High-gloss thermal mounting protection thermal transfer ribbon with high weather resistance and assistant migration resistance

Abstract

The invention belongs to the technical field of thermal mounting thermal transfer ribbons, and particularly relates to a high-gloss thermal mounting protective thermal transfer ribbon with high weather resistance and assistant migration resistance and a preparation method of the high-gloss thermal mounting protective thermal transfer ribbon. The invention discloses a high-gloss thermal mounting protection thermal transfer ribbon with high weather resistance and assistant migration resistance. The high-gloss thermal mounting protection thermal transfer ribbon comprises a back coating layer, a base material, a release layer, a protection layer and a bonding layer which are arranged in sequence. The protective thermal transfer ribbon suitable for the hot laminating process, provided by the invention, can bring better luminosity performance and excellent weather resistance, has good assistant migration resistance, and can resist erosion of extremely severe natural environments.

Description

Technical Field

[0001] The present invention belongs to the technical field of thermal lamination carbon ribbons, and particularly relates to a high-gloss thermal lamination protective carbon ribbon with high weather resistance and resistance to migration of additives and a preparation method thereof. Background Art

[0002] Traffic reflective film plays a crucial role in the modern traffic system and is indispensable for ensuring road traffic safety and improving traffic operation efficiency. However, the application environment it is in is extremely complex and harsh, facing many threats, which makes it of great background significance to effectively protect traffic reflective film.

[0003] Currently, coloring the reflective film by thermal transfer or inkjet is a relatively reliable and economical method. However, since the road traffic reflective film prepared in this way needs to be used outdoors all year round, high requirements are put forward for its weather resistance. In this regard, a common method is to add a transparent protective film outside the ink layer. The functions of the protective film include not only preventing external damage and pollution, but also having an ultraviolet protection function to avoid ultraviolet rays accelerating the aging of the ink and affecting the chromaticity and reflective performance of the traffic reflective film. The traditional transparent protective film is attached to the ink layer by the way of full thermal transfer by a print head. Therefore, the thickness of the protective carbon ribbon used should not be too thick, otherwise it is easy to have the problem of incomplete transfer due to insufficient heat supply, but if it is too thin, the weather resistance of the protective film layer will seriously decline and cannot withstand the test of extreme climate conditions in the natural environment for the traffic reflective film.

[0004] Currently, the most common way to protect the reflective film on the market is to apply a UV protective film. Although this film material has strong applicability, it has disadvantages. There are often bubbles that cannot be eliminated in the film laminating process, and the cost is relatively high. In addition, the thermal transfer protective carbon ribbon is attached to the ink layer by the way of pressurization by a thermal print head. Increasing the thickness of the protective carbon ribbon coating can more efficiently improve the weather resistance, but the thermal transfer method has thickness limitations. Consumables that are too thick cannot be transferred or are incompletely transferred by the way of heating and pressurization by the print head, which has limitations compared with the thermal lamination process; at the same time, the thermal transfer protective carbon ribbon will add too many additives to meet its better weather resistance and scratch resistance, but there is a risk that the additives will migrate to the surface during the aging process, which will exacerbate the problem of the sharp decline in the photometric performance in the outdoor harsh environment. After the protective carbon ribbon with an increased coating thickness is laminated by a suitable thermal lamination process, the photometric performance can be significantly improved. Therefore, in more severe scenarios, the advantages of the thermal lamination process over the thermal transfer process are obvious.

[0005] The current transparent protective film on the market is attached to the ink layer by the method of full transfer printing with a print head. Therefore, the thickness of the protective carbon tape used should not be too thick, otherwise it is easy to have the problem of incomplete transfer due to insufficient heat supply. However, if it is too thin, the weather resistance of the protective film layer will seriously decline, and it cannot pass the test of the extreme climate conditions in the natural environment for traffic reflective films. Summary of the Invention

[0006] To solve the deficiencies of the prior art, the present invention provides a high-gloss thermal lamination protective carbon tape with high weather resistance and resistance to additive migration, and a preparation method thereof. The protective carbon tape applicable to the thermal lamination process provided by the present invention can bring better photometric performance, better excellent weather resistance, and also has good resistance to additive migration, and can withstand the erosion of extremely harsh natural environments.

[0007] The technical solutions provided by the present invention are as follows:

[0008] A high-gloss thermal lamination protective carbon tape with high weather resistance and resistance to additive migration, including a back coating, a substrate, a release layer, a protective layer, and an adhesive layer arranged in sequence.

[0009] Based on the above technical solutions:

[0010] Including the matrix, having a thicker thickness, matching the thermal lamination process;

[0011] The release layer is the outermost layer after thermal lamination. Through specific wax powder, it is more wear-resistant and more suitable for outdoor use;

[0012] In the protective layer, resins with larger molecular weights are used. On the one hand, it matches the thermal lamination process, and on the other hand, it can stably coat reactive ultraviolet absorbers to improve weather resistance.

