High-weather-resistance outdoor heat transfer printing thermal transfer ribbon assembly and pattern heat transfer printing method

Abstract

The invention relates to a high-weather-resistance outdoor heat transfer printing thermal transfer ribbon assembly and a pattern heat transfer printing method.The high-weather-resistance outdoor heat transfer printing thermal transfer ribbon assembly comprises a color thermal transfer ribbon and a protective thermal transfer ribbon, and the color thermal transfer ribbon comprises a first base material layer, a first back coating layer, a stripping layer and a color layer; the first back coating layer and the stripping layer are respectively arranged on two opposite side surfaces of the first base material layer, and the color layer is arranged on the surface of the stripping layer; the protection thermal transfer ribbon comprises a second base material layer, a second back coating layer, a barrier layer and an auxiliary agent layer, the second back coating layer and the barrier layer are arranged on the two opposite side faces of the second base material layer respectively, and the auxiliary agent layer is arranged on the surface of the barrier layer. According to the high-weather-resistance outdoor heat transfer printing thermal transfer ribbon assembly, through combined use of the color thermal transfer ribbon and the protection thermal transfer ribbon, the display effect of printed patterns and the reliability of outdoor use can be effectively improved, operation is easy, and economical efficiency is good.

Description

Technical Field

[0001] The present invention relates to the technical field of thermal transfer ribbons, and particularly relates to a high-weather-resistant outdoor thermal transfer ribbon assembly and a method for thermal transfer of patterns. Background Art

[0002] Thermal transfer outdoor products have been widely used in the identification fields such as electric power, petroleum, chemical industry, and transportation, and are accepted by a large number of customers. As an important application field of outdoor products, there is no precedent for using thermal transfer to produce outdoor advertisements. With the development of thermal transfer equipment, it has become possible to produce outdoor advertisements by thermal transfer, but new requirements are put forward for thermal transfer imaging materials. For outdoor advertisement use, in addition to the original weather resistance requirements, new requirements are put forward for color retention and color display effects. For example, for a door head light box advertisement, it is required that the display effects are consistent when observed from various angles and during day and night, and at the same time, within the normal service life of 5 years, extremely high color consistency is required, and the color retention requirement is extremely high, which puts forward higher requirements for weather resistance and display effects. Summary of the Invention

[0003] The present invention provides a high-weather-resistant outdoor thermal transfer ribbon assembly and a method for thermal transfer of patterns to solve one or several of the technical problems existing in the prior art.

[0004] The technical solution of the present invention for solving the above technical problems is as follows: A high-weather-resistant outdoor thermal transfer ribbon assembly includes a color ribbon and a protective ribbon. The color ribbon includes a first substrate layer, a first back coating layer, a release layer, and a color layer. The first back coating layer and the release layer are respectively disposed on opposite side surfaces of the first substrate layer, and the color layer is disposed on the surface of the release layer;

[0005] The protective ribbon includes a second substrate layer, a second back coating layer, a barrier layer, and an additive layer. The second back coating layer and the barrier layer are respectively disposed on opposite side surfaces of the second substrate layer, and the additive layer is disposed on the surface of the barrier layer.

[0006] The beneficial effect of the present invention is that: By combining the use of the color ribbon and the protective ribbon, the high-weather-resistant outdoor thermal transfer ribbon assembly of the present invention can effectively improve the display effect of the printed pattern and the reliability of outdoor use, with simple operation and good economy.

[0007] On the basis of the above technical solution, the present invention can also be improved as follows.

[0008] Optionally, the thickness of the first substrate layer is 4 - 10 μm, preferably 4 - 6 μm; the thickness of the first back coating layer is 0.1 - 0.5 μm, preferably 0.2 - 0.4 μm; the thickness of the release layer is 0.1 - 0.3 μm, preferably 0.1 - 0.2 μm; the thickness of the color layer is 0.1 - 0.6 μm, preferably 0.8 - 1.0 μm.

[0009] The thickness of the second substrate layer is 4 - 10 μm, preferably 4 - 6 μm; the thickness of the second back coating layer is 0.1 - 0.5 μm, preferably 0.2 - 0.4 μm; the thickness of the barrier layer is 1.3 - 2 μm, preferably 1.5 - 1.8 μm; the thickness of the additive layer is 0.4 - 0.8 μm, preferably 0.5 - 0.6 μm.

[0010] In the present invention, the first substrate layer and the second substrate layer can each be made of one of polyethylene terephthalate (PET) film, 1,4 - cyclohexylene dimethylene terephthalate film, polyethylene naphthalate (PEN) film, polyphenylene sulfide film, polystyrene (PS) film, polypropylene (PP) film, polyethylene (PE) film, polyvinyl chloride film, nylon film, polyimide film, etc.

