A white resin ribbon and its preparation method

Abstract

This invention discloses a white resin ribbon and its preparation method. The white resin ribbon includes: a substrate layer, which is a flexible transparent plastic film; a front layer disposed on the front side of the substrate layer; and a back coating layer disposed on the back side of the substrate layer. The front layer sequentially includes a base coating layer and two white ink layers, with one white ink layer sandwiched between the base coating layer and the other white ink layer. The middle white ink layer is the first white ink layer, and the other white ink layer is the second white ink layer. The base coating layer is bonded to the front side of the substrate layer. The white resin ribbon provided by this invention has excellent opacity and yellowing resistance, effectively improving the color performance of transfer film printing and significantly increasing the color density of the final image. Furthermore, it combines the function of a transfer ribbon with the white ribbon functionality.

Description

Technical Field

[0001] This invention belongs to the field of thermal sublimation printing technology, and particularly relates to a white resin ribbon and its preparation method. Background Technology

[0002] Using a retransfer film as an intermediate medium allows for the unrestricted formation of printed images on the substrate. This method requires first applying thermal sublimation printing to the retransfer film to create the image. However, in practice, significant light loss occurs because light cannot be directly reflected after passing through the coating, resulting in lower color density in both actual testing and visual perception. Furthermore, the thicker substrate required for the retransfer film necessitates greater heat during transfer, leading to dye sublimation loss, significant color differences, increased production costs, and damage to the retransfer film substrate. Additionally, printing text on non-white substrates necessitates the addition of white and bonding carbon ribbons. Currently available thermal sublimation retransfer films generally suffer from poor applicability and low color density. Moreover, the inventors discovered in experiments that commercially available white carbon ribbons, when used in conjunction with thermal sublimation retransfer films, typically exhibit poor adhesion, narrow applicability, insufficient yellowing resistance, and poor opacity. Summary of the Invention

[0003] In order to solve the above-mentioned technical problems, the purpose of this invention is to provide a white resin ribbon with strong adhesion, good resistance to yellowing, and good hiding power.

[0004] To achieve the above objectives, the technical solution of the present invention is as follows: a white resin ribbon, comprising:

[0005] The substrate layer is a flexible, transparent plastic film;

[0006] A front layer disposed on the front side of the substrate layer; and

[0007] A back coating layer disposed on the back side of the substrate layer;

[0008] The front layer comprises a base coating and two white ink layers, wherein one of the white ink layers is sandwiched between the base coating and the other white ink layer, the middle white ink layer is the first white ink layer, and the other white ink layer is the second white ink layer, and the base coating is bonded to the front of the substrate layer.

[0009] In the above technical solution, the substrate layer is one of polypropylene film, polyethylene naphthalate film, polyethylene terephthalate film, polyethylene film, polyvinyl alcohol film, and polymethyl methacrylate film, and / or the thickness of the substrate layer is 3-12 μm; the coating thickness of the bottom coating layer is 0.8-5 μm; the coating thickness of the back coating layer is 0.4-1.2 μm; and the coating thickness of the white ink layer is 1-5 μm.

[0010] The raw materials for the primer layer in the above technical solution include primer resin one, primer resin two, and primer resin three; wherein, primer resin one is acrylic resin, vinyl chloride-vinyl acetate copolymer, vinyl chloride-acrylic copolymer, or EVA resin; primer resin two is one or two of polyester resin, polyurethane resin, and chloroether resin; and primer resin three is a crystalline polyester resin with a softening point of -70℃ to 10℃, a melting point below 110℃, and a melt viscosity not higher than 1000 dPa.s.

[0011] In the above technical solution, the mass ratio of primer resin material one to primer resin material two is 1:1-3; and / or the amount of primer resin material three added is 5-20 phr of the total weight of primer resin material one.

[0012] The raw materials for the back coating layer described in the above technical solution include a back coating resin, an isocyanate compound, inorganic fillers, and a release agent. The back coating resin is a polyester resin, polyacrylate resin, polyvinyl acetate resin, styrene-acrylate resin, polyurethane resin, polyethylene resin, polypropylene resin, and other polyolefin resins, polystyrene resins, polyvinyl chloride resins, polyether resins, polyamide resins, polyimide resins, polyamide-imide resins, polycarbonate resins, polyacrylamide resins, polyvinyl chloride resins, polyvinyl butyral resins, polyvinyl acetal resins, and polyvinyl alcohol acetal resins. The product comprises one or more of the following: lipids and their silicone-modified derivatives; the isocyanate compound is one or more of the following: toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, benzyl toluidine diisocyanate, and terephthalic diisocyanate; the inorganic filler is one or more of the following: talc, kaolin, calcium carbonate, aluminum hydroxide, silicon dioxide, graphite, and boron nitride; the release agent