CN115923367A - Protective resin carbon ribbon for outdoor printing products and preparation method thereof - Google Patents

Abstract

The invention relates to a protective resin thermal transfer ribbon for outdoor printing products and a preparation method thereof, belonging to the technical field of soft label printing. The protective resin carbon ribbon for the outdoor printing product comprises an adhesion layer, a protective layer, a demolding layer, a base body and a back coating which are sequentially attached from top to bottom; the protective layer is formed by mixing and coating the following raw materials in parts by weight: 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 type curing agent, 0.1-1 part of light stabilizer and 0.1-1 part of light absorber. The invention also discloses a preparation method of the protective resin carbon tape for outdoor printing products. Has the advantages that: the protective layer is printed on the outermost layer only by a thermal transfer printing mode after the adhesive layer is printed, and the same protective effects of spraying or film coating and the like can be realized; moreover, the protective layer after printing has good light transmission and has small influence on the chromaticity and luminosity performance of the coloring material.

Description

Protective resin carbon ribbon for outdoor printing products and preparation method thereof

Technical Field

The invention belongs to the technical field of soft label printing, and particularly relates to a protective resin thermal transfer ribbon for an outdoor printing product and a preparation method thereof.

Background

Outdoor printing products have high requirements on weather resistance, chemical resistance and the like because of the need to face various complicated environments. The base material selected for outdoor products is resin with better weather resistance and chemical resistance, such as acrylic acid and the like. For different application scenes, the surface is usually processed differently, for example, the surface is printed with a desired pattern to play a role of warning. However, the colored part is generally difficult to have good chemical resistance and weather resistance, for example, the colored part is easy to crack and fall off or is covered by dirt such as dust due to long-term sunlight irradiation. Therefore, a protective layer is often coated on the outside of the adhesive layer to meet the needs of various environments. Generally, a coloring layer is protected by a film coating or protective layer spraying mode, the operation is complex or a solvent is volatilized when the coloring layer is used, and the influence on the chromaticity and the luminosity performance of a coloring material is large.

Therefore, a protective resin carbon tape for outdoor printing products and a preparation method thereof are provided to solve the defects in the prior art.

Disclosure of Invention

The invention provides a protective resin carbon ribbon for outdoor printing products to solve the technical problems, and the protective resin carbon ribbon can realize the same protective effect in the modes of spraying or film coating and the like only by printing a protective layer on the outermost layer in a thermal transfer printing mode after printing an adhesive layer; moreover, the protective layer after printing has good light transmission and small influence on the chromaticity and luminosity performance of the coloring material, and is an economic, green and reliable printing method.

The technical scheme for solving the technical problems is as follows: the protective resin carbon ribbon for the outdoor printing product comprises an adhesive layer, a protective layer, a demolding layer, a base body and a back coating which are sequentially attached from top to bottom; the protective layer is formed by coating the following raw materials in parts by weight: 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 type curing agent, 0.1-1 part of light stabilizer and 0.1-1 part of light absorber.

Has the advantages that: after the adhesion layer is printed, the protective layer is printed on the outermost layer in a thermal transfer printing mode, and the same protection effect in spraying or film coating modes can be achieved; moreover, the protective layer after printing has good light transmission and small influence on the chromaticity and luminosity performance of the coloring material, and is an economic, green and reliable printing method.

Description of the principle: the thermosetting fluorocarbon resin is used as main resin, and a certain amount of thermosetting acrylic resin and thermoplastic acrylic resin are added to improve the adhesion to a transferred body. The characteristic that thermosetting resin is crosslinked into a film under the action of a curing agent is utilized. Meanwhile, the C-F bond energy is large (460 kJ/mol), the stability is high, and fluorine atoms arranged in a spiral shape play a good role in shielding and protecting a carbon main chain and can effectively prevent the exposure of carbon atoms and carbon chains. And, the main chain of the acrylic resin is a carbon-carbon bond, which is very stable to light, heat, acid and alkali. So that the protective layer has excellent weather resistance, corrosion resistance, chemical medium resistance, light transmission and the like. During the film forming process, the fluoroalkyl with extremely low surface energy can preferentially migrate to the surface, so that the surface of the coating film has excellent characteristics of hydrophobicity, oleophobicity, stain resistance and the like. In this way, the protective layer can be directly attached to the transferred body by thermal transfer printing. Compared with a spraying or film covering mode, the operation is simpler, and the printing process is green, environment-friendly, economical and reliable.

