A protective resin carbon ribbon for outdoor printing products and a preparation method thereof

Abstract

The present invention relates to a protective resin carbon ribbon for outdoor printing products and a preparation method thereof, and belongs to the field of soft label printing technology. The protective resin carbon ribbon for outdoor printing products comprises an adhesive layer, a protective layer, a release layer, a substrate and a back coating layer which are sequentially laminated from top to bottom; the protective layer is formed by mixing the following raw materials in parts by weight and then coating: 100-200 parts of solvent, 30-50 parts of main resin, 3-8 parts of second thermoplastic acrylic resin, 8-12 parts of thermosetting acrylic resin, 3-8 parts of isocyanate curing agent, 0.1-1 parts of light stabilizer and 0.1-1 parts of light absorber. The present invention also discloses a preparation method of the protective resin carbon ribbon for outdoor printing products. Beneficial effect: after printing the adhesive layer, the protective layer is printed on the outermost layer by thermal transfer, and the same protective effect as spraying or laminating can be achieved; moreover, the printed protective layer has good light transmittance and has little effect on the color and photometric properties of the coloring material.

Description

Technical Field

[0001] The invention belongs to the technical field of soft label printing, and in particular relates to a protective resin carbon ribbon for outdoor printing products and a preparation method thereof. Background Art

[0002] Outdoor printing products have to face various complex environments, so they have high requirements for weather resistance and chemical resistance. Usually, the substrates selected for outdoor products are resins with good weather resistance and chemical resistance, such as acrylic acid. For different application scenarios, the surface is usually treated differently, such as printing the required pattern on the surface to serve as a warning. However, it is generally difficult for the colored part to have good chemical resistance and weather resistance. For example, the colored part is prone to cracking and falling off or being covered by dirt such as dust if it is exposed to sunlight for a long time. Therefore, a protective layer is often covered on the outside of the adhesive layer to meet the needs of various environments. The general practice is to protect the coloring layer by laminating or spraying a protective layer. The operation is more complicated or the solvent will evaporate during use, which has a great impact on the color and photometric properties of the coloring material.

[0003] Therefore, a protective resin carbon ribbon for outdoor printing products and a preparation method thereof are proposed to solve the deficiencies in the prior art. Summary of the invention

[0004] In order to solve the above technical problems, the present invention provides a protective resin carbon ribbon for outdoor printing products. After printing the adhesive layer, the protective layer is printed on the outermost layer by thermal transfer, so that the same protective effect as spraying or laminating can be achieved. Moreover, the printed protective layer has good light transmittance and has little effect on the color and photometric properties of the coloring material. It is an economical, green and reliable printing method.

[0005] The technical solution of the present invention to solve the above technical problems is as follows: the protective resin carbon ribbon for outdoor printing products includes an adhesive layer, a protective layer, a release layer, a substrate and a back coating layer which are sequentially laminated from top to bottom; the protective layer is coated with the following raw materials in parts by weight: 100-200 parts of a solvent, 30-50 parts of a main resin, 3-8 parts of a second thermoplastic acrylic resin, 8-12 parts of a thermosetting acrylic resin, 3-8 parts of an isocyanate curing agent, 0.1-1 parts of a light stabilizer and 0.1-1 parts of a light absorber.

[0006] Beneficial effect: After printing the adhesive layer, the protective layer is printed on the outermost layer by thermal transfer, so as to achieve the same protective effect as spraying or laminating. Moreover, the printed protective layer has good light transmittance and has little effect on the color and photometric properties of the coloring material. It is an economical, green and reliable printing method.