[0013] Substrate:

[0014] For the thermal lamination protective carbon tape of the present invention, the substrate is a transparent flexible plastic film, such as polypropylene (PP), polyethylene naphthalate (PEN), polyethylene terephthalate (PET), polyethylene (PE), polyvinyl alcohol (PVA), polymethyl methacrylate (PMMA), etc. Among them, PET is preferred.

[0015] Furthermore, the thickness of the substrate is 4 - 130 μm. Considering that the thermal lamination process has requirements for the heat resistance of the substrate, thicker substrates are preferably considered. Preferably, the thickness of the matrix is 10 - 50 μm.

[0016] Generally speaking, surface treatment of the substrate is a common process before coating. A simple and efficient method often uses corona treatment, and the surface dyne value of the substrate > 38 meets the requirements.

[0017] Release layer:

[0018] Setting a release layer between the protective layer and the substrate can ensure better detachment of the protective layer and the substrate during the thermal lamination process. At the same time, after thermal lamination, the release layer on the surface of the protective layer can also achieve a smooth effect, improving the friction resistance of the protective layer.

[0019] Furthermore, the release layer is composed of an adhesive resin and wax powder.

[0020] Furthermore, the adhesive resin is mainly composed of one or more of acrylic resin, vinyl chloride-vinyl acetate, vinyl chloride-vinyl isobutyl ether, polyurethane, ethylene-vinyl acetate, rosin resin, terpene resin, polyester resin, etc. To ensure a certain adhesion between the release layer and the substrate as well as the protective layer, the adhesive resin is preferably ethylene-vinyl acetate.

[0021] Furthermore, the wax powder in the release layer can be one or more of Fischer-Tropsch wax, polyethylene wax (PE wax), polytetrafluoroethylene wax, polypropylene wax (PP wax), ethylene-vinyl acetate copolymer wax (EVA wax), oxidized polyethylene wax, carnauba wax, beeswax, etc., or substances obtained by chemically modifying the above waxes.

[0022] Furthermore, the wax powder in the release layer is preferably polyethylene-based, and more preferably polyethylene wax powder modified with polytetrafluoroethylene.

[0023] Furthermore, the dropping melting point of the wax powder is 90-130°C, and the median particle size is 3-8μm.

[0024] Furthermore, the ratio of the adhesive resin to the wax powder in the release layer is 1:9-3:7. The release layer within this range has good cold and hot peeling effects and appropriate adhesion to the substrate and the protective layer.

[0025] Furthermore, the release layer may also contain inorganic particles, such as metal oxide particles such as aluminum particles, zirconia particles, calcium carbonate particles, silica particles, titanium oxide, zinc oxide particles, etc.

[0026] The thickness of the release layer is 0.5-20μm, preferably 1-10μm.

[0027] The release layer can be formed in the following manner: Disperse or dissolve the above materials in a suitable solvent, and use a grinder to grind so that the particle size D50 of the release coating liquid is maintained at 0.1-0.5μm, which can ensure a delicate coating film surface. Coating it on the surface of the substrate by gravure coating or slot coating and heating and drying can form the release layer.

[0028] The solvent includes at least one of 2-butanone, toluene, xylene, ethyl acetate, butyl acetate, or propylene glycol methyl ether acetate.

[0029] Protective layer:

[0030] In the present invention, the protective layer is obtained by cross-linking reaction of a thermosetting fluorocarbon resin, a thermosetting acrylic resin and a reactive ultraviolet absorber through a cross-linking agent. The prepared polymer resin can be further combined with a thermoplastic resin and a lubricant.

[0031] The main resin used in the protective layer of the present invention is a fluorocarbon resin modified by acrylic acid. The C-F bond energy in the fluorocarbon resin is large (460 kJ / mol), with high stability. The helically arranged fluorine atoms play a good "shielding protection" role for the carbon main chain, which can effectively prevent the exposure of carbon atoms and carbon chains, making the fluorinated acrylate have excellent weather resistance, corrosion resistance, chemical medium resistance, etc. During the film-forming process, the fluorine alkyl group with extremely low surface energy will preferentially migrate to the surface, making the surface of the coating film have excellent hydrophobic, oleophobic, stain-resistant and other properties. After being modified by acrylic acid, the adhesion of the fluorocarbon resin to the substrate is improved, and the cross-linking degree and the solvent resistance of the resin are further enhanced.

[0032] Furthermore, the thermosetting fluorocarbon resin used in the present invention refers to a copolymer of chlorotrifluoroethylene / tetrafluoroethylene and vinyl ether / vinyl ester containing a hydroxyl functional group in the resin main chain.

[0033] Furthermore, the fluorine content in the thermosetting fluorocarbon resin used in the present invention is 10-45%, preferably 15-40%. If the fluorine content is too low, its weather resistance and self-cleaning performance will decline. If the fluorine content is too high, the adhesion of the resin will decrease.