On the basis of the technical scheme, the invention can be further improved as follows.

Further, the matrix is any one of polypropylene, polyethylene naphthalate, polyethylene terephthalate, polyethylene, polyvinyl alcohol and polymethyl methacrylate.

Has the advantages that: the film is adopted as the base material, so that the back coating layer and the demolding layer can be better ensured to be effectively coated on the surface of the base material.

Further, the solvent is one or the combination of two of butanone and toluene.

Has the beneficial effects that: can ensure the components in the adhesive layer, the protective layer, the demoulding layer and the back coating to be fully dispersed and mixed.

Further, the main resin is thermosetting fluorocarbon resin.

Has the beneficial effects that: can effectively prevent the exposure of carbon atoms and carbon chains, so that the fluorinated acrylate has excellent weather resistance, corrosion resistance, chemical medium resistance and the like.

Further, the thermosetting fluorocarbon resin is at least one of copolymer of chlorotrifluoroethylene containing hydroxyl functional groups and tetrafluoroethylene and copolymer of vinyl ether and vinyl ester containing hydroxyl functional groups, the molecular weight of the thermosetting fluorocarbon resin is 3000-50000, the glass transition temperature Tg =40-120 ℃, and the hydroxyl value is 10-100mgKOH/g.

Has the beneficial effects that: can effectively prevent the exposure of carbon atoms and carbon chains, so that the fluorinated acrylate has excellent weather resistance, corrosion resistance, chemical medium resistance and the like. During the film forming process, the fluoroalkyl with extremely low surface energy can preferentially migrate to the surface, so that the surface of the coating film has excellent hydrophobicity, oleophobicity and stain resistance.

Further, the thickness of the substrate is 4-25 μm, the thickness of the adhesion 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.

Has the beneficial effects that: the thickness of the thermal transfer ribbon can be ensured within the thickness range, and the adhesive force and the wear resistance to the base material are good.

Further, the first thermoplastic acrylic resin has a molecular weight of 5000 to 300000 and a glass transition temperature Tg =40 to 120 ℃.

Has the beneficial effects that: improve the adhesion between the protective layer and the adhesion layer.

Further, the back coating is one or two of polyurethane modified organic silicon resin and acrylic acid modified organic silicon resin.

Has the beneficial effects that: heat transfer and abrasion prevention, and protection of the printing head and the printing substrate.

The invention also provides a preparation method of the protective resin carbon ribbon for outdoor printing products, which comprises the following steps:

s1: preparing a liquid:

respectively preparing a bonding solution, a film removing solution and a back coating solution for later use; adding 30-50 parts of main body resin, 3-8 parts of second thermoplastic acrylic resin, 8-12 parts of thermosetting acrylic resin and 3-8 parts of isocyanate type curing agent into 100-200 parts of organic solvent for dissolving, then adding 0.1-1 part of light stabilizer and 0.1-1 part of light absorbent, stirring and mixing to prepare a protection solution for later use;

s2: corona is formed;

providing a substrate, and applying corona on two sides of the substrate;

s3: coating;

coating the back coating liquid prepared in the step S1 on one corona-coated surface of the substrate in the step S2, and then drying to form a back coating for later use;

then coating the demolding liquid prepared in the step S1 on one surface, far away from the back coating, of the substrate in the step S2, and then drying to form a demolding layer for later use;

coating the protective solution prepared in the step S1 on one surface, away from the base, of the demolding layer in the step S2, and then drying to form a protective layer for later use;

and finally, coating the bonding liquid prepared in the step S1 on one surface, far away from the demolding layer, of the protective layer in the step S2 to obtain the protective resin carbon ribbon for the outdoor printing product.

Further, in step S3, coating the adhesive liquid by using a ceramic anilox roller with 200-250 lines, wherein the coating speed is 60-100m/min; the drying temperature is 60-100 ℃; coating the protective solution by using a ceramic anilox roller with 200-250 lines, wherein the coating speed is 60-100m/min; the drying temperature is 20-100 ℃; coating the demolding liquid by adopting a ceramic anilox roller with 200-250 lines, wherein the coating speed is 60-100m/min; the drying temperature is 20-100 ℃; coating back coating liquid by adopting a ceramic anilox roller with 200-250 lines, wherein the coating speed is 60-100m/min; the drying temperature is 20-100 ℃.