[0007] Principle description: Thermosetting fluorocarbon resin is the main resin, and a certain amount of thermosetting acrylic resin and thermoplastic acrylic resin are added to enhance the adhesion to the transferred body. The thermosetting resin is cross-linked to form a film under the action of a curing agent. At the same time, the CF bond energy is large (460kJ / mol) and the stability is high. The spirally arranged fluorine atoms play a good "shielding protection" role on the carbon main chain, which can effectively prevent the exposure of carbon atoms and carbon chains. In addition, the main chain of acrylic resin is a carbon-carbon bond, which is very stable to light, heat, acid and alkali. The protective layer has excellent weather resistance, corrosion resistance, chemical resistance and light transmittance. During the film formation process, the fluoroalkyl group with extremely low surface energy will preferentially migrate to the surface, making the coating surface have excellent hydrophobic, oleophobic, and anti-fouling properties. In this way, a protective layer can be directly attached to the transferred body by thermal transfer printing. Compared with spraying or laminating, the operation is relatively simple, the printing process is green and environmentally friendly, and economical and reliable.

[0008] Based on the above technical solution, the present invention can also be improved as follows.

[0009] Furthermore, the matrix is ​​any one of polypropylene, polyethylene naphthalate, polyethylene terephthalate, polyethylene, polyvinyl alcohol, and polymethyl methacrylate.

[0010] Beneficial effect: Using the above film as a substrate can better ensure that the back coating layer and the release layer can be effectively coated on the surface of the substrate.

[0011] Furthermore, the solvent is one or a combination of butanone and xylene.

[0012] Beneficial effect: It can ensure that the components in the adhesive layer, protective layer, release layer and back coating layer are fully dispersed and mixed.

[0013] Furthermore, the main resin is a thermosetting fluorocarbon resin.

[0014] Beneficial effects: It can effectively prevent the exposure of carbon atoms and carbon chains, making the fluorinated acrylate have excellent weather resistance, corrosion resistance, chemical resistance, etc.

[0015] Furthermore, the thermosetting fluorocarbon resin is at least one of a copolymer of chlorotrifluoroethylene and tetrafluoroethylene containing a hydroxyl functional group and a copolymer of vinyl ether and vinyl ester containing a hydroxyl functional group, and the thermosetting fluorocarbon resin has a molecular weight of 3000-50000, a glass transition temperature Tg=40-120°C, and a hydroxyl value of 10-100 mgKOH / g.

[0016] Beneficial effects: It can effectively prevent the exposure of carbon atoms and carbon chains, making fluorinated acrylates have excellent weather resistance, corrosion resistance, chemical resistance, etc. During the film-forming process, the fluoroalkyl groups with extremely low surface energy will preferentially migrate to the surface, making the coating surface have excellent hydrophobicity, oleophobicity, and stain resistance.

[0017] Furthermore, the thickness of the substrate is 4-25 μm, the thickness of the adhesive layer is 0.2-2.0 μm, the thickness of the release layer is 0.2-2.0 μm, the thickness of the protective layer is 0.5-20.0 μm, and the thickness of the back coating layer is 0.5-1.2 μm.

[0018] Beneficial effect: The thickness of the thermal transfer ribbon can be guaranteed within this thickness range, and at the same time, the adhesion and wear resistance to the substrate are good.

[0019] Furthermore, the molecular weight of the first thermoplastic acrylic resin is 5000-300000, and the glass transition temperature Tg=40-120°C.

[0020] Beneficial effect: Improve the adhesion between the protective layer and the adhesive layer.

[0021] Furthermore, the back coating layer is one or a combination of polyurethane-modified silicone resin and acrylic-modified silicone resin.

[0022] Beneficial effects: heat transfer and anti-friction, protection of print head and printing substrate.

[0023] To achieve the second objective of the present invention, a method for preparing a protective resin ribbon for outdoor printing products is provided, comprising the following steps:

[0024] S1: Prepare solution:

[0025] Prepare adhesive solution, stripping solution and back coating solution respectively for standby use; add 30-50 parts of main resin, 3-8 parts of second thermoplastic acrylic resin, 8-12 parts of thermosetting acrylic resin and 3-8 parts of isocyanate curing agent to 100-200 parts of organic solvent to dissolve, then add 0.1-1 parts of light stabilizer and 0.1-1 parts of light absorber and stir and mix to prepare protective solution for standby use;

[0026] S2: stunning;

[0027] Providing a substrate, and applying corona on both sides of the substrate;

[0028] S3: coating;

