL-017. Stearamide was purchased from Kao EB-FF of Japan. The modified acrylic multi-polymer ammonium salt dispersant was purchased from BASF's DISPEX Ultra PX 4290. The epoxy-modified acrylic resin was purchased from Zhanxin Resins EBECRYL® 600. Purchase polyether-modified silicone oil from Xinyue KF-6048. Chitosan quaternary ammonium salt was purchased from Xi'an Qiyue Quaternized Chitosan 100K-300K. The PNIPAM-grafted modified silica was purchased from Xi'an Qiyue Biotechnology Co., Ltd. (QYS-PNIPAM-SiO2), with a grafting rate of 15-25%. Hexamethylene diisocyanate (HDI) curing agent was purchased from Covestro Desmodur N3390. The carnauba wax was purchased from Pontes, a Brazilian company, in the Carnauba T3 variety. The hindered phenolic antioxidant was purchased from ADEKA China, specifically ADK STAB AO-60. Erucamide was purchased from Crodamide ER in the UK. Cellulose acetate: Eastman Cellulose Acetate CA-398-10 (USA) Nano silica was purchased from Evonik (Degussa) AEROSIL R972. The carbon black was purchased from Cabot Black Pearls 4350. N-Vinylcaprolactam (NVCL monomer): Sigma-Aldrich analytical grade ≥98%. Silane coupling agent: γ-methacryloyloxypropyltrimethoxysilane (KH-570) was purchased from Jiangxi Chenguang New Materials. Initiator: Azobisisobutyronitrile (AIBN) was purchased from Hangzhou Dingyue. Base film, biaxially oriented PET film, purchased from Jiaozuo Zhuoli Film Material Co., Ltd., film thickness 4.5-5μm. The acrylic-modified silicone resin was purchased from Anhui Aiyota Silicone Oil Co., Ltd. as IOTA 6146. Example 1

[0043] 1. Formulation (by weight, the formulations of the three parallel samples are identical).

[0044] Bottom protective layer (100 parts): 65 parts polyester resin (Toyobo Vylon® 103, Japan, number average molecular weight 23000, glass transition temperature 47℃), 24 parts stearamide, 8 parts lignin (hydrophobic modified nanocellulose TL-017), 2 parts nano silica, 1 part BASF DISPEX Ultra PX 4290 dispersant (the bottom protective layer has a porosity of 2.5% and a thickness of 1.8μm). Top oil-resistant layer (100 parts): 65 parts of EBECRIL® 600 epoxy-modified acrylic resin, 15 parts of Shin-Etsu KF-6048 polyether-modified silicone oil, 12 parts of Xi'an Qiyue chitosan quaternary ammonium salt, 5 parts of Xi'an Qiyue QYS-PNIPAM-SiO2 PNIPAM grafted modified silica, and 3 parts of isocyanate curing agent (the top oil-resistant layer has a contact angle of 110° and a thickness of 1.5μm). Heat transfer ink layer (100 parts): 39 parts saturated polyester resin, 2.5 parts polyurethane, 20 parts carnauba wax, 30 parts carbon black, 8 parts Wuzhou Richeng 130# rosin resin, 0.5 parts Aidi Ke AO-60 antioxidant (the coating amount of the heat transfer ink layer is 1.8 g / m², and the fineness is 2.1 μm); Backing adhesive: Dilute acrylic-modified silicone resin with methyl ethyl ketone (MEK) to a solid content of 6% to obtain acrylic-modified silicone resin diluent. 2. Preparation method (see process flow diagram) Figure 3 ).

[0045] Preparation of the bottom protective layer coating solution: Add each raw material to a toluene-ethyl acetate (1:1, volume ratio) mixed solvent, stir at 2000 r / min for 45 min, and grind with three rollers to a fineness of 2.5 μm to obtain a bottom protective layer coating solution with a solid content of 35%. Preparation of top anti-oil coating liquid: Add each raw material to a mixed solvent of butanone-isopropanol (1:0.6, volume ratio), disperse by ultrasonication at 400W for 30min, filter through a 150-mesh filter to obtain a top anti-oil coating liquid with a solid content of 30%. Preparation of thermal transfer ink: All raw materials except carbon black and antioxidant are added to a mixed solvent of butanone-toluene (1:1.5, volume ratio), stirred and dissolved at 95℃ for 100 min, carbon black and antioxidant are added at 40℃, stirred and dispersed at 300 r / min for 2 h, and then ground 3 times with a horizontal rod-pin nano-sand mill filled with 0.5 mm ultrafine zirconia beads at a linear speed of 12 m / s. The ink fineness is 2.1 μm, and thermal transfer ink is obtained. Composite Molding: 1) Apply an acrylic-modified silicone resin diluent to one side of the base film using a ceramic gravure coating method at a speed of 120 m / min. Dry under 120℃ hot air circulation to form an adhesive backing layer, then proceed to the next process; 2) Apply a bottom protective layer coating liquid to the other side of the base film with the adhesive backing layer using a ceramic gravure coating method at a speed of 120 m / min. Dry and cure for 45 seconds under 115℃ and 4.5 m / s hot air circulation; then apply a top anti-oil layer coating liquid using the same coating method. Dry and cure for 1 minute under 100℃ hot air circulation; finally, apply heat transfer ink using the same coating method. Dry and cure for 45 seconds under 95℃ hot air circulation, and then wind up under 40N winding tension to obtain the finished carbon ribbon. A schematic diagram of the cross-sectional structure of the carbon ribbon is shown below. Figure 1 As shown. Example 2