Has the advantages that: the carbon ribbon prepared by the preparation method can realize the same protection effect in the modes of spraying or film coating and the like only by printing the transfer printing layer containing the protective layer on the outermost layer of the outdoor printing product in a thermal transfer printing mode; the printed product has excellent weather resistance, chemical resistance and stain resistance. Moreover, the transfer printing layer after printing has good light transmission, has little influence on the chromaticity and luminosity performance of coloring materials, and is an economic, green and reliable printing method.

Drawings

FIG. 1 is a schematic view of a layer structure of a carbon ribbon according to the present invention;

Detailed Description

The principles and features of this invention are described below in conjunction with the following drawings, which are set forth by way of illustration only and are not intended to limit the scope of the invention.

Among them, 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), and the like. Among them, PET and PEN are preferable.

Further, the thickness of the substrate is 4 to 25 μm, and 4 to 10 μm is preferable.

Release layer

The release layer may be composed of a wax, a silicone resin, a silicone-modified resin, a fluororesin, a fluorine-modified resin, polyvinyl alcohol, an acrylic resin, a thermally crosslinkable epoxy-amino resin, a polyester, or the like. The release layer may be composed of 1 kind of resin, or may be composed of 2 or more kinds of resins.

Further, the releasing layer may contain inorganic particles such as metal oxide particles of aluminum particles, zirconium oxide particles, calcium carbonate particles, silica particles, titanium oxide, zinc oxide particles, and the like.

The thickness of the release layer is 0.2 to 2 μm, preferably 0.3 to 1.0. Mu.m.

The release layer may be formed by: the above materials are dispersed or dissolved in water or a suitable solvent, coated on the surface of a substrate by gravure coating or slit coating, and heated and dried, whereby a release layer can be formed.

Protective layer

The main resin used by the protective layer is thermosetting fluorocarbon resin, the C-F bond energy in the fluorocarbon resin is large (460 kJ/mol), the stability is high, and the fluorine atoms arranged in a spiral shape play a good role in shielding and protecting a carbon main chain, so that the exposure of the carbon atoms and the carbon chains can be effectively prevented, and the fluorinated acrylate has excellent weather resistance, corrosion resistance, chemical medium resistance and the like. During the film forming process, fluoroalkyl with extremely low surface energy can preferentially migrate to the surface, so that the surface of a coating film has excellent characteristics of hydrophobicity, oleophobicity, stain resistance and the like.

Further, in order to improve the affinity with the acrylic adhesive layer and the transferred object, the protective layer further contains a part of a thermosetting acrylic resin.

Furthermore, in order to improve the adhesion between the protective layer and the adhesive layer, the protective layer further comprises a part of thermoplastic acrylic resin.

Furthermore, in order to realize mutual crosslinking between the thermosetting acrylic resins and the thermosetting fluorocarbon resins or between the thermosetting acrylic resins and the thermosetting fluorocarbon resins, a part of isocyanate type curing agent exists in the protective layer.

Further, the thermosetting fluorocarbon resin used in the present invention refers to chlorotrifluoroethylene/tetrafluoroethylene and vinyl ether/vinyl ester copolymers containing hydroxyl functional groups in the resin backbone.

Further, the thermosetting acrylic resin used in the present invention is an acrylic resin prepared by radical polymerization of a hard monomer such as styrene or methyl methacrylate, a soft monomer such as ethyl acrylate, butyl acrylate or butyl methacrylate, and a functional monomer containing a hydroxyl group such as hydroxyethyl (propyl) acrylate or hydroxyethyl (propyl) methacrylate as raw materials under the action of a molecular chain regulator.

Further, the thermoplastic resin used in the present invention is mainly an acrylic resin obtained by polymerizing acrylic acid. In order to ensure the viscosity and solubility of the thermoplastic acrylic resin, the acrylic resin may be prepared by copolymerizing methyl methacrylate and other methacrylic monomers.

Further, the isocyanate curing agent used in the present invention is a polyisocyanate compound having 2 or more isocyanate groups, such as compounds of isophorone diisocyanate, toluene diisocyanate and diphenylmethane diisocyanate, and oligomers thereof.