[0029] The back coating liquid prepared in step S1 is coated on the side of the substrate subjected to corona treatment in step S2, and then dried to form a back coating layer for standby use;

[0030] Then, the demoulding liquid prepared in step S1 is coated on the side of the substrate away from the back coating layer in step S2, and then dried to form a demoulding layer for standby use;

[0031] Then, the protective liquid prepared in step S1 is coated on the side of the release layer in step S2 away from the substrate, and then dried to form a protective layer for standby use;

[0032] Finally, the adhesive solution prepared in step S1 is coated on the side of the protective layer in step S2 away from the release layer, so as to obtain a protective resin carbon tape for outdoor printing products.

[0033] Further, in step S3, a ceramic anilox roller with a line of 200 to 250 is used to coat the adhesive liquid, and the coating speed is 60-100 m / min; the drying temperature is 60-100°C; a ceramic anilox roller with a line of 200 to 250 is used to coat the protective liquid, and the coating speed is 60-100 m / min; the drying temperature is 20-100°C; a ceramic anilox roller with a line of 200 to 250 is used to coat the release liquid, and the coating speed is 60-100 m / min; the drying temperature is 20-100°C; a ceramic anilox roller with a line of 200 to 250 is used to coat the back coating liquid, and the coating speed is 60-100 m / min; the drying temperature is 20-100°C.

[0034] Beneficial effects: The carbon ribbon prepared by the above preparation method can achieve the same protection effect as spraying or laminating by simply printing the transfer layer containing the protective layer on the outermost layer of the outdoor printing product by thermal transfer; the printed product has excellent weather resistance, chemical resistance and stain resistance. Moreover, the printed transfer layer has good light transmittance and has little effect on the color and photometric properties of the coloring material. It is an economical, green and reliable printing method. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] Figure 1 Schematic diagram of the layer structure of the carbon ribbon of the present invention; DETAILED DESCRIPTION

[0036] The principles and features of the present invention are described below in conjunction with the accompanying drawings. The examples given are only used to explain the present invention and are not used to limit the scope of the present invention.

[0037] 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. PET and PEN are preferred.

[0038] Furthermore, the thickness of the substrate is 4-25 μm, preferably 4-10 μm.

[0039] Release layer

[0040] The components of the release layer may be waxes, silicone waxes, silicone resins, silicone-modified resins, fluororesins, fluoro-modified resins, polyvinyl alcohol, acrylic resins, heat-crosslinkable epoxy-amino resins, polyesters, etc. In addition, the release layer may be composed of one resin or two or more resins.

[0041] Furthermore, the release layer may also contain inorganic particles, such as aluminum particles, zirconium oxide particles, calcium carbonate particles, silicon dioxide particles, titanium oxide, zinc oxide particles and other metal oxide particles.

[0042] The thickness of the release layer is 0.2-2 μm, preferably 0.3-1.0 μm.

[0043] The release layer can be formed by dispersing or dissolving the above materials in water or a suitable solvent, coating the materials on the surface of the substrate by gravure coating or slit coating, and heating and drying the materials to form the release layer.

[0044] Protective layer

[0045] The main resin used in the protective layer of the present invention is a thermosetting fluorocarbon resin. The CF bond energy in the fluorocarbon resin is large (460 kJ / mol), and the stability is high. The helically arranged fluorine atoms play a good "shielding protection" role on the carbon main chain, which can effectively prevent the exposure of carbon atoms and carbon chains, so that the fluorinated acrylate has excellent weather resistance, corrosion resistance, chemical resistance, etc. In the film formation process, the fluoroalkyl group with extremely low surface energy will preferentially migrate to the surface, so that the coating surface has excellent hydrophobic, oleophobic, and anti-fouling properties.

[0046] Furthermore, in order to improve the affinity with the acrylic adhesive layer and the transfer object, the protective layer also contains a portion of thermosetting acrylic resin.

[0047] Furthermore, in order to improve the adhesion between the protective layer and the adhesive layer, the protective layer also contains a portion of thermoplastic acrylic resin.