[0046] 1. Formula adjustment (the rest is the same as in Example 1) The bottom protective layer is made up of 25 parts of Crodamide ER erucamide and 7 parts of Eastman cellulose acetate, which are used as plant-based oil-resistant agents. (The bottom protective layer has a porosity of 2.8% and a thickness of 1.7 μm.) Top oil-resistant layer: The temperature-sensitive oil-resistant agent is replaced with 6 parts of poly(N-vinylcaprolactam) grafted modified silica (grafting rate 22%, LCST 68℃) (the top oil-resistant layer has a contact angle of 108° and a thickness of 1.6μm).

[0047] 2. Preparation method: Same as in Example 1 (3 parallel samples).

[0048] 3. In Example 2, the temperature-sensitive anti-oil agent poly-N-vinylcaprolactam grafted modified silica (its temperature-contact angle response curve is shown in Figure 2) Figure 2 The synthesis method of (as shown) is as follows: Step 1, Silica KH-570 silane modification; (1) Silica ethanol dispersion: Add 5000g of silica to a 100L four-necked reactor, add 40L of anhydrous ethanol, and ultrasonically disperse for 30 min until there are no visible agglomerated particles. (2) Preparation of silane hydrolysate: Add 5L of anhydrous ethanol and 5L of deionized water to a 20L reactor and mix evenly. Slowly add glacial acetic acid, stir to adjust the pH to 4.0, add 6500g of silane coupling agent KH-570, stir at room temperature for 1 h until the solution is completely transparent. (3) Grafting reaction: Transfer all the hydrolysate to silica ethanol dispersion, continuously purging with nitrogen for protection; stir at 300 r / min, heat to 70℃ and stir for 6 h to complete the vinyl functionalization grafting on the silica surface; Step 2, In-situ free radical polymerization grafting of N-vinylcaprolactam (NVCL); (1) Remove ethanol and water from the four-necked reactor system by vacuum distillation at 70℃, leaving only modified silica solid in the reactor; add 30L toluene, sonicate for 20min to redisperse evenly, and purge with nitrogen for 30min. (2) Prepare monomer initiator pre-solution: add 5L toluene, 4200g NVCL, and 120g AIBN to a 20L reactor and stir until completely dissolved; (3) Isothermal grafting polymerization reaction: under nitrogen protection, add the monomer initiator pre-solution prepared in (2) to the four-necked reactor, stir at 350 r / min, and react at 72℃ for 16h; this temperature is the core control point, which directly determines the LCST and grafting rate range of the product; Step 3, post-processing; (1) Solid-liquid separation: The reaction system is naturally cooled to room temperature, transferred to a high-speed centrifuge and centrifuged at 9000 r / min for 10 min, discard the upper toluene mother liquor and collect the lower solid; (2) Purification and washing: Add 20 L of n-hexane each time, sonicate for 10 min to fully soak and wash, centrifuge at 9000 r / min, and repeat the washing 3 times; (3) Drying and pulverizing: Transfer the wet solid to a vacuum drying oven, set the temperature to 60℃, and vacuum dry for 12 h; after cooling to room temperature, lightly grind and break up the clumps to obtain white thermosensitive silica powder product with a grafting rate of 15-25%. Example 3

[0049] 1. Process adjustments (the rest is the same as the formulation in Example 1) Underlying protective coating solution: Stir at 2500 rpm for 30 minutes; Top layer anti-oil coating liquid: ultrasonically dispersed at 500W for 25 minutes; Composite molding: Coating speed 150m / min (other curing parameters are the same as in Example 1).

[0050] 2. Preparation method: The rest is the same as in Example 1 (3 parallel samples).

[0051] Comparative Specifications Comparative Example 1 (CN 110452573 A): Saturated polyester resin + epoxy resin film formation, fluorinated anti-oil agent, single-layer protection, coating porosity 8%, transfer speed ≤200mm / s;

[0052] Comparative Example 2 (CN 114261223 B): Saturated polyester + acrylic + chloroacetic acid film formation, no special anti-oil agent, multi-layer coating, coating contact angle 75°, transfer speed ≤50mm / s; Performance test results: see Tables 1 to 5.