[0011] In the present invention, the purpose of both the first back coating layer and the second back coating layer is to prevent the adverse effects caused by sticking or wrinkling due to the heating of the temperature - sensitive heating head during thermal transfer. The main components of the first back coating layer and the second back coating layer are cellulose acetate propionate, polyvinyl acetal - based resin, and polyvinyl butyral - based resin. These two back coating layers often also need to add high - adhesion resins such as polyester and polyurethane; lubricants such as phosphate esters, zinc stearate, glycerol dioleate, and glycerol monooleate are often added to the back coating layer; fillers with self - cleaning effects such as inorganic fine particles like talc powder, kaolin, calcium carbonate, aluminum hydroxide, silicon dioxide, graphite, and boron nitride are often added to the back coating layer. One or more of a leveling agent, a dispersant, and an antistatic agent are often added to the back coating layer. A cross - linking agent such as an isocyanate compound is often added to the back coating layer. The preparation method of the first back coating layer and the second back coating layer is as follows: dissolve the above - mentioned materials with 2 - butanone and toluene to make a back coating coating solution, and then use a 300 - line ceramic gravure roll to coat the back coating coating solution on the substrate with an intaglio coater, and dry it at 60 - 100 °C, with a coating speed of 60 - 100 m / min.

[0012] Further, the components of the release layer include thermoplastic acrylic resin A and thermoplastic acrylic resin B. The molecular weight of the thermoplastic acrylic resin A is 20,000 - 35,000, preferably 25,000 - 30,000, and the glass transition temperature Tg value is 60 - 110°C, preferably 70 - 90°C; the molecular weight of the thermoplastic acrylic resin B is 100,000 - 150,000, preferably 130,000 - 140,000, and the glass transition temperature Tg value is 100 - 110°C, preferably 100 - 105°C;

[0013] By weight percentage, the proportion of the thermoplastic acrylic resin A in the release layer is 70% - 90%, and the proportion of the thermoplastic acrylic resin B in the release layer is 10% - 30%.

[0014] The beneficial effects of adopting the above further scheme are as follows: The release layer uses thermoplastic acrylic resin, which has good thermal release properties and can help the color ribbon achieve good peeling and transfer properties after the thermal print head is heated. By using a combination of high and low molecular weight thermoplastic acrylic resins A and B in the release layer, with the low molecular weight thermoplastic acrylic resin A as the main component and controlling the thickness of the release layer, the resolution during transfer can be effectively improved to meet the requirement of providing fine printing.

[0015] Further, the preparation method of the release layer is as follows: Dissolve and grind the thermoplastic acrylic resin A and the thermoplastic acrylic resin B with a solvent to make a release layer coating solution, and then use a 500-line ceramic gravure roll to coat the back coating solution on the substrate layer with a gravure coater, and dry it at 80 - 100°C, and the coating speed is 60 - 100 m / min.

[0016] Further, the components of the color layer include polyolefin-modified acrylic resin, thermoplastic methyl methacrylate, pigment, and plasticizer;

[0017] The molecular weight of the thermoplastic methyl methacrylate is 200,000 - 300,000, preferably 200,000 - 250,000, and the glass transition temperature Tg value is greater than 100°C, preferably 100 - 105°C; the particle size of the pigment is D50 < 0.08 μm and D100 < 0.1 μm;

[0018] By weight percentage, the proportion of the polyolefin-modified acrylic resin in the color layer is 5% - 15%, the proportion of the thermoplastic methyl methacrylate in the color layer is 30% - 45%, the proportion of the pigment in the color layer is 45% - 60%, and the proportion of the plasticizer in the color layer is 0 - 10%.

[0019] The beneficial effects of adopting the above further solution are as follows: Thermoplastic methyl methacrylate has good light transmittance, excellent light and weather resistance, and good transferability, which can ensure that the carbon ribbon has good transfer printing ability. The selection of high molecular weight can effectively ensure the outdoor use reliability of the pattern after transfer printing. At the same time, with the precise design of the release layer, problems such as insufficient resolution can be effectively avoided. The content of polyolefin-modified acrylic resin in the color layer is 5% - 15%; the polyolefin-modified acrylic resin can improve the substrate adaptability of the color carbon ribbon and also has good transferability on olefin-based printing substrates.

[0020] The pigment is a high weather-resistant pigment, and high weather-resistant pigments of different colors such as yellow (such as 110 yellow, 150 yellow, 138 yellow), red (such as 177 red, 149 red, 254 red, 264 red), blue (phthalocyanine blue, ultramarine blue), green (phthalocyanine blue), black (carbon black) can be selected. The proportion in the color layer is between 45% - 60%. Selecting this type of pigment has good light and weather resistance and can ensure the outdoor use reliability of the pattern after printing. If the pigment content in the color layer is insufficient, the light resistance and weather resistance will decline; the color layer is ground to control its particle size D50 < 0.08um and D100 < 0.1um, which can make the pigment evenly distributed in the coating. Under the action of light, and there are no other solid substances in the color layer, so the absorption and reflection of light with different wavelengths in the color layer are relatively consistent, and the entire film surface presents a uniform color effect, avoiding color differences caused by pigment agglomeration or uneven distribution.