[0048] Furthermore, in order to achieve cross-linking between the thermosetting acrylic resins and the thermosetting fluorocarbon resins themselves or between the two, a portion of isocyanate curing agent exists in the protective layer.

[0049] 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 main chain of the resin.

[0050] 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, butyl methacrylate, and hydroxyl-containing functional monomers such as hydroxyethyl (propylene) acrylate and hydroxyethyl (propylene) methacrylate as raw materials under the action of a molecular chain regulator.

[0051] Furthermore, the thermoplastic resin used in the present invention is mainly an acrylic resin obtained by polymerization of acrylic acid. To ensure the viscosity and solubility of the thermoplastic acrylic resin, the acrylic resin may be an acrylic resin obtained by copolymerization of methyl methacrylate and other methacrylic acid monomers.

[0052] Furthermore, the isocyanate curing agent used in the present invention is a polyisocyanate compound having two or more isocyanate groups, such as isophorone diisocyanate, toluene diisocyanate and diphenylmethane diisocyanate and the like compounds and oligomers formed therefrom.

[0053] Furthermore, the molecular weight of the thermosetting fluorocarbon resin in the present invention is Mn=3000-50000, preferably 4000-22000, the hydroxyl value is 10-100 mgKOH / g, preferably 20-80 mgKOH / g, and the total mass ratio of the protective layer is 40-95 wt%, preferably 60-80 wt%.

[0054] Furthermore, the molecular weight of the thermosetting acrylic resin in the present invention is Mn=2000-60000, preferably 12000-32000, the hydroxyl value is 10-100 mgKOH / g, preferably 20-70 mgKOH / g, and the total mass ratio of the protective layer is 5-40wt%, preferably 10-20wt%.

[0055] Furthermore, the amount of curing agent added is determined according to the hydroxyl value of the thermosetting resin and the isocyanate content of the curing agent, and preferably the molar ratio of hydroxyl to isocyanate is n(-OH) / n(-NCO)=0.9-1.1.

[0056] Furthermore, the molecular weight of the thermoplastic acrylic resin in the present invention is Mn=5000-300000, preferably 30000-150000, the glass transition temperature Tg=40-120°C, preferably 60-110°C, and the total mass ratio of the protective layer is 1-30wt%, preferably 3-10wt%.

[0057] Furthermore, a small amount of additives such as light stabilizers, light absorbers and lubricants may be added to the resin to further enhance its aging resistance and provide better demoulding and wear resistance.

[0058] Furthermore, the light stabilizer includes one or more combinations of salicylates, benzophenones, benzotriazoles, substituted acrylonitriles, and triazine ultraviolet absorbers, and the mass of the light stabilizer accounts for 0.1-2wt% of the mass of the protective layer resin.

[0059] Furthermore, the lubricant may be organic particles, such as acrylic particles such as non-crosslinked acrylic particles, crosslinked acrylic particles, polyamide particles, fluorine particles, polyethylene wax, silicone particles, etc. It may also be inorganic particles, such as aluminum particles, zirconium oxide particles, calcium carbonate particles, silicon dioxide particles, titanium oxide, zinc oxide particles, etc. Metal oxide particles, etc. It may also be both, and the lubricant accounts for 0.1-2wt% of the mass of the protective layer resin.

[0060] Furthermore, the thickness of the protective layer is 0.5-20 μm, preferably 1-10 μm.

[0061] The protective layer is prepared by dissolving a certain amount of resin in a solvent such as butanone or toluene, adding a certain amount of auxiliary agent to obtain a protective layer coating, coating the protective layer on the surface of the substrate by gravure coating or slit coating, and heating and drying to solidify the coating.

[0062] Next layer:

[0063] In order to make the protective layer adhere better to the transferred body, an adhesive layer must be provided on the side of the protective layer away from the substrate.

[0064] Furthermore, in order to provide good adhesion, the resin used in the next layer is mainly a thermoplastic acrylic resin prepared by polymerization of acrylic acid, methacrylic acid and their derivatives (such as esters, nitriles, amides).