[0053] Table 1. Durability test results under combined working conditions (average value of 3 parallel tests)

[0054] The data in Table 1 show that under the combined conditions of 100℃ high temperature and 50 cycles of reciprocating friction, the barcode grade and color density retention of the samples in the embodiments of the present invention are far superior to those of the comparative examples of the prior art; the overall color density loss of the embodiments is ≤5%, meeting the design specifications. Only Example 3 showed a slight performance decline due to the increased coating speed, but it was still within the acceptable range, proving that the formulation and coating system of the present invention have excellent high-temperature wear resistance and durability.

[0055] Table 2. Results of transfer efficiency test (average of 3 parallel tests, barcode grade A)

[0056] The data in Table 2 shows that the carbon ribbon of this invention achieves a stable maximum transfer speed of 300 mm / s on two types of mainstream food packaging film materials, which is 1.5-30 times higher than the existing technology and can be fully adapted to the high-speed production line of the food industry. The formula and process fine-tuning did not affect the high-speed transfer performance, and the product transfer stability and versatility are outstanding.

[0057] Table 3 Results of grease immersion test (average of 3 parallel tests, with a mark clarity retention rate ≥90% to be considered qualified).

[0058] The data in Table 3 show that the present invention achieves differentiated protection against animal and vegetable oils, with a immersion time of ≥122h for animal oils and ≥165h for vegetable oils, both meeting the preset technical indicators. The immersion tolerance time is 2-7 times that of the prior art. This proves that the layered design of the bottom protective layer and the top oil-resistant layer can effectively block the penetration of saturated fatty acids and inhibit the adhesion of unsaturated fatty acids. The differentiated oil-resistant technology solution has significant effects.

[0059] Table 4. Environmental and food safety test results (average values ​​of 3 parallel tests)

[0060] The data in Table 4 show that the present invention uses a plant-based oil-resistant agent to completely replace the fluorinated adjuvant, with no PFOA / PFOS residues and heavy metal leaching of <0.005mg / kg. It also meets multiple food contact standards of EU REACH, China GB 4806.1-2016, and US FDA. The product retains ≥95% of its performance after 12 months of storage at room temperature, exhibits excellent long-term storage stability, and is superior to existing products in terms of environmental friendliness, safety, and shelf life.

[0061] Table 5 Results of low temperature / high temperature environment adaptability test (-10℃ / 120℃, 24h, average value of 3 parallel tests)

[0062] Note: Coating adhesion test method: The interlayer adhesion is tested using a tensile tester according to GB / T 2792-2014. The carbon ribbon in Table 5 is installed on a thermal transfer printer, and a 25 mm × 150 mm black block is printed on a PET / CPP substrate. An electronic tensile testing machine is used to perform an interlayer peel test on the coating at a uniform speed of 50 mm / min. The peel strength value is the coating adhesion.

[0063] The data in Table 5 show that under extreme conditions of -10℃ low temperature and 120℃ high temperature, the imprint clarity retention rate of the sample of the present invention is ≥96%, and the interlayer bonding force is ≥3.0MPa, which is far higher than the existing technology; proving that the resin system, temperature-sensitive anti-oil agent and overall coating structure are suitable for a wide temperature range of food processing applications and have strong environmental adaptability.

[0064] Based on the above test results, the following analysis is performed: The products of Examples 1-3 of this invention are significantly superior to the prior art (Comparative Examples 1-2) in terms of durability under composite working conditions, transfer efficiency, and resistance to grease immersion. Moreover, all data are the average values ​​of 3 parallel tests with an error of ≤3%, proving that the product performance has good repeatability and stability. The performance differences between Examples 1-3 due to minor adjustments to the formulation / process are ≤5%, all within a reasonable optimization range, and all achieve the purpose of the invention, proving that the formulation and process of the present invention have good adaptability; The product of this invention complies with EU REACH, Chinese GB 4806.1-2016 and US FDA food contact standards, and has a performance retention rate of ≥95% after 12 months of storage. It has excellent adaptability to low temperature / high temperature environments and is suitable for all scenarios of food processing.

Claims

1. An oil-resistant, environmentally friendly TTO carbon ribbon, characterized in that, The product includes a base film, one side of which is an adhesive backing layer, and the other side of the base film, from bottom to top, consists of a bottom protective layer, a top anti-oil layer, and a heat transfer ink layer. The bottom protective layer, in 100 parts by weight, comprises: 60-75 parts polyester resin, 15-25 parts fatty acid amide, 5-10 parts plant-based anti-oil agent, 1-3 parts nano silica, and 0.5-2 parts modified acrylic multi-polymer ammonium salt dispersant.