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

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

Further, the amount of the curing agent to be added is determined in accordance with the hydroxyl value of the thermosetting resin and the isocyanate content of the curing agent, and it is preferable that the molar ratio of the hydroxyl group to the isocyanate is n (-OH)/n (-NCO) =0.9 to 1.1.

Further, the molecular weight Mn =5000 to 300000, preferably 30000 to 150000, and the glass transition temperature Tg =40 to 120 ℃, preferably 60 to 110 ℃, of the thermoplastic acrylic resin in the present invention accounts for 1 to 30wt%, preferably 3 to 10wt%, of the total mass ratio of the protective layer.

Furthermore, a small amount of additives such as light stabilizer, light absorbent, lubricant and the like can be added into the resin, so that the aging resistance and the demolding and wear resistance of the resin are further improved.

Further, the light stabilizer comprises one or more of salicylic acid esters, benzophenones, benzotriazoles, substituted acrylonitrile and triazine ultraviolet absorbers, and the mass of the light stabilizer accounts for 0.1-2wt% of the mass of the protective layer resin.

Further, the lubricant may be organic particles such as acrylic particles such as non-crosslinked acrylic particles and crosslinked acrylic particles, polyamide particles, fluorine particles, polyethylene wax, silicone particles, and the like. Inorganic particles such as aluminum particles, zirconium oxide particles, calcium carbonate particles, silica particles, titanium oxide, zinc oxide particles, and the like metal oxide particles may be used. Or both, the lubricant accounts for 0.1-2wt% of the protective layer resin.

Further, the thickness of the protective layer is 0.5 to 20 μm, preferably 1 to 10 μm

The preparation method of the protective layer comprises the steps of dissolving a certain amount of resin in solvents such as butanone and toluene, then adding a certain amount of auxiliary agent to obtain a protective layer coating, then coating the protective layer coating on the surface of a base material in a gravure coating or slit coating mode, and heating, drying and curing.

And (3) a following layer:

in order to make the protective layer adhere to the transferred object better, an adhesion layer is required to be arranged on the side of the protective layer far away from the base material.

Further, in order to provide good adhesion, the resin for the adhesive layer is mainly a thermoplastic acrylic resin prepared by polymerizing acrylic acid, methacrylic acid and derivatives thereof (such as esters, nitriles, amides).

Further, in order to make the adhesive layer have good solvent resistance and aging resistance, it is preferable that the resin is a thermoplastic acrylic resin prepared by radical polymerization mainly using a methyl methacrylate monomer.

Further, the molecular weight Mn =5000 to 300000, preferably 25000 to 150000, and the glass transition temperature Tg =40 to 120 ℃, preferably 60 to 110 ℃ of the thermoplastic acrylic resin in the present invention.

Further, the thickness of the adhesive layer is 0.2 to 2 μm, preferably 0.3 to 0.9. Mu.m.

The preparation method of the adhesive layer comprises the steps of dissolving a certain amount of resin in a solvent such as butanone and toluene, coating the resin on the surface of the protective layer by a gravure coating or slot coating mode, and drying.

Back coating

A layer provided for preventing adverse effects such as stickiness or generation of wrinkles due to heating from the back surface side of the base material (the side of the base material on which the protective layer is not provided) during thermal transfer.

Further, the resin of the back layer is not particularly limited, and may be an acrylic resin, a cellulose-based resin, a fluorocarbon-based resin, a silicone-based resin, a polycarbonate-based resin, a polyvinyl alcohol acetal-based resin, a polyvinyl alcohol-based resin, or the like.

Further, the back surface layer is preferably a resin which can be cured by crosslinking with a crosslinking agent. The crosslinking agent may be a polyisocyanate or the like.

Further, the back layer contains a lubricant, particles, and the like. In the back layer containing a lubricant, particles, or the like, the back layer has good sliding properties.

Further, the lubricant may be silicone oil, polyethylene wax, paraffin wax, higher fatty acid ester, higher fatty acid amide, higher aliphatic alcohol, organopolysiloxane, anionic surfactant, cationic surfactant, amphoteric surfactant, nonionic surfactant, fluorine-based surfactant, organic carboxylic acid and its derivative, metal soap, or the like.