[0021] The plasticizer can select common plasticizers such as epoxidized soybean oil, dioctyl phthalate, dibutyl phthalate, etc. The content is generally 1% - 10% of the methacrylic copolymer. The use of the plasticizer can improve the use reliability of the pattern after printing;

[0022] At the same time, to further improve the weather resistance of the pattern after printing, anti-aging additives such as light absorbers, light stabilizers, and antioxidants can also be considered to be added to the color layer.

[0023] Furthermore, the preparation method of the color layer is as follows: Dissolve the polyolefin-modified acrylic resin, thermoplastic methyl methacrylate, pigment, and plasticizer with a solvent, then grind and formulate it into a color layer coating solution. Use a 250-line ceramic gravure roll and apply the color layer on the substrate layer with a gravure coater, and dry it at 80 - 100°C. The coating speed is 60 - 100 m / min.

[0024] Furthermore, the components of the barrier layer include thermoplastic acrylic resin C, thermoplastic acrylic resin D, micro wax powder, and solid filler;

[0025] The molecular weight of the thermoplastic acrylic resin C is 20,000 to 35,000, preferably 30,000 to 35,000, and the glass transition temperature Tg is 90 to 110 °C, preferably 100 to 105 °C; the molecular weight of the thermoplastic acrylic resin D is 100,000 to 350,000, preferably 200,000 to 250,000, and the glass transition temperature Tg is 100 to 110 °C, preferably 100 to 105 °C;

[0026] By weight percentage, the proportion of the thermoplastic acrylic resin C in the barrier layer is 40% to 60%, the proportion of the thermoplastic acrylic resin D in the barrier layer is 40% to 60%, the proportion of the micro wax powder in the barrier layer is 2% to 8%, and the proportion of the solid filler in the barrier layer is 2% to 8%.

[0027] The beneficial effect of adopting the above further scheme is that the barrier layer uses the thermoplastic acrylic resin C with a relatively low molecular weight, which has good thermal peelability and can help protect the carbon ribbon to achieve good peel transferability after the thermal print head is heated. The thermoplastic acrylic resin D has a large molecular weight, which can form a dense coating on the barrier layer, has a good barrier effect on air, oxygen, water vapor, etc., and can also prevent the migration of additives in the additive layer.

[0028] The micro wax powder can be PE wax, Fischer-Tropsch wax, etc., preferably PE wax. The proportion of wax in the anti-glare protective layer is between 2% and 8%, the particle size is between 1 and 10 μm, preferably below 7 μm, and the melting point is between 80 and 120 °C; introducing micro wax powder into the anti-glare protective layer can improve the scratch and wear resistance of the printed pattern.

[0029] For the solid filler, silica matting powder, talc powder, kaolin, etc. can be selected, preferably silica matting powder; the content of the solid filler in the barrier layer is 2% - 8%. The filler can effectively reduce glare, make the reflection of light on the film surface more uniform and soft, reduce the bright spots or dark areas caused by the concentrated reflection of light, and help maintain the color uniformity in the reflection and projection environments, enabling viewers to feel the same color performance from different angles.

[0030] Further, the preparation method of the barrier layer is as follows: dissolve and grind and disperse the thermoplastic acrylic resin C, thermoplastic acrylic resin D, micro wax powder, and solid filler with a solvent to make a barrier layer coating solution, and then use a 200-line ceramic gravure roll to coat the back coating solution on the substrate layer with an intaglio coater, and dry it at 80 - 100 °C, and the coating speed is 60 - 100 m / min.

[0031] Further, the components of the additive layer include thermoplastic methyl methacrylate, ultraviolet absorber, and hindered amine light stabilizer;

[0032] The molecular weight of the thermoplastic methyl methacrylate is 10,000 - 50,000, preferably 30,000 - 40,000, and the glass transition temperature Tg value is 60 - 90 °C, preferably 70 - 80 °C; the molecular weight of the ultraviolet absorber is greater than 600, and the molecular weight of the hindered amine light stabilizer is greater than 2,000;

[0033] By weight percentage, the proportion of the thermoplastic methyl methacrylate in the additive layer is 20% - 40%, the proportion of the ultraviolet absorber in the additive layer is 20% - 40%, and the proportion of the hindered amine light stabilizer in the additive layer is 20% - 40%.

[0034] The beneficial effects of adopting the above further scheme are as follows: The thermoplastic methyl methacrylate has a relatively low molecular weight, has good compatibility with ultraviolet absorbers, light stabilizers, etc., and at the same time has a relatively low Tg value, which can provide good adhesion during transfer printing, has good transferability to various printing substrates, and has good adhesion after transfer printing. The ultraviolet absorber is salicylate, benzophenone, benzotriazole, substituted acrylonitrile, triazine, etc. The preferred is the hydroxyphenyltriazine ultraviolet absorber in triazine. Its molecular weight is greater than 600. The content of the ultraviolet absorber in the barrier layer is between 20% - 40%. This type of ultraviolet absorber has extremely high extinction ability, can provide excellent protection for coatings, photosensitive substrates and other polymer materials, especially has very excellent effects in the thin film system, and has low migration, and can be stably used in thin coatings. The content of the hindered amine light stabilizer in the additive layer is between 20% - 40%, and the molecular weight is greater than 2,000. Selecting this type of light stabilizer has low volatility, low migration, good compatibility with materials, and can also improve the thermal oxidation aging resistance of materials.