[0034] Furthermore, in the present invention, the molecular weight of the thermosetting fluorocarbon resin is Mn = 1000-20000, preferably 2000-10000. The hydroxyl value is 10-100 mgKOH / g, preferably 30-80 mgKOH / g.

[0035] Furthermore, the thermosetting acrylic resin used in the present invention refers to an acrylic resin prepared by free radical polymerization of hard monomers such as styrene and methyl methacrylate, soft monomers such as ethyl acrylate, butyl acrylate and butyl methacrylate, and hydroxyl-containing functional monomers such as hydroxyethyl (propyl) acrylate and hydroxyethyl (propyl) methacrylate under the action of a molecular chain regulator.

[0036] Furthermore, styrene, acrylonitrile and higher alkyl esters of methacrylic acid are introduced into the monomers for synthesizing the thermosetting acrylic resin to improve the ethanol resistance and reduce the ester group content. To balance the weather resistance and ethanol resistance, the two can be considered for use together. The higher alkyl esters of methacrylic acid include lauryl methacrylate, stearyl methacrylate, etc.

[0037] The content of the soft monomer in the thermosetting acrylic resin is 30%-40%. If it is too high, the surface hardness of the paint film will be too low. If it is too low, the compatibility with the thermosetting fluorocarbon resin will be relatively poor.

[0038] In the further present invention, the molecular weight of the thermosetting acrylic resin is Mn = 1000 - 20000, preferably 2000 - 10000, and the hydroxyl value is 10 - 100 mgKOH / g, preferably 30 - 80 mgKOH / g.

[0039] As an example of the reactive ultraviolet absorber, a substance obtained by introducing an addition polymerizable double bond such as a vinyl group, an acryloyl group, or a methacryloyl group into a non-reactive ultraviolet absorber such as a salicylate-based, benzophenone-based, benzotriazole-based, triazine-based, substituted acrylonitrile-based, nickel chelate-based, or hindered amine-based ultraviolet absorber, which is publicly known, or a substance selected from alcoholic hydroxyl groups, amino groups, carboxyl groups, epoxy groups, isocyanate groups, etc. can be cited.

[0040] Furthermore, as the reactive ultraviolet absorber, a reactive ultraviolet absorber having an alcoholic hydroxyl group is selected, and the selected reactive ultraviolet absorber contains at least one or more alcoholic hydroxyl groups.

[0041] Furthermore, to achieve crosslinking between thermosetting acrylic resins and between thermosetting fluorocarbon resins themselves or between the two, and with the reactive ultraviolet absorber, an isocyanate-based curing agent is added as a crosslinking agent during the reaction.

[0042] Furthermore, the isocyanate-based curing agent is a polyisocyanate compound containing three or more isocyanate groups. For example, oligomers formed from compounds such as isophorone diisocyanate, toluene diisocyanate, and diphenylmethane diisocyanate.

[0043] Furthermore, in the preparation process of the crosslinked resin, first, the thermosetting fluorocarbon resin and the thermosetting acrylic resin are dissolved in a suitable solvent, the required crosslinking agent is added, and a prepolymer is prepared by reacting at 50 - 90 °C. Then, the required reactive ultraviolet absorber is added, and the final resin is prepared by reacting at 50 - 90 °C.

[0044] Furthermore, in the preparation process of the crosslinked resin, for the thermosetting fluorocarbon resin, its mass ratio during the crosslinking reaction is 50 wt% - 80 wt%; for the other thermosetting acrylic resin, its mass ratio during the crosslinking reaction is 10 wt% - 40 wt%; for the reactive ultraviolet absorber, its mass ratio during the crosslinking reaction is 10 wt% - 30 wt%.

[0045] Furthermore, in the preparation of the crosslinked resin, the crosslinking agent is calculated based on the hydroxyl value of the reactants, and preferably the molar ratio of hydroxyl to isocyanate is n(-OH) / n(-NCO) = 0.8 - 1.2.

[0046] Furthermore, to improve the adhesion between the protective layer and the adhesive layer, the protective layer may further contain a thermoplastic resin, such as one or more components selected from acrylic resins, vinyl chloride-vinyl acetate resins, vinyl chloride-vinyl isobutyl ether resins, polyurethane resins, ethylene-vinyl acetate resins, etc.

[0047] Furthermore, to further enhance the UV resistance of the protective layer, a radical scavenger is added to the protective layer. The main type of the radical scavenger is hindered amines.

[0048] Furthermore, to ensure better stability of the radical scavenger and extend its action time, the used radical scavenger has a molecular weight greater than 3000. The addition amount is 1 wt% - 20 wt%, preferably 3 wt% - 10 wt%.

[0049] Furthermore, the thickness of the protective layer is 0.5 - 20 μm, preferably 1 - 10 μm.

[0050] The preparation method of the protective layer is to dissolve a certain amount of resin in solvents such as methyl ethyl ketone and toluene, then add a certain amount of additives to obtain the protective layer coating, and then coat it on the surface of the release layer by gravure coating or slot coating and heat it for drying and curing.