Further, the particles may be organic particles, inorganic particles, or the like. Organic particles: fluorine particles, acrylic particles, nylon particles, PTFE (polytetrafluoroethylene) particles, styrene particles, nylon particles, and the like. Inorganic particles: silica, oxidizability, talc, and the like.

Further, the thickness of the back coating is 0.2-1.2 μm

The preparation method of the back coating comprises the following steps: dissolving the polymer material into water or a corresponding solvent to prepare a coating, coating the coating on the side of the surface of the substrate far away from the protective layer by a gravure coating or slot coating mode, and drying.

Finally, when the protective layer, the coloring layer and the back coating paint are prepared, a small amount of assistants such as a leveling agent and a defoaming agent are added according to requirements in addition to the main materials.

As a method for transferring the transfer layer to the transfer object by the protective resin thermal transfer ribbon for outdoor printing products, known methods such as hot stamping (foil stamping) by thermal imprint, transfer of the entire surface or a band by a heat roller, and a thermal printer (also referred to as a thermal transfer printer) by a thermal head (thermal print head) can be used.

Has the beneficial effects that: the transfer printing layer containing the protective layer is printed on the outermost layer of the outdoor printed product only through a thermal transfer printing mode, and the same protection effects of spraying or film coating and the like can be achieved; the printed product has excellent weather resistance, chemical resistance and stain resistance. Moreover, the transfer printing layer after printing has good light transmission, has little influence on the chromaticity and luminosity performance of the coloring material, and is an economic, green and reliable printing method.

Example 1:

the embodiment provides a protection resin carbon ribbon for outdoor printing product, including back coating, base member, release layer, printing ink layer and the layer of gluing that top-down laminated in proper order set up.

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 first thermoplastic acrylic resin (Tg is 105 ℃, and the molecular weight is 35000);

the protective layer is formed by coating the following raw materials in parts by weight: 100 parts of 2-butanone, 100 parts of toluene, 35 parts of thermosetting fluorocarbon resin (the hydroxyl value is 23 mgKOH. G < -1 >), 4 parts of second thermoplastic acrylic resin (the Tg is 105 ℃, and the molecular weight is 100000), 10 parts of thermosetting acrylic resin (the hydroxyl value is 23 mgKOH. G < -1 >), 4 parts of isocyanate type curing agent (-NCO content is 19 wt%), leveling agent parts, defoaming agent parts, 0.5 part of light stabilizer and 0.5 part of light absorber;

the demolding layer is formed by coating the following raw materials in parts by weight: 45 parts of 2-butanone, 45 parts of toluene, 7 parts of organic silicon resin, 1 part of polystyrene and 1.5 parts of polyester resin; 0.5 part of polyethylene wax;

the back coating 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 organic silicon resin and 5 parts of acrylic acid modified organic silicon resin.

Example 2:

this example is different from example 1 in that;

the protective layer is formed by coating the following raw materials in parts by weight: 100 parts of 2-butanone, 100 parts of toluene, 35 parts of thermosetting fluorocarbon resin (the hydroxyl value is 55mgKOH g < -1 >), 4 parts of second thermoplastic acrylic resin (the Tg is 105 ℃, and the molecular weight is 100000), 10 parts of thermosetting acrylic resin (the hydroxyl value is 23mgKOH g < -1 >), 8.5 parts of isocyanate type curing agent (-NCO content is 19 wt%), leveling agent parts, defoaming agent parts, 0.5 part of light stabilizer and 0.5 part of light absorber.

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 first thermoplastic acrylic resin (Tg is 105 ℃, and the molecular weight is 100000);

example 3

The present embodiment is different from embodiment 2;

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 first thermoplastic acrylic resin (the Tg is 85 ℃, and the molecular weight is 65000);

example 4

The present example differs from example 2 in that;

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 first thermoplastic acrylic resin (Tg is 105 ℃, and the molecular weight is 35000);

example 5:

this example is different from example 1 in that;

the protective layer is formed by coating 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 72mgKOH g < -1 >), 4 parts of second thermoplastic acrylic resin (Tg is 105 ℃, molecular weight is 100000), 10 parts of thermosetting acrylic resin (hydroxyl value is 23mgKOH g < -1 >), 11 parts of isocyanate type curing agent (-NCO content is 19 weight percent), 0.5 part of light stabilizer and 0.5 part of light absorber.