[0035] Further, the preparation method of the additive layer is as follows: Dissolve the thermoplastic methyl methacrylate, ultraviolet absorber, and hindered amine light stabilizer with a solvent, then prepare an additive layer coating solution, use a 2800-line ceramic gravure roll, and coat the additive layer coating solution on the barrier layer on one side of the substrate layer by an intaglio coater, and dry it at a temperature of 80 - 100 °C, and the coating speed is 60 - 100 m / min.

[0036] A thermal transfer method for a pattern includes the following steps: Using a thermal transfer printer, heating the above-mentioned color ribbon through a thermal print head to form a color pattern layer on the printing substrate, and then continuing to heat the above-mentioned protective ribbon through the thermal print head to form a protective coating on the color pattern layer to obtain the pattern. Brief Description of the Drawings

[0037] Figure 1 It is a schematic structural diagram of the color ribbon of the present invention;

[0038] Figure 2This is a schematic structural diagram of the protective carbon ribbon of the present invention;

[0039] Figure 3 This is a schematic structural diagram of the patterns printed by the color carbon ribbon and the protective carbon ribbon of the present invention.

[0040] In the attached drawings, the list of components represented by each reference numeral is as follows:

[0041] 1. First base material layer; 2. Release layer; 3. Color layer; 4. First back coating layer; 5. Second base material layer; 6. Second back coating layer; 7. Barrier layer; 8. Auxiliary agent layer; 9. Substrate to be printed; 10. Protective coating layer; 11. Color pattern layer. Detailed implementation mode

[0042] The principles and features of the present invention will be described below with reference to the attached drawings. The examples given are only used to explain the present invention and are not intended to limit the scope of the present invention.

[0043] Example 1

[0044] As Figure 1 and Figure 2 shown, a high weather resistance outdoor thermal transfer carbon ribbon assembly of this embodiment includes a color carbon ribbon and a protective carbon ribbon. The color carbon ribbon includes a first base material layer 1, a first back coating layer 4, a release layer 2 and a color layer 3. The first back coating layer 4 and the release layer 2 are respectively arranged on the opposite two side surfaces of the first base material layer 1, and the color layer 3 is arranged on the surface of the release layer 2;

[0045] The protective carbon ribbon includes a second base material layer 5, a second back coating layer 6, a barrier layer 7 and an auxiliary agent layer 8. The second back coating layer 6 and the barrier layer 7 are respectively arranged on the opposite two side surfaces of the second base material layer 5, and the auxiliary agent layer 8 is arranged on the surface of the barrier layer 7.

[0046] Both the first base material layer 1 and the second base material layer 5 are made of polyethylene terephthalate (PET) film.

[0047] The raw materials of the first back coating layer 4 are weighed according to the following parts by weight: 60 parts of 2-butanone, 25 parts of toluene, 10 parts of cellulose acetate propionate, 0.5 part of polyester resin, 0.3 part of zinc stearate, 0.25 part of phosphate ester, 0.2 part of glycerol dioleate, 2 parts of isocyanate, 0.3 part of talc, 0.2 part of silicon dioxide, and 0.3 part of antistatic agent. The preparation method of the first back coating layer 4 is as follows: First, dissolve cellulose acetate propionate and polyester resin in a mixed solvent of 2-butanone and toluene, then add zinc stearate, phosphate ester, glycerol dioleate, talc, silicon dioxide and antistatic agent and stir well for 2 hours, and then add isocyanate and stir for 0.5 hour to obtain the back coating liquid.

[0048] The release layer 2 weighs the raw materials according to the following parts by weight: 45 parts of 2-butanone, 45 parts of toluene, 8 parts of thermoplastic acrylic resin A, and 2 parts of thermoplastic acrylic resin B. The molecular weight of the thermoplastic acrylic resin A is 25,000, and the glass transition temperature Tg value is 65 °C; the molecular weight of the thermoplastic acrylic resin B is 120,000, and the glass transition temperature Tg value is 105 °C; the preparation method of the release layer is as follows: dissolve and grind the thermoplastic acrylic resin A and the thermoplastic acrylic resin B with a solvent to make a release layer coating solution, and then use a 500-line ceramic gravure roll to coat the back coating solution on the substrate layer with a gravure coater, and dry it at 80-100 °C, and the coating speed is 60-100 m / min.