[0051] Adhesive layer:

[0052] To enable the protective layer to better adhere to the transfer body and adapt to a variety of different substrates, an adhesive layer can be provided on the side of the protective layer away from the substrate.

[0053] Furthermore, to provide good adhesion, the resin used in the adhesive layer is mainly composed of one or more components selected from acrylic resins, vinyl chloride-vinyl acetate resins, vinyl chloride-vinyl isobutyl ether resins, polyurethane resins, ethylene-vinyl acetate resins, etc.

[0054] Furthermore, to enable the adhesive layer to also have good aging resistance, the preferred resin is a thermoplastic acrylic resin.

[0055] In the resin used in the adhesive layer, the acrylic resin includes polymers or their derivatives of acrylic acid or methacrylic acid, polymers or their derivatives of acrylate or methacrylate, copolymers or their derivatives of acrylic acid or methacrylic acid with reactive monomers, and copolymers or their derivatives of acrylate or methacrylate with reactive monomers.

[0056] As the reactive monomers, for example, aromatic hydrocarbons, aryl-containing compounds, amide group-containing compounds, vinyl chloride, etc., styrene, benzyl styrene, phenoxyethyl methacrylate, acrylamide, and methacrylamide can be cited.

[0057] Furthermore, in the present invention, the molecular weight Mn of the thermoplastic acrylic resin is 5000 - 300000, preferably 5000 - 15000, and the glass transition temperature Tg is 40 - 120°C, preferably 60 - 90°C.

[0058] Furthermore, the thickness of the adhesive layer is 0.1 - 2 μm, preferably 0.2 - 0.4 μm.

[0059] The preparation method of the adhesive layer is to dissolve a certain amount of resin in solvents such as methyl ethyl ketone and toluene, and then coat it on the surface of the protective layer by gravure coating or slot coating and dry it.

[0060] Back coating:

[0061] The function of the back coating is to provide a smooth effect on the heating roller in the thermal laminating process, and it also helps to optimize heat transfer to ensure that the heat generated by the heating roller of the thermal laminator can be transferred to the ink layer of the protective carbon ribbon more evenly and effectively. Moreover, in the wound protective carbon ribbon, it can prevent the carbon ribbon itself from sticking. The components of the back coating can be selected from known thermoplastic resins and the like. As such thermoplastic resins, for example, polyester resins, polyacrylate resins, polyvinyl acetate resins, styrene acrylate resins, polyurethane resins, polyethylene resins, polypropylene resins and other polyolefin resins, polystyrene resins, polyvinyl chloride resins, polyether resins, polyamide resins, polyimide resins, polyamideimide resins, polycarbonate resins, polyacrylamide resins, polyvinyl chloride resins, polyvinyl butyral resins, polyvinyl acetal resins and other polyvinyl acetal resins such as polyvinyl acetal resins, their silicone modifications, etc. Polyvinyl butyral resin is preferred.

[0062] Furthermore, to improve the heat resistance of the back coating during the printing process, improve the adhesion between the back coating and PET, and reduce the viscosity at high temperatures. An isocyanate compound can be added to the above-mentioned resin. There is no particular limitation on the type of the isocyanate compound, and known substances can be used, such as toluene diisocyanate (TDI), isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), dicyclohexylmethane diisocyanate (HMDI), hexamethylene diisocyanate (HDI), lysine diisocyanate (LDI), etc. Aromatic isocyanate compounds are preferably used. As aromatic isocyanate compounds, for example, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, tolidine diisocyanate, p-phenylene diisocyanate, etc. can be cited. The dosage is 0.1% - 2% by mass of the total amount.

[0063] Furthermore, to maintain excellent smoothness of the protective carbon ribbon during hot laminating, inorganic fillers such as talc, kaolin, calcium carbonate, aluminum hydroxide, silicon dioxide, graphite, boron nitride, etc., and release agents such as phosphate ester compounds, metal soaps, silicone oil, surfactants, etc. need to be added to the back coating. The preferred inorganic filler is talc, with a mesh number of 5000 - 11000, and the addition amount is 1% - 5% by mass of the resin, preferably 3% - 5% by mass. The preferred release agent is phosphate ester, and the addition amount is 1% - 10% by mass of the resin, preferably 3% - 5% by mass. Further, to ensure the uniform dispersion of inorganic fillers in the resin, improve the good thermal conductivity of the back coating, enhance the gloss after transfer, reduce the surface roughness, and improve the wear resistance, it is necessary to control the overall particle size and particle size distribution of the back coating fillers. The required D50 particle size of the fillers is 1.0 - 5μm, and the D90 particle size is 3 - 10μm. If the requirements are not met, grinding treatment is required.