Example 6:

this example is different from example 1 in that;

the protective layer is formed by coating the following raw materials in parts by weight: 100 parts of 2-butanone, 10 parts of toluene, 35 parts of thermosetting fluorocarbon resin (the hydroxyl value is 55mgKOH g < -1 >), 4 parts of second thermoplastic acrylic resin (the Tg is 105 ℃, and the molecular weight is 100000), 10 parts of thermosetting acrylic resin (the hydroxyl value is 66mgKOH g < -1 >), 10 parts of isocyanate type curing agent (-NCO content is 19wt percent), 0.5 part of light stabilizer and 0.5 part of light absorber.

Example 7:

the present embodiment is different from embodiment 1 in that;

the protective layer is formed by coating the following raw materials in parts by weight: 100 parts of 2-butanone, 100 parts of toluene, 30 parts of thermosetting fluorocarbon resin (the hydroxyl value is 55mgKOH g < -1 >), 4 parts of second thermoplastic acrylic resin (the Tg is 105 ℃, and the molecular weight is 100000), 15 parts of thermosetting acrylic resin (the hydroxyl value is 23mgKOH g < -1 >), 8 parts of isocyanate type curing agent (-the NCO content is 19 weight percent), 0.5 part of light stabilizer and 0.5 part of light absorber.

Example 8:

this example is different from example 1 in that;

the protective layer is formed by coating the following raw materials in parts by weight: 100 parts of 2-butanone, 100 parts of toluene, 40 parts of thermosetting fluorocarbon resin (the hydroxyl value is 55mgKOH g < -1 >), 4 parts of second thermoplastic acrylic resin (the Tg is 105 ℃, and the molecular weight is 100000), 7.5 parts of thermosetting acrylic resin (the hydroxyl value is 23mgKOH g < -1 >), 9.5 parts of isocyanate type curing agent (-NCO content is 19wt percent), 0.5 part of light stabilizer and 0.5 part of light absorber.

Finally, when the protective layer, the coloring layer and the back coating paint are prepared, a small amount of assistants such as a leveling agent and a defoaming agent are added according to requirements in addition to the main materials.

Comparative example 1:

the same formulations of release layer, adhesive layer and back coat, coating thickness, coating method and printing method as in example 2 were used, but the resin in the protective layer was changed to 70 parts of the thermosetting fluorocarbon resin used in example 2 and 17 parts of the curing agent used in example 2.

Comparative example 2:

the same formulations of release layer, adhesive layer and back coat, coating thickness, coating method and printing method as in example 2 were used, but the resin in the protective layer was changed to 20 parts of the thermosetting acrylic resin used in example 2 and 2 parts of the curing agent used in example 2.

Comparative example 3:

the same formulations of release layer, adhesive layer and back coat, coating thickness, coating method, and printing method as in example 2 were used, but the resin in the protective layer was changed to the thermoplastic acrylic resin used in example 2.

Examples 1-8 and comparative examples 1-3 were tested for the performance of the printed samples.

Evaluating the printing effect of the carbon ribbon by judging whether the phenomena of block falling, carbon ribbon adhesion, poor edge cutting performance and the like exist during printing

The solvent resistance is tested for ethanol resistance and gasoline resistance according to the national standard GB-T23989-2009 paint solvent resistance wiping determination method.

The stain resistance test is carried out according to the national standard GB-T9780-2013 test method for stain resistance of architectural coating.

The adhesion test is carried out according to the national standard GB/T9286-2021 painted lacquer and varnish test.

The weather resistance of the sample was evaluated by:

using a xenon lamp aging test box for 1800 hours, and observing whether the surface of the xenon lamp aging test box has the phenomena of wrinkles, bubbles, cracks and the like;

the color difference before and after accelerated aging was measured using a xenon lamp aging test chamber for 1800 hours.

And (3) testing results:

/>

in summary, the above printing test results, examples 1 to 8, compared with comparative examples 1 to 3, show that the addition of the thermosetting fluorocarbon resin, the thermosetting acrylic resin, and the thermoplastic acrylic resin to the protective layer can improve the adhesion to the transferred object.

In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.