[0049] The color layer 3 weighs the raw materials according to the following parts by weight: 40 parts of 2-butanone, 40 parts of toluene, 2 parts of polyolefin-modified acrylic resin, 8 parts of thermoplastic methyl methacrylate, and 10 parts of pigment. The molecular weight of the thermoplastic methyl methacrylate is 250,000, and the glass transition temperature Tg value is greater than 100 °C; the particle size of the pigment is D50 < 0.08 um and D100 < 0.1 um; the preparation method of the color layer is as follows: dissolve the polyolefin-modified acrylic resin, thermoplastic methyl methacrylate, pigment, and plasticizer with a solvent, and then grind and prepare a color layer coating solution, and use a 250-line ceramic gravure roll to coat the color layer on the substrate layer with a gravure coater, and dry it at 80-100 °C, and the coating speed is 60-100 m / min.

[0050] The barrier layer 7 weighs the raw materials according to the following parts by weight: 40 parts of 2-butanone, 40 parts of toluene, 9 parts of thermoplastic acrylic resin C, 9 parts of thermoplastic acrylic resin D, 1 part of micro wax powder, and 1 part of solid filler; the molecular weight of the thermoplastic acrylic resin C is 30,000, and the glass transition temperature Tg is 100 °C; the molecular weight of the thermoplastic acrylic resin D is 350,000, and the glass transition temperature Tg is 105 °C; the preparation method of the barrier layer is as follows: dissolve and grind the thermoplastic acrylic resin C, thermoplastic acrylic resin D, micro wax powder, and solid filler with a solvent to make a barrier layer coating solution, and then use a 200-line ceramic gravure roll to coat the back coating solution on the substrate layer with a gravure coater, and dry it at 80-100 °C, and the coating speed is 60-100 m / min.

[0051] The auxiliary layer 8 weighs the raw materials according to the following parts by weight: 43 parts of 2-butanone, 42 parts of toluene, 5 parts of thermoplastic methyl methacrylate, 5 parts of ultraviolet absorber, and 5 parts of hindered amine light stabilizer; the molecular weight of the thermoplastic methyl methacrylate is 35,000, and the glass transition temperature Tg value is 75 °C; the molecular weight of the ultraviolet absorber is greater than 600, and the molecular weight of the hindered amine light stabilizer is greater than 2,000; the preparation method of the auxiliary layer is: dissolve the thermoplastic methyl methacrylate, ultraviolet absorber, and hindered amine light stabilizer with a solvent, and then prepare an auxiliary layer coating solution. Use a ceramic gravure roll with 2,800 lines to coat the auxiliary layer coating solution on the barrier layer on one side of the substrate layer with a gravure coater, and dry it at a temperature of 80-100 °C, and the coating speed is 60-100 m / min.

[0052] A thermal transfer method for a pattern includes the following steps: using a thermal transfer printer, heating the above-mentioned color ribbon through a thermal print head to form a color pattern layer 11 on the printing substrate 9, and then continuing to heat the above-mentioned protective ribbon through the thermal print head to form a protective coating 10 on the color pattern layer 11 to obtain the pattern, as Figure 3 shown.

[0053] Example 2

[0054] The color layer of this example weighs the raw materials according to the following parts by weight: 40 parts of 2-butanone, 40 parts of toluene, 0.5 part of polyolefin-modified acrylic resin, 8 parts of thermoplastic methyl methacrylate, and 11 parts of pigment.

[0055] The auxiliary layer of this example weighs the raw materials according to the following parts by weight: 43 parts of 2-butanone, 42 parts of toluene, 4 parts of thermoplastic methyl methacrylate, 6.5 parts of ultraviolet absorber, and 4.5 parts of hindered amine light stabilizer.

[0056] The rest is the same as in Example 1.

[0057] Example 3

[0058] The release layer of this example weighs the raw materials according to the following parts by weight: 45 parts of 2-butanone, 45 parts of toluene, 7 parts of thermoplastic acrylic resin A, and 3 parts of thermoplastic acrylic resin B. The rest is the same as in Example 1.

[0059] The color layer of this example weighs the raw materials according to the following parts by weight: 40 parts of 2-butanone, 40 parts of toluene, 2 parts of polyolefin-modified acrylic resin, 7 parts of thermoplastic methyl methacrylate, and 11 parts of pigment.

[0060] The auxiliary layer of this example weighs the raw materials according to the following parts by weight: 43 parts of 2-butanone, 42 parts of toluene, 4 parts of thermoplastic methyl methacrylate, 4 parts of ultraviolet absorber, and 7 parts of hindered amine light stabilizer.

[0061] The rest is the same as in Example 1.

[0062] Example 4

[0063] The raw materials of the release layer in this example are weighed according to the following parts by weight: 45 parts of 2-butanone, 45 parts of toluene, 7 parts of thermoplastic acrylic resin A, and 3 parts of thermoplastic acrylic resin B.