[0064] The preparation method of the back coating is to dissolve a certain amount of resin in a conventional organic solvent. There is no special limitation on the type of conventional organic solvent. Preferably, the resin can be dissolved in the organic solvent and has a viscosity of 100 - 500 mPa·s at 25°C. For example, the organic solvent can be acetone, 2-butanone, cyclohexanone, isophorone, tetrahydrofuran, ethyl acetate, butyl acetate, propyl acetate, toluene, xylene, DMF, etc. Preferably, 2-butanone and toluene are miscible, and the ratio of 2-butanone to toluene is controlled between 8:2 - 1:1, and the content is preferably more than 50% by mass and less than 80% by mass of the total mass of the adhesive layer. Then, a certain amount of additives is added to obtain the adhesive layer coating, which is coated on the surface of the substrate by gravure coating or slot coating and dried. The drying temperature is 60 - 120°C, and the drying time is 60 - 120 s.

[0065] The coating thickness of the back coating is generally 0.4μm - 1.2μm, preferably 0.4 - 0.6μm.

[0066] The present invention also provides a preparation method of a high-gloss hot-laminating protective carbon ribbon with high weather resistance and resistance to additive migration, including the following steps: treating the surface of the substrate, then preparing a back coating on one side of the substrate, and sequentially preparing a release layer, a protective layer, and an adhesive layer on the other side of the substrate.

[0067] The present invention also provides an application of a high-gloss hot-laminating protective carbon ribbon with high weather resistance and resistance to additive migration. It is transferred to a traffic reflective film by hot laminating to form a protective film.

[0068] Hot laminating speed: 2.5 - 5 cm / s.

[0069] Hot laminating temperature: 100 - 120°C.

[0070] The beneficial effects of the present invention are as follows:

[0071] 1) After thermal lamination, it exhibits higher gloss performance than before lamination, with a maximum increase of 13.4%.

[0072] 2) Using a reactive protective layer system can make the xenon lamp aging resistance duration > 3600h, with no obvious color difference before and after. Description of the Drawings

[0073] Figure 1 It is a schematic structural diagram of the high-gloss thermal lamination protective carbon ribbon with high weather resistance and resistance to additive migration provided by the present invention.

[0074] Figure 2 It is a comparative diagram of the pattern transfer effect of the thermal lamination protective carbon ribbon.

[0075] Appendix Figure 1 In the appendix, the list of structures represented by each reference numeral is as follows:

[0076] 1. Back coating; 2. Substrate; 3. Release layer; 4. Protective layer; 5. Adhesive layer. Detailed Embodiments

[0077] The principles and features of the present invention are described below. The examples given are only used to explain the present invention and are not intended to limit the scope of the present invention.

[0078] Unless otherwise specified, the test methods used in the examples are all conventional methods; the materials, reagents, etc. used, unless otherwise specified, are reagents and materials that can be obtained commercially.

[0079] In a specific embodiment, as Figure 1 shown, the high-gloss thermal lamination protective carbon ribbon with high weather resistance and resistance to additive migration includes a back coating 1, a substrate 2, a release layer 3, a protective layer 4, and an adhesive layer 5 arranged in sequence.

[0080] The specific preparation method is as follows:

[0081] Use a PET film with a thickness of 12μm as the base material. Corona is applied to one side of the base material to make the surface dyne value of the substrate > 38, which meets the requirements. The coating liquid for forming the back coating with the following composition is coated on the corona-applied side of the base material by gravure coating, and after drying, it is 0.4μm to form the back coating. The coating liquid for forming the release layer with the following composition is coated on the other side of the base material, and after drying, it is 3μm to form the release layer. Then, the coating liquid for forming the protective layer with the following composition is coated on the release layer by slot coating, and after drying, it is 3μm to form the protective layer. Then, the coating liquid for forming the adhesive layer with the following composition is coated on the protective layer by gravure coating, and after drying, it is 0.4μm to form the adhesive layer.

[0082] Example 1 of the thermal lamination protective carbon ribbon

[0083] Substrate: A 12 μm thick PET film (Lμmirror, Toray, Japan) was used.

[0084] The coating liquid formulas are as follows:

[0085] Release layer:

[0086] 2 parts of ethylene-vinyl acetate copolymer (Mitsui Chemicals 210W)

[0087] PE wax powder (Tianshi wax powder PEW-0200) 8 parts

[0088] 30 parts of butanone

[0089] Toluene 60 parts

[0090] The prepared dispersion was ground by a grinder (horizontal grinder, zirconium bead particle size 0.6 mm) to obtain an average particle size D50 of 0.1-0.4 μm, thereby obtaining a release layer coating liquid, which was coated using a slit coater.