The present invention is not limited to the above preferred embodiments, and any modifications, equivalent replacements, improvements, etc. within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. A protective resin carbon ribbon for outdoor printing products is characterized by comprising an adhesion layer, a protective layer, a demolding layer, a base body and a back coating which are sequentially attached from top to bottom;

the protective layer is formed by mixing and coating the following raw materials in parts by weight: 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 type curing agent, 0.1-1 part of light stabilizer and 0.1-1 part of light absorber.

2. The protective resin carbon tape for outdoor printing products according to claim 1, wherein the substrate is any one of polypropylene, polyethylene naphthalate, polyethylene terephthalate, polyethylene, polyvinyl alcohol, and polymethyl methacrylate.

3. The protective resin carbon tape for outdoor printed products according to claim 1, wherein the solvent is one or a combination of two of butanone and di-toluene.

4. The protective resin carbon tape for outdoor printed products of claim 1, wherein the host resin is a thermosetting fluorocarbon resin.

5. The protective resin carbon tape for outdoor printing products according to claim 4, wherein the thermosetting fluorocarbon resin is at least one of a copolymer of chlorotrifluoroethylene and tetrafluoroethylene having a hydroxyl functional group and a copolymer of vinyl ether and vinyl ester having a hydroxyl functional group, and the thermosetting fluorocarbon resin has a molecular weight of 3000 to 50000, a glass transition temperature Tg =40 to 120 ℃, and a hydroxyl value of 10 to 100mgKOH/g.

6. The protective resin carbon tape for outdoor printing products according to claim 1, wherein the thickness of the substrate is 4 to 25 μm, the thickness of the adhesion layer is 0.2 to 2.0 μm, the thickness of the release layer is 0.2 to 2.0 μm, the thickness of the protective adhesion layer is 0.5 to 20.0 μm, and the thickness of the back coating layer is 0.5 to 1.2 μm.

7. A protective resin carbon tape for outdoor printed products according to claim 1, characterized in that the molecular weight of the thermoplastic acrylic resin is 5000-300000 and the glass transition temperature Tg =40-120 ℃.

8. The protective resin carbon tape for outdoor printed products according to claim 1, wherein the back coating layer is one or a combination of two of polyurethane modified silicone resin and acrylic modified silicone resin.

9. A method for preparing a protective resin carbon tape for outdoor printed products according to any one of claims 1 to 8, comprising the steps of:

s1: preparing a liquid:

respectively preparing a bonding solution, a membrane removing solution and a back coating solution for later use; adding 30-50 parts of main body resin, 3-8 parts of second thermoplastic acrylic resin, 8-12 parts of thermosetting acrylic resin and 3-8 parts of isocyanate type curing agent into 100-200 parts of organic solvent for dissolving, then adding 0.1-1 part of light stabilizer and 0.1-1 part of light absorbent, stirring and mixing to prepare a protection solution for later use;

s2: corona is formed;

providing a substrate, and applying corona on two sides of the substrate;

s3: coating;

coating the back coating liquid prepared in the step S1 on one corona-coated surface of the substrate in the step S2, and then drying to form a back coating for later use;

then coating the demolding liquid prepared in the step S1 on one surface, far away from the back coating, of the substrate in the step S2, and then drying to form a demolding layer for later use;

coating the protective solution prepared in the step S1 on one surface, away from the base, of the demolding layer in the step S2, and then drying to form a protective layer for later use;

and finally, coating the bonding liquid prepared in the step S1 on one surface, far away from the demolding layer, of the protective layer in the step S2 to obtain the protective resin carbon ribbon for the outdoor printing product.

10. The method for preparing a protective resin carbon tape for outdoor printing products according to claim 9, wherein in step S3, the adhesive liquid is coated by using a ceramic anilox roller of 200 to 250 lines at a speed of 60 to 100m/min; the drying temperature is 60-100 ℃; coating protective liquid by using a ceramic anilox roller with 200-250 lines, wherein the coating speed is 60-100m/min; the drying temperature is 20-100 ℃; coating demolding liquid with a ceramic anilox roller of 200-250 lines at the coating speed of 60-100m/min; the drying temperature is 20-100 ℃; coating back coating liquid by adopting a linear ceramic anilox roller, wherein the coating speed is 60-100m/min; the drying temperature is 20-100 ℃.

Images