[0064] The raw materials of the color layer in this example are weighed according to the following parts by weight: 40 parts of 2-butanone, 40 parts of toluene, 1 part of polyolefin-modified acrylic resin, 9 parts of thermoplastic methyl methacrylate, and 10 parts of pigment.

[0065] The raw materials of the additive layer in this example are weighed according to the following parts by weight: 43 parts of 2-butanone, 42 parts of toluene, 7 parts of thermoplastic methyl methacrylate, 4 parts of ultraviolet absorber, and 4 parts of hindered amine light stabilizer.

[0066] The rest is the same as in Example 1.

[0067] Example 5

[0068] The raw materials of the release layer in this example are weighed according to the following parts by weight: 45 parts of 2-butanone, 45 parts of toluene, 9 parts of thermoplastic acrylic resin A, and 1 part of thermoplastic acrylic resin B. The rest is the same as in Example 1.

[0069] Example 6

[0070] The raw materials of the color layer in this example are weighed according to the following parts by weight: 40 parts of 2-butanone, 40 parts of toluene, 3 parts of polyolefin-modified acrylic resin, 6 parts of thermoplastic methyl methacrylate, and 11 parts of pigment.

[0071] Example 7

[0072] The raw materials of the barrier layer in this example are weighed according to the following parts by weight: 40 parts of 2-butanone, 40 parts of toluene, 10 parts of thermoplastic acrylic resin C, 8 parts of thermoplastic acrylic resin D, 1.6 parts of micro wax powder, and 0.4 part of solid filler.

[0073] Example 8

[0074] The raw materials of the barrier layer in this example are weighed according to the following parts by weight: 40 parts of 2-butanone, 40 parts of toluene, 8 parts of thermoplastic acrylic resin C, 10.6 parts of thermoplastic acrylic resin D, 0.4 part of micro wax powder, and 1 part of solid filler.

[0075] Comparative Example 1

[0076] The colored carbon ribbon used in this Comparative Example 1 is the same as that in Example 1, without a protective carbon ribbon.

[0077] Comparative Example 2

[0078] The protective carbon tape used in Comparative Example 2 is the same as that in Example 1. The raw materials of the release layer of the color carbon tape are weighed according to the following parts by weight: 45 parts of 2-butanone, 45 parts of toluene, 9 parts of thermoplastic acrylic resin A, and 1 part of micro wax powder.

[0079] The raw materials of the color layer of the color carbon tape are weighed according to the following parts by weight: 40 parts of 2-butanone, 40 parts of toluene, 8 parts of polyolefin-modified acrylic resin, 8 parts of thermoplastic methyl methacrylate, and 4 parts of pigment.

[0080] Comparative Example 3

[0081] The color carbon tape used in Comparative Example 3 is the same as that in Example 1, and the barrier layer of the protective carbon tape is also the same as that in Example 1;

[0082] The raw materials of the additive layer are weighed according to the following parts by weight: 43 parts of 2-butanone, 42 parts of toluene, 14 parts of thermoplastic methyl methacrylate, 3 parts of ultraviolet absorber, and 3 parts of hindered amine light stabilizer.

[0083] Test Example

[0084] The transfer integrity of the printed color carbon tape, the abrasion resistance of the printed pattern, the display effect of the printed pattern, and the accelerated aging test of the printed pattern are carried out according to the following methods;

[0085] Transfer integrity test of color carbon tape:

[0086] Use a thermal transfer traffic sign printer (manufactured by Hunan Dingyi Zhizao Co., Ltd., model DTP-1300) and a color carbon tape to print a set pattern on 3M PⅡ light box cloth;

[0087] Visually confirm the formed image and evaluate it according to the following evaluation criteria:

[0088] A: No untransferred pattern area is observed in the image;

[0089] B: <0.1% of untransferred pattern is observed in the image;

[0090] C: <1% of untransferred pattern is observed in the image;

[0091] NG: >1% of untransferred pattern is observed in the image.

[0092] Abrasion resistance test of transferred pattern:

[0093] Use a thermal transfer traffic sign printer (manufactured by Hunan Dingyi Zhizao Co., Ltd., model DTP-1300), a color carbon tape, and a protective carbon tape to print a set pattern on 3M PⅡ light box cloth in sequence.

[0094] Test with a wear resistance tester, with a load of 2 kg, and rub with Dowling paper 500 times, and evaluate according to the following evaluation criteria:

[0095] OK: After the friction test, there is no exposed white.

[0096] NG: After the friction test, there is exposed white.

[0097] Display effect test:

[0098] Use a thermal transfer traffic sign printer (manufactured by Hunan Dingyi Zhizao Co., Ltd., model DTP-1300), a color ribbon, and a protective ribbon to print the set pattern on 3M PⅡ light box cloth in sequence. Observe the color under transmission and reflection modes respectively, and evaluate it according to the following evaluation criteria:

[0099] OK: There is no obvious difference in color display under transmission and reflection;

[0100] NG: There is an obvious difference in color display under transmission and reflection.