[0091] Protective layer:

[0092] 100 parts of cross-linked resin solution

[0093] Free radical scavengers ( UV-622, Tianjin Lianlong New Materials Co., Ltd.) 3 parts

[0094] 5 parts of thermoplastic resin (MB-2660, Mitsubishi Chemical Corporation)

[0095] The mass fraction of the cross-linked resin raw material is as follows

[0096] Butanone 50 parts

[0097] Toluene 23 parts

[0098] Thermosetting acrylic resin: YZ-H638 hydroxy acrylic resin (Yak Chemical) (hydroxyl value: 55 mgKOH / g; molecular weight: 4000) 6 parts

[0099] Thermosetting fluorocarbon resin: Jotunheim F100 ( Jotun ) (Hydroxy value: 65 mgKOH / g; Molecular weight: 3000) 15 parts

[0100] Reactive UV absorber (2-hydroxy-4-(2-hydroxy-3-decyloxypropoxy)benzophenone) 3 parts

[0101] 3 parts of polyisocyanate compound (-NCO content: 19%)

[0102] Coating with slot coater

[0103] Subsequent layer:

[0104] 45 parts of methyl ethyl ketone

[0105] 45 parts of toluene

[0106] 10 parts of thermoplastic acrylic resin (BR-83, Mitsubishi Chemical Corporation)

[0107] Coated using a gravure coater

[0108] Back coating:

[0109] 3 parts of polyvinyl butyral (B265H-B, Guangzhou Hongshang)

[0110] 7 parts of cellulose acetate butyrate (CAB393-3, Eastman, USA)

[0111] Isocyanate ( MDI-50, Wanhua Chemical) 2.5 parts

[0112] 0.5 part of talcum powder (LJ-320, Liangjiang Chemical Industry)

[0113] 0.2 part of silicone oil (KF-6001, Shin-Etsu Silicone)

[0114] 57.8 parts of 2-butanone

[0115] 29 parts of toluene

[0116] The prepared dispersion is ground in a grinding machine (horizontal grinding machine, zirconium bead particle size is 0.6 mm), and grinding for 30 min is sufficient, with no particle size requirement. Thus, the release layer coating liquid is obtained. Coated using a gravure coater.

[0117] The hot laminating parameters of the hot laminating protective carbon ribbon prepared as above are as follows:

[0118] Hot laminating speed: 2.5 cm / s.

[0119] Hot laminating temperature: 100 °C.

[0120] Example 2 of hot laminating protective carbon ribbon

[0121] The substrate thickness is set to 6 μm, and the coating liquid formulation and process, and hot laminating process are as in Example 1.

[0122] Example 3 of hot laminating protective carbon ribbon

[0123] The hot laminating temperature is set to 120 °C, and the substrate thickness, coating liquid formulation and process, and hot laminating speed are as in Example 1.

[0124] Example 4 of hot laminating protective carbon ribbon

[0125] The hot lamination speed is set at 5 cm / s, and the substrate thickness, coating solution formulation and process, and hot lamination temperature are the same as those in Example 1.

[0126] Hot Lamination Protective Ribbon Comparative Example 1

[0127] The substrate thickness is set at 25 μm, and the coating solution formulation and process, and hot lamination process are the same as those in Example 1.

[0128] Hot Lamination Protective Ribbon Comparative Example 2

[0129] The hot lamination temperature is set at 80 °C, and the substrate thickness, coating solution formulation and process, and hot lamination speed are the same as those in Example 1.

[0130] Hot Lamination Protective Ribbon Comparative Example 3

[0131] The hot lamination speed is set at 10 cm / s, and the substrate thickness, coating solution formulation and process, and hot lamination temperature are the same as those in Example 1.

[0132] Hot Lamination Protective Ribbon Comparative Example 4

[0133] The coating thickness of the release layer and the protective layer is reduced to 1.5 μm, and the coating solution formulation, back coating, adhesive layer process, and hot lamination process are the same as those in Example 1.

[0134] Hot Lamination Protective Ribbon Comparative Example 5

[0135] Use the company's self-developed traffic printer DTP-1300 for thermal transfer lamination, and the preparation process is exactly the same as that in Example 1.

[0136] Hot Lamination Protective Ribbon Comparative Example 6

[0137] Use the company's self-developed traffic printer DTP-1300 for thermal transfer lamination, and the preparation process is exactly the same as that in Comparative Example 4.

[0138] Hot Lamination Protective Ribbon Comparative Example 7

[0139] Only the formulation of the protective layer is changed, and the rest is the same as in Example 1

[0140] Protective layer:

[0141] 39 parts of methyl ethyl ketone

[0142] 40 parts of toluene

[0143] 10 parts of thermoplastic acrylic resin (BR-83 Mitsubishi Chemical Corporation)

[0144] 5 parts of ultraviolet absorber (UV-460 solid, BASF)

[0145] 5 parts of ultraviolet absorber (UV-120 solid, Milan Chemical)

[0146] 1 part of talcum powder (MICRO ACE P-3 Japanese talc powder)

[0147] Coating is carried out using a gravure coater and a slot coater.

[0148] Performance test plan:

[0149] Preparation of heat-laminated protective carbon ribbon printed samples: After transferring the high-weather-resistant yellow ribbon independently developed by our company to 3M Class V reflective film using the traffic printer DTP-1300 independently developed by our company, the protective carbon ribbon is transferred to the ink layer using a Yanpai 120-type 1700H fully automatic integrated low-temperature heat laminator.