[0065] Furthermore, in order to make the adhesive layer also have good solvent resistance and aging resistance, the preferred resin is a thermoplastic acrylic resin prepared by free radical polymerization with methyl methacrylate monomer as the main component.

[0066] Furthermore, the molecular weight of the thermoplastic acrylic resin in the present invention is Mn=5000-300000, preferably 25000-150000, and the glass transition temperature Tg=40-120°C, preferably 60-110°C.

[0067] Furthermore, the thickness of the adhesive layer is 0.2-2 μm, preferably 0.3-0.9 μm.

[0068] The preparation method of the adhesive layer is to dissolve a certain amount of resin in a solvent such as butanone or toluene, and then coat it on the surface of the protective layer by gravure coating or slit coating and dry it.

[0069] Back coating

[0070] A layer provided to prevent adverse effects such as stickiness or wrinkles caused by heating from the back side of the substrate (the side of the substrate where the protective layer is not provided) during thermal transfer.

[0071] Furthermore, the resin of the back layer is not particularly limited, and may be acrylic resin, cellulose resin, fluorocarbon resin, silicone resin, polycarbonate resin, polyvinyl acetal resin, polyvinyl alcohol resin, or the like.

[0072] Furthermore, the back layer is preferably a resin that can be cross-linked and cured with a cross-linking agent, such as polyisocyanate.

[0073] Furthermore, the back surface layer contains a lubricant, particles, etc. In the back surface layer containing a lubricant, particles, etc., the back surface layer has good sliding properties.

[0074] Furthermore, the lubricant can be silicone oil, polyethylene wax, paraffin, higher fatty acid esters, higher fatty amides, higher fatty alcohols, organopolysiloxanes, anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, fluorine-based surfactants, organic carboxylic acids and their derivatives, and metal soaps, etc.

[0075] Furthermore, the particles may be organic particles, inorganic particles, etc. Organic particles: fluorine particles, acrylic particles, nylon particles, PTFE (polytetrafluoroethylene) particles, styrene particles, nylon particles, etc. Inorganic particles: silica, oxidic acid, talc, etc.

[0076] Furthermore, the thickness of the back coating is 0.2-1.2 μm.

[0077] The back coating layer is prepared by dissolving the polymer material in water or a corresponding solvent to prepare a coating, and then coating the coating on the side of the substrate surface away from the protective layer by gravure coating or slit coating and drying the coating.

[0078] Finally, it should be noted that when preparing the protective layer, coloring layer and back coating of the present invention, in addition to the above-mentioned main materials, a small amount of leveling agent, defoaming agent and other auxiliary agents should be added according to needs.

[0079] As a method for transferring the transfer layer to the transfer body by the protective resin carbon ribbon for outdoor printing products described above, known methods such as hot stamping (foil pressing) based on thermal engraving, full-surface or strip transfer using a heat roller, and a thermal printer (sometimes also called a thermal transfer printer) using a thermal head (thermal print head) can be used.

[0080] Beneficial effects: By simply printing the transfer layer containing the protective layer on the outermost layer of the outdoor printed product through thermal transfer, the same protective effect as spraying or laminating can be achieved; the printed product has excellent weather resistance, chemical resistance and stain resistance. Moreover, the printed transfer layer has good light transmittance and has little effect on the color and photometric properties of the coloring material. It is an economical, green and reliable printing method.

[0081] Embodiment 1:

[0082] The present embodiment provides a protective resin carbon ribbon for outdoor printing products, comprising a back coating layer, a substrate, a release layer, an ink layer and an adhesive layer which are sequentially laminated from top to bottom.