[0101] Accelerated aging test of the transferred pattern:

[0102] Use a thermal transfer traffic sign printer (manufactured by Hunan Dingyi Zhizao Co., Ltd., model DTP-1300) to print the set pattern on 3M PⅡ light box cloth;

[0103] According to the operation method of "GB / T 16422.2-2014 Plastics - Methods of exposure to laboratory light sources - Part 2: Xenon - arc lamps", the test cycle is 1800h:

[0104] Use a color difference meter to measure the Lab values of the pattern before and after the accelerated aging test, and evaluate it according to the following evaluation criteria:

[0105] OK: Color difference ΔE ≤ 5;

[0106] NG: Color difference ΔE > 5;

[0107] The color difference calculation formula is as follows:

[0108] Color difference ΔE = ((L value before test - L value after test)^2 + (a value before test - a value after test)^2 + (b value before test - b value after test))^0.5.

[0109] The test results of Examples 1 to 8 and Comparative Examples 1 to 3 are shown in the following table.

[0110] Table 1 Test results of Examples 1 to 8

[0111]

[0112] Table 2 Test results of Comparative Examples 1 to 3

[0113] Comparative Example 1 Comparative Example 2 Comparative Example 3 Color transfer integrity test OK NG OK Wear resistance test NG OK OK Display effect test NG OK OK Accelerated aging test NG NG NG

[0114] As can be seen from Table 1 and Table 2, compared with Example 1, in Comparative Example 1, there is no protective carbon ribbon, and when using a color carbon ribbon alone to print a pattern, it shows low smoothness and poor abrasion resistance. At the same time, without a protective carbon ribbon, the weather resistance protection and display effect are improved, but after xenon lamp accelerated aging, the fading is obvious; compared with Example 1, in Comparative Example 2, the pigment content in the color carbon ribbon is relatively low, and the resolution during transfer is poor, and incomplete transfer is likely to occur. Moreover, when the pigment content is low, after the pigment ages, the coloring power is insufficient and the color difference is large; compared with Example 1, in Comparative Example 3, the additive content in the additive layer of the protective carbon ribbon is low. After a long-term xenon lamp aging test, the additive fails and the protective effect disappears, and it cannot provide long-term protection.

[0115] In addition, the terms "first" and "second" are used for descriptive purposes only and cannot be construed as indicating or implying relative importance or implicitly specifying the quantity of the indicated technical features. Thus, features defined with "first" and "second" may explicitly or implicitly include at least one of these features.

[0116] In the present invention, unless otherwise clearly defined and limited, the first feature being "on" or "under" the second feature may be that the first and second features are in direct contact, or the first and second features are indirectly in contact through an intermediate medium. Moreover, the first feature being "above", "over" and "on top of" the second feature may be that the first feature is directly above or obliquely above the second feature, or merely indicates that the first feature has a higher horizontal height than the second feature. The first feature being "under", "below" and "beneath" the second feature may be that the first feature is directly below or obliquely below the second feature, or merely indicates that the first feature has a lower horizontal height than the second feature.

[0117] In the description of this specification, the description with reference to terms such as "one embodiment", "some embodiments", "example", "specific example", or "some examples" means that the specific features, structures, materials, or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials, or characteristics described may be combined in any one or more embodiments or examples in a suitable manner. In addition, without conflict, those skilled in the art may combine and combine the different embodiments or examples described in this specification and the features of the different embodiments or examples.

[0118] Although the embodiments of the present invention have been shown and described above, it can be understood that the above embodiments are exemplary and should not be construed as limiting the present invention. Those of ordinary skill in the art can make changes, modifications, substitutions, and variations to the above embodiments within the scope of the present invention.

Claims

1. A highly weather-resistant outdoor thermal transfer ribbon assembly, characterized in that: It comprises a color carbon ribbon and a protective carbon ribbon, wherein the color carbon ribbon comprises a first substrate layer, a first back coating layer, a peeling layer and a color layer, wherein the first back coating layer and the peeling layer are respectively arranged on two opposite sides of the first substrate layer, and the color layer is arranged on the surface of the peeling layer; The protective carbon tape comprises a second substrate layer, a second back coating layer, a barrier layer and an auxiliary agent layer. The second back coating layer and the barrier layer are respectively arranged on two opposite sides of the second substrate layer, and the auxiliary agent layer is arranged on the surface of the barrier layer.

2. The highly weather-resistant outdoor thermal transfer ribbon assembly according to claim 1, characterized in that: The components of the peeling layer include thermoplastic acrylic resin A and thermoplastic acrylic resin B, wherein the molecular weight of the thermoplastic acrylic resin A is 20,000 to 35,000, and the glass transition temperature Tg value is 60 to 110° C.; the molecular weight of the thermoplastic acrylic resin B is 100,000 to 150,000, and the glass transition temperature Tg value is 100 to 105° C.; In terms of weight percentage, the thermoplastic acrylic resin A accounts for 70% to 90% of the peeling layer, and the thermoplastic acrylic resin B accounts for 10% to 30% of the peeling layer.

3. The highly weather-resistant outdoor thermal transfer ribbon assembly according to claim 2, characterized in that: The preparation method of the peeling layer is as follows: thermoplastic acrylic resin A and thermoplastic acrylic resin B are dissolved and ground and dispersed by solvent to prepare a peeling layer coating liquid, and then a 500-line ceramic anilox roller and a gravure coater are used to coat the back coating liquid on the substrate layer, and the back coating liquid is dried at 80-100° C. The coating speed is 60-100 m / min.

4. The highly weather-resistant outdoor thermal transfer ribbon assembly according to claim 1, characterized in that: The components of the color layer include polyolefin modified acrylic resin, thermoplastic methyl methacrylate, pigment, and plasticizer; The molecular weight of the thermoplastic methyl methacrylate is 200,000 to 300,000, and the glass transition temperature Tg value is greater than 100° C. The particle size of the pigment is D50 < 0.08 um, D100 < 0.1 um; In terms of weight percentage, the polyolefin modified acrylic resin accounts for 5% to 15% of the color layer, the thermoplastic methyl methacrylate accounts for 30% to 45% of the color layer, the pigment accounts for 45% to 60% of the color layer, and the plasticizer accounts for 0% to 10% of the color layer.

5. The highly weather-resistant outdoor thermal transfer ribbon assembly according to claim 4, characterized in that: The preparation method of the color layer is as follows: polyolefin modified acrylic resin, thermoplastic methyl methacrylate, pigment and plasticizer are dissolved in a solvent, and then ground to prepare a color layer coating liquid, and the color layer is coated on the substrate layer by a 250-line ceramic anilox roller and a gravure coater, and then dried at 80-100° C., and the coating speed is 60-100 m / min.

6. The highly weather-resistant outdoor thermal transfer ribbon assembly according to claim 1, characterized in that: The components of the barrier layer include thermoplastic acrylic resin C, thermoplastic acrylic resin D, micro wax powder, and solid filler; The molecular weight of the thermoplastic acrylic resin C is 20,000 to 35,000, and the glass transition temperature Tg is 90 to 110° C.; the molecular weight of the thermoplastic acrylic resin D is 100,000 to 350,000, and the glass transition temperature Tg is 100 to 110° C.; In terms of weight percentage, the thermoplastic acrylic resin C accounts for 40% to 60% of the barrier layer, the thermoplastic acrylic resin D accounts for 40% to 60% of the barrier layer, the micro wax powder accounts for 2% to 8% of the barrier layer, and the solid filler accounts for 2% to 8% of the barrier layer.

7. A highly weather-resistant outdoor thermal transfer ribbon assembly according to claim 6, characterized in that: The preparation method of the barrier layer is as follows: thermoplastic acrylic resin C, thermoplastic acrylic resin D, micro wax powder and solid filler are dissolved in a solvent, ground and dispersed to prepare a barrier layer coating liquid, and then a 200-line ceramic anilox roller and a gravure coater are used to coat the back coating liquid on the substrate layer, and the back coating liquid is dried at 80-100° C. The coating speed is 60-100 m / min.

8. The highly weather-resistant outdoor thermal transfer ribbon assembly according to claim 1, characterized in that: The components of the auxiliary agent layer include thermoplastic methyl methacrylate, ultraviolet absorber, and hindered amine light stabilizer; The molecular weight of the thermoplastic methyl methacrylate is 10,000 to 50,000, and the glass transition temperature Tg value is 60 to 90° C.; the molecular weight of the ultraviolet absorber is greater than 600, and the molecular weight of the hindered amine light stabilizer is greater than 2,000; In terms of weight percentage, the thermoplastic methyl methacrylate accounts for 20% to 40% in the auxiliary agent layer, the ultraviolet absorber accounts for 20% to 40% in the auxiliary agent layer, and the hindered amine light stabilizer accounts for 20% to 40% in the auxiliary agent layer.

9. The highly weather-resistant outdoor thermal transfer ribbon assembly according to claim 8, characterized in that: The preparation method of the auxiliary agent layer is as follows: thermoplastic methyl methacrylate, ultraviolet absorber and hindered amine light stabilizer are dissolved in a solvent, and then prepared into an auxiliary agent layer coating liquid, and the auxiliary agent layer coating liquid is coated on the barrier layer on one side of the substrate layer by a 2800-line ceramic anilox roller and a gravure coater, and dried at a temperature of 80 to 100° C., and the coating speed is 60 to 100 m / min.

10. A method for thermal transfer of a pattern, characterized in that: The method comprises the following steps: using a thermal transfer printer to heat the color ribbon according to any one of claims 1 to 9 by a thermal print head to form a color pattern layer on a printing substrate, and then continuing to heat the protective ribbon according to any one of claims 1 to 9 by a thermal print head to form a protective coating on the color pattern layer to obtain the pattern.

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