2. The grease-resistant, environmentally friendly TTO carbon ribbon as described in claim 1, characterized in that, The weight of each raw material in the top anti-oil layer, calculated per 100 parts, is as follows: 55-70 parts epoxy-modified acrylic resin, 10-18 parts polyether-modified silicone oil, 8-15 parts plant-based anti-oil agent, 3-8 parts temperature-sensitive anti-oil agent, and 2-5 parts isocyanate curing agent.

3. The grease-resistant, environmentally friendly TTO carbon ribbon as described in claim 1, characterized in that, The total weight of each raw material in the heat transfer ink layer, per 100 parts, is as follows: 33-45 parts saturated polyester resin, 2-5 parts polyurethane, 15-20 parts carnauba wax, 25-35 parts carbon black, 5-10 parts tackifying resin, and 0.3-1 parts antioxidant.

4. The grease-resistant, environmentally friendly TTO carbon ribbon as described in claim 1, characterized in that, In the bottom protective layer, the number average molecular weight of the polyester resin is 20,000-30,000, and the glass transition temperature is 40-65℃; the fatty acid amide is one of stearamide and erucamide.

5. The grease-resistant, environmentally friendly TTO carbon ribbon as described in claim 1, characterized in that, In the top oil-resistant layer, the epoxy-modified acrylic resin is obtained by graft copolymerization of bisphenol A type epoxy resin and acrylate monomer; the polyether-modified silicone oil is a polyoxyethylene-polyoxypropylene block modified silicone oil.

6. The grease-resistant, environmentally friendly TTO carbon ribbon as described in claim 1, characterized in that, In the heat transfer ink layer, the tackifying resin is one or more of rosin resin, terpene resin, and petroleum resin; the antioxidant is a hindered phenolic antioxidant or a phosphite antioxidant.

7. The grease-resistant, environmentally friendly TTO carbon ribbon as described in claim 1 or 2, characterized in that, The plant-based oil-resistant agent is one of cork sulfate lignin, chitosan quaternary ammonium salt, and cellulose acetate; the temperature-sensitive oil-resistant agent is poly(N-isopropylacrylamide) grafted modified silica or poly(N-vinylcaprolactam) grafted modified silica.

8. The grease-resistant, environmentally friendly TTO carbon ribbon as described in claim 1 or 2, characterized in that, The thickness of the bottom protective layer is 1.5-2.0 μm; the thickness of the top oil-resistant layer is 1.5-2.0 μm; the coating amount of the heat transfer ink layer is 1.7-1.9 g / m², and the ink fineness is ≤3 μm; the base film is a polyethylene terephthalate film with a thickness of 4.5-5 μm.

9. A method for preparing the grease-resistant, environmentally friendly TTO carbon ribbon according to any one of claims 1 to 8, characterized in that, Includes the following steps: (1) Preparation of the bottom protective layer coating liquid: Polyester resin, fatty acid amide, plant-based anti-oil agent, nano silica and modified acrylic multi-polymer ammonium salt dispersant are added to the solvent, stirred and dispersed, and ground to fineness ≤3μm to obtain a bottom protective layer coating liquid with a solid content of 30-40%. (2) Preparation of top anti-oil coating liquid: Epoxy modified acrylic resin, polyether modified silicone oil, plant-based anti-oil agent, temperature-sensitive anti-oil agent and isocyanate curing agent are added to solvent, ultrasonically dispersed and filtered to obtain a top anti-oil coating liquid with a solid content of 25-35%. (3) Preparation of heat transfer ink: Saturated polyester resin, polyurethane, carnauba wax and tackifying resin are mixed and added to a solvent, stirred and dissolved at 90-100℃, cooled to below 40℃ and then carbon black and antioxidant are added, stirred and dispersed, and ground until the ink fineness is ≤3μm to obtain heat transfer ink; (4) Composite molding: Coat one side of the base film with acrylic modified silicone resin diluent and dry and cure at 110-120℃ to form a backing layer; coat the other side of the base film with the backing layer with a bottom protective layer coating liquid and dry and cure at 110-120℃; then coat the top anti-oil layer coating liquid and dry and cure at 100-110℃; finally coat the heat transfer ink and dry and cure at 90-100℃ to obtain the final product.

10. The application of the grease-resistant, environmentally friendly TTO carbon ribbon according to any one of claims 1 to 8, characterized in that, The carbon ribbon is used in high-oil scenarios such as meat processing, vegetable oil production, fried food packaging, or dairy product packaging at ambient temperatures of -10℃ to 120℃, to achieve clear transfer of barcodes, traceability information, or identification patterns on polyethylene, polypropylene, polyvinyl chloride, or composite film substrates; in the high-oil scenarios, the contact between oil and the carbon ribbon is through direct immersion, spraying, or wiping, and the performance retention rate of the carbon ribbon is ≥95% after 12 months of storage at room temperature.

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