[0083] The adhesive layer is formed by coating the following raw materials in parts by weight: 45 parts of 2-butanone, 45 parts of toluene, and 8 parts of a first thermoplastic acrylic resin (Tg is 105° C., molecular weight is 35,000);

[0084] The protective layer is coated with the following raw materials in parts by weight: 100 parts of 2-butanone, 100 parts of toluene, 35 parts of thermosetting fluorocarbon resin (hydroxyl value is 23 mgKOH·g-1), 4 parts of a second thermoplastic acrylic resin (Tg is 105°C, molecular weight is 100000), 10 parts of a thermosetting acrylic resin (hydroxyl value is 23 mgKOH·g-1), 4 parts of an isocyanate curing agent (-NCO content is 19wt%), 1 part of a leveling agent, 1 part of a defoaming agent, 0.5 parts of a light stabilizer, and 0.5 parts of a light absorber;

[0085] The demoulding layer is coated with the following raw materials in parts by weight: 45 parts of 2-butanone, 45 parts of toluene, 7 parts of silicone resin, 1 part of polystyrene, 1.5 parts of polyester resin; and 0.5 parts of polyethylene wax.

[0086] The back coating layer is formed by coating the following raw materials in parts by weight: 45 parts of 2-butanone, 45 parts of toluene, 5 parts of polyurethane-modified silicone resin, and 5 parts of acrylic acid-modified silicone resin.

[0087] Embodiment 2:

[0088] The difference between this embodiment and embodiment 1 is that:

[0089] The protective layer is coated with the following raw materials in parts by weight: 100 parts of 2-butanone, 100 parts of toluene, 35 parts of thermosetting fluorocarbon resin (hydroxyl value is 55 mgKOH·g-1), 4 parts of a second thermoplastic acrylic resin (Tg is 105°C, molecular weight is 100,000), 10 parts of a thermosetting acrylic resin (hydroxyl value is 23 mgKOH·g-1), 8.5 parts of an isocyanate curing agent (-NCO content is 19wt%), 1 part of a leveling agent, 1 part of a defoaming agent, 0.5 parts of a light stabilizer, and 0.5 parts of a light absorber.

[0090] The adhesive layer is formed by coating the following raw materials in parts by weight: 45 parts of 2-butanone, 45 parts of toluene, and 10 parts of a first thermoplastic acrylic resin (Tg is 105° C., molecular weight is 100,000);

[0091] Example 3

[0092] The difference between this embodiment and embodiment 2 is that:

[0093] The adhesive layer is formed by coating the following raw materials in parts by weight: 45 parts of 2-butanone, 45 parts of toluene, and 10 parts of a first thermoplastic acrylic resin (Tg is 85° C., molecular weight is 65,000);

[0094] Example 4

[0095] The difference between this embodiment and embodiment 2 is that:

[0096] The adhesive layer is formed by coating the following raw materials in parts by weight: 45 parts of 2-butanone, 45 parts of toluene, and 10 parts of a first thermoplastic acrylic resin (Tg is 105° C., molecular weight is 35,000);

[0097] Embodiment 5:

[0098] The difference between this embodiment and embodiment 1 is that:

[0099] The protective layer is coated with the following raw materials in parts by weight: 100 parts of 2-butanone, 100 parts of toluene, 35 parts of thermosetting fluorocarbon resin (hydroxyl value is 72 mgKOH·g-1), 4 parts of a second thermoplastic acrylic resin (Tg is 105°C, molecular weight is 100000), 10 parts of a thermosetting acrylic resin (hydroxyl value is 23 mgKOH·g-1), 11 parts of an isocyanate curing agent (-NCO content is 19wt%), 0.5 parts of a light stabilizer, and 0.5 parts of a light absorber.

[0100] Embodiment 6:

[0101] The difference between this embodiment and embodiment 1 is that:

[0102] The protective layer is coated with the following raw materials in parts by weight: 100 parts of 2-butanone, 10 parts of toluene, 35 parts of thermosetting fluorocarbon resin (hydroxyl value is 55 mgKOH·g-1), 4 parts of a second thermoplastic acrylic resin (Tg is 105°C, molecular weight is 100,000), 10 parts of a thermosetting acrylic resin (hydroxyl value is 66 mgKOH·g-1), 10 parts of an isocyanate curing agent (-NCO content is 19wt%), 0.5 parts of a light stabilizer, and 0.5 parts of a light absorber.