[0150] Preparation of thermal transfer protective carbon ribbon printed samples: After transferring the high-weather-resistant yellow ribbon independently developed by our company to 3M Class V reflective film using the traffic printer DTP-1300 independently developed by our company, the protective layer carbon ribbon is simultaneously transferred onto the ink layer.

[0151] Comparative Example 5 and Comparative Example 6 adopt the thermal transfer method.

[0152] For the light transmittance of the protective layer, the retroreflective coefficient before and after transferring the protective layer is measured using a retroreflective test system (observation angle 0.2°, incident angle -4°), and the light transmittance is calculated through the following formula:

[0153]

[0154] Test method for ultraviolet light transmittance: Refer to "GB / T 17032-1997 Test Method for Ultraviolet Light Transmittance of Textiles and Fabrics".

[0155] The solvent resistance performance test was carried out for ethanol and gasoline resistance tests with reference to the national standard "GB-T 23989-2009 Determination Method for Solvent Rub Resistance of Coatings".

[0156] The stain resistance performance test was carried out with reference to the national standard "GB-T 9780-2013 Test Method for Stain Resistance of Architectural Coating Coatings".

[0157] The adhesion test was carried out with reference to the national standard "GB / T 9286-2021 Cross-Cut Test for Paints and Varnishes".

[0158] The weather resistance of the samples was evaluated in the following way:

[0159] With reference to the xenon lamp aging conditions in the national standard "GB / T 18833-2012 Road Traffic Reflective Films", the samples were aged for 3600 hours using a xenon lamp aging test chamber, and whether wrinkles, bubbles, cracks, etc. appeared on their surfaces were observed; and the color difference before and after accelerated aging was measured.

[0160]

[0161]

[0162] As Figure 2 shown, it is a comparative diagram of the pattern transfer effect of the thermal lamination protection carbon ribbon. The left part is the effect of the sample after 3600h aging in Example 1, and the protective layer uses a reactive resin and a reactive auxiliary agent; the right part is the effect of the sample after 3600h aging in Comparative Example 7, and both the resin and the auxiliary agent of the protective layer are non-reactive. It can be seen from the figure that Comparative Example 1 with non-reactive resin and auxiliary agent has poor resistance to auxiliary agent migration.

[0163] In addition, the thickness of Comparative Example 5 is not suitable for thermal transfer. Although Comparative Example 6 can be transferred after reducing the thickness, its aging performance is inferior to that obtained by thermal lamination.

[0164] The above are only the preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A high gloss thermal lamination protective carbon tape with high weather resistance and resistance to additive migration, characterized in that: The invention comprises a back coating layer, a substrate, a release layer, a protective layer and an adhesive layer which are arranged in sequence.

2. The high gloss thermal lamination protective carbon tape with high weather resistance and resistance to additive migration according to claim 1, characterized in that: The release layer comprises an adhesive resin and wax powder in a weight ratio of (1:9)-(3:7); The release layer has a thickness of 0.5-20 μm.

3. The high gloss thermal lamination protective carbon tape with high weather resistance and resistance to additive migration according to claim 2, characterized in that: The adhesive resin is selected from any one or more combinations of acrylic resin, vinyl chloride-vinyl acetate resin, vinyl chloride-vinyl isobutyl ether resin, polyurethane, ethylene-vinyl acetate, rosin resin, terpene resin or polyester resin; The wax powder is selected from any one or more combinations of modified or unmodified polyethylene wax, Fischer-Tropsch wax, polytetrafluoroethylene wax, polypropylene wax, ethylene-vinyl acetate copolymer wax, oxidized polyethylene wax, carnauba wax or beeswax; or, the wax powder is polytetrafluoroethylene-modified polyethylene wax powder; The wax powder has a drop melting point of 90-130°C and a medium particle size of 3-8 μm; The release layer further comprises 0.1wt%-5wt% of inorganic particles, wherein the inorganic particles are selected from any one or more combinations of aluminum particles, zirconium oxide particles, calcium carbonate particles, silicon dioxide particles, titanium oxide particles or zinc oxide particles; The release layer has a thickness of 1-10 μm.

4. The high gloss thermal lamination protective carbon tape with high weather resistance and resistance to additive migration according to claim 1, characterized in that: The protective layer is obtained by reacting a cross-linking component and an isocyanate type curing agent, wherein the cross-linking component comprises the following components in percentage by weight: 50wt%-80wt% of a thermosetting fluorocarbon resin, 10wt%-40wt% of a thermosetting acrylic resin, and 10wt%-30wt% of a reactive ultraviolet absorber; the molar ratio of the hydroxyl group in the cross-linking component to the isocyanate in the isocyanate type curing agent is: n(-OH) / n(-NCO)=0.8-1.2; The weight percentage of fluorine in the thermosetting fluorocarbon resin is 10%-45%; The molecular weight of the thermosetting fluorocarbon resin is Mn=1000-20000; The hydroxyl value of the thermosetting fluorocarbon resin is 10-100 mgKOH / g; The content of soft monomer in the thermosetting acrylic resin is 30%-40%; The molecular weight of the thermosetting acrylic resin is Mn=1000-20000; The thermosetting acrylic resin has a hydroxyl value of 10-100 mgKOH / g; The thickness of the protective layer is 0.5-20 μm.