[0103] Embodiment 7:

[0104] The difference between this embodiment and embodiment 1 is that:

[0105] The protective layer is coated with the following raw materials in parts by weight: 100 parts of 2-butanone, 100 parts of toluene, 30 parts of thermosetting fluorocarbon resin (hydroxyl value is 55 mgKOH·g-1), 4 parts of a second thermoplastic acrylic resin (Tg is 105°C, molecular weight is 100,000), 15 parts of a thermosetting acrylic resin (hydroxyl value is 23 mgKOH·g-1), 8 parts of an isocyanate curing agent (-NCO content is 19wt%), 0.5 parts of a light stabilizer, and 0.5 parts of a light absorber.

[0106] Embodiment 8:

[0107] The difference between this embodiment and embodiment 1 is that:

[0108] The protective layer is coated with the following raw materials in parts by weight: 100 parts of 2-butanone, 100 parts of toluene, 40 parts of thermosetting fluorocarbon resin (hydroxyl value is 55 mgKOH·g-1), 4 parts of a second thermoplastic acrylic resin (Tg is 105°C, molecular weight is 100000), 7.5 parts of a thermosetting acrylic resin (hydroxyl value is 23 mgKOH·g-1), 9.5 parts of an isocyanate curing agent (-NCO content is 19wt%), 0.5 parts of a light stabilizer, and 0.5 parts of a light absorber.

[0109] Finally, it should be noted that when preparing the protective layer, coloring layer and back coating of the present invention, in addition to the above-mentioned main materials, a small amount of leveling agent, defoaming agent and other auxiliary agents should be added according to needs.

[0110] Comparative Example 1:

[0111] The same release layer, adhesive layer and back coating formulation, coating thickness, coating method and printing method as those in Example 2 are used, but the resin in the protective layer is replaced with 70 parts of the thermosetting fluorocarbon resin used in Example 2 and 17 parts of the curing agent used in Example 2.

[0112] Comparative Example 2:

[0113] The same release layer, adhesive layer and back coating formulation, coating thickness, coating method and printing method as those in Example 2 are used, but the resin in the protective layer is replaced with 20 parts of the thermosetting acrylic resin used in Example 2 and 2 parts of the curing agent used in Example 2.

[0114] Comparative Example 3:

[0115] The same release layer, adhesive layer and back coating formulations, coating thickness, coating method and printing method as those in Example 2 are used, but the resin in the protective layer is replaced by the thermoplastic acrylic resin used in Example 2.

[0116] Performance testing of printed samples of Examples 1-8 and Comparative Examples 1-3.

[0117] Evaluate the printing effect of the carbon ribbon by checking whether there is any phenomenon such as falling off, sticking to the carbon ribbon, or poor cutting edge during printing.

[0118] The solvent resistance performance was tested for ethanol and gasoline resistance in accordance with the national standard "GB-T 23989-2009 Determination of Solvent Resistance of Coatings".

[0119] The stain resistance test is carried out in accordance with the national standard "GB-T 9780-2013 Test method for stain resistance of architectural coatings".

[0120] The adhesion test is carried out in accordance with the national standard "GB / T 9286-2021 Scratch Test for Paints and Varnishes".

[0121] The weather resistance of the samples was evaluated by the following methods:

[0122] Use a xenon lamp aging test chamber for 1800 hours to observe whether the surface has wrinkles, bubbles, cracks, etc.

[0123] Use a xenon lamp aging test chamber for 1800 hours to measure the color difference before and after accelerated aging.

[0124] Test results:

[0125]

[0126]

[0127]

[0128] In summary, based on the above printing test results, comparing Examples 1-8 with Comparative Examples 1-3, adding thermosetting fluorocarbon resin, thermosetting acrylic resin and thermoplastic acrylic resin into the protective layer can enhance the adhesion to the transferred body.

[0129] In the description of this specification, the description with reference to the terms "one embodiment", "some embodiments", "example", "specific example", or "some examples" etc. means that the specific features, structures, materials or characteristics described in conjunction 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, 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, without contradiction.