5. The high gloss thermal lamination protective carbon tape with high weather resistance and resistance to additive migration according to claim 4, characterized in that: The thermosetting fluorocarbon resin is a copolymer of chlorotrifluoroethylene, tetrafluoroethylene, vinyl ether or vinyl ester containing a hydroxyl functional group in the main chain; The fluorine content in the thermosetting fluorocarbon resin is 15%-40%; The thermosetting fluorocarbon resin Mn=2000-10000; The hydroxyl value of the thermosetting fluorocarbon resin is 30-80 mgKOH / g; The thermosetting acrylic resin is prepared by free radical polymerization of 30wt%-40wt% of a hard monomer, 30wt%-40wt% of a soft monomer and 10wt%-20wt% of a hydroxyl-containing functional monomer under the action of a molecular chain regulator; The hard monomer is selected from styrene or methyl methacrylate; The soft monomer is selected from ethyl acrylate, butyl acrylate or butyl methacrylate; The hydroxyl-containing functional monomer is selected from hydroxyethyl (propyl) acrylate or hydroxyethyl (propyl) methacrylate; The thermosetting acrylic resin has a Mn of 2000-10000; The hydroxyl value of the thermosetting acrylic resin is 30-80 mgKOH / g; The reactive ultraviolet absorber is selected from any one or more combinations of salicylate, benzophenone, benzotriazole, triazine, substituted acrylonitrile, nickel chelate or hindered amine reactive ultraviolet absorbers having vinyl, acryloyl, methacryloyl, alcoholic hydroxyl, amino, carboxyl, epoxy or isocyanate groups; Isocyanate-type curing agents are polyisocyanate compounds containing three or more isocyanate groups; The protective layer also includes a thermoplastic resin; the added amount is 20wt%-30wt%; The protective layer also includes a free radical scavenger; the molecular weight of the free radical scavenger is greater than 3000; the added amount is 1wt%-20wt%; The thickness of the protective layer is 1-10 μm.

6. The high gloss thermal lamination protective carbon tape with high weather resistance and resistance to additive migration according to claim 1, characterized in that: The resin material of the bonding layer is selected from any one or more of acrylic resin, vinyl chloride-vinyl acetate, vinyl chloride-vinyl isobutyl ether, polyurethane or ethylene-vinyl acetate; or, the resin material of the bonding layer is a thermoplastic acrylic resin with a molecular weight Mn of 5000-300000 and a glass transition temperature Tg of 40-120°C; The thickness of the adhesive layer is 0.1-2 μm.

7. The high gloss thermal lamination protective carbon tape with high weather resistance and resistance to additive migration according to claim 6, characterized in that: The acrylic resin is selected from polymers of acrylic acid or methacrylic acid or derivatives thereof, polymers of acrylate or methacrylate or derivatives thereof, copolymers of acrylic acid or methacrylic acid and its reactive monomer or derivatives thereof, copolymers of acrylate or methacrylate and its reactive monomer or derivatives thereof; The reactive monomer is selected from a compound containing an aromatic group, a compound containing an amide group, vinyl chloride, styrene, benzyl styrene, phenoxyethyl methacrylate, acrylamide or methacrylamide; The molecular weight Mn of the thermoplastic acrylic resin is 5000-15000, and the glass transition temperature Tg is 60-90°C.

8. The high gloss thermal lamination protective carbon tape with high weather resistance and resistance to additive migration according to claim 1, characterized in that: The substrate is selected from a transparent polypropylene film, a polyethylene naphthalate film, a polyethylene terephthalate film, a polyethylene film, a polyvinyl alcohol film or a polymethyl methacrylate film; The thickness of the substrate is 4-130 μm; The back coating layer comprises the following components in percentage by weight: 5wt%-20wt% of a back coating layer thermoplastic resin, 15wt%-30wt% of a back coating layer isocyanate compound in an amount of resin addition, and 0.1wt%-2wt% of a release agent; The thickness of the back coating layer is 0.4 μm-1.2 μm.

9. A method for preparing a high-gloss heat-mounted protective carbon tape with high weather resistance and resistance to auxiliary agent migration according to any one of claims 1 to 8, characterized in that: The following steps are involved: The surface of the substrate is treated, and then a back coating layer is prepared on one side of the substrate, and a release layer, a protective layer and an adhesive layer are sequentially prepared on the other side of the substrate.

10. An application of the high gloss thermal lamination protective carbon tape with high weather resistance and resistance to additive migration according to any one of claims 1 to 8, characterized in that: It is transferred to the traffic reflective film by heat lamination to form a protective film.

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