[0130] The above are only preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

Claims

1. A protective resin ribbon for outdoor printing products, characterized in that: It includes an adhesive layer, a protective layer, a release layer, a substrate and a back coating layer which are sequentially laminated from top to bottom; The protective layer is formed by mixing the following raw materials in parts by weight and then coating: 100-200 parts of solvent, 30-50 parts of main resin, 3-8 parts of thermoplastic acrylic resin, 8-12 parts of thermosetting acrylic resin, 3-8 parts of isocyanate curing agent, 0.1-1 parts of light stabilizer and 0.1-1 parts of light absorber; The main resin is a thermosetting fluorocarbon resin; The thermosetting fluorocarbon resin is at least one of a copolymer of chlorotrifluoroethylene and tetrafluoroethylene containing a hydroxyl functional group and a copolymer of vinyl ether and vinyl ester containing a hydroxyl functional group, the molecular weight of the thermosetting fluorocarbon resin is 3000-50000, the glass transition temperature Tg=40-120°C, and the hydroxyl value is 10-100 mgKOH / g; The molecular weight of the thermoplastic acrylic resin is 5000-300000, and the glass transition temperature Tg is 40-120°C; The method for preparing the protective resin ribbon for outdoor printing products comprises the following steps: S1: Prepare solution: Prepare adhesive solution, stripping solution and back coating solution respectively for standby use; add 30-50 parts of main resin, 3-8 parts of second thermoplastic acrylic resin, 8-12 parts of thermosetting acrylic resin and 3-8 parts of isocyanate curing agent to 100-200 parts of organic solvent to dissolve, then add 0.1-1 parts of light stabilizer and 0.1-1 parts of light absorber and stir and mix to prepare protective solution for standby use; S2: stunning; Providing a substrate, and applying corona on both sides of the substrate; S3: coating; The back coating liquid prepared in step S1 is coated on the side of the substrate subjected to corona treatment in step S2, and then dried to form a back coating layer for standby use; Then, the demoulding liquid prepared in step S1 is coated on the side of the substrate away from the back coating layer in step S2, and then dried to form a demoulding layer for standby use; Then, the protective liquid prepared in step S1 is coated on the side of the release layer in step S2 away from the substrate, and then dried to form a protective layer for standby use; Finally, the adhesive solution prepared in step S1 is coated on the side of the protective layer in step S2 away from the release layer, so as to obtain a protective resin carbon tape for outdoor printing products.

2. The protective resin ribbon for outdoor printing products according to claim 1, characterized in that: The matrix is ​​any one of polypropylene, polyethylene naphthalate, polyethylene terephthalate, polyethylene, polyvinyl alcohol, and polymethyl methacrylate.

3. The protective resin ribbon for outdoor printing products according to claim 1, characterized in that: The solvent is one or a combination of butanone and xylene.

4. The protective resin ribbon for outdoor printing products according to claim 1, characterized in that: The thickness of the substrate is 4-25 μm, the thickness of the adhesive layer is 0.2-2.0 μm, the thickness of the demoulding layer is 0.2-2.0 μm, the thickness of the protective layer is 0.5-20.0 μm, and the thickness of the back coating layer is 0.5-1.2 μm.

5. The protective resin ribbon for outdoor printing products according to claim 1, characterized in that: The back coating layer is one or a combination of polyurethane modified silicone resin and acrylic modified silicone resin.

6. The protective resin ribbon for outdoor printing products according to claim 1, characterized in that: In step S3, a ceramic anilox roller with 200 to 250 lines is used to apply the adhesive liquid, and the coating speed is 60-100 m / min; the drying temperature is 60-100°C; a ceramic anilox roller with 200 to 250 lines is used to apply the protective liquid, and the coating speed is 60-100 m / min; the drying temperature is 20-100°C; a ceramic anilox roller with 200 to 250 lines is used to apply the release liquid, and the coating speed is 60-100 m / min; the drying temperature is 20-100°C; a ceramic anilox roller with 200 to 250 lines is used to apply the back coating liquid, and the coating speed is 60-100 m / min; the drying temperature is 20-100°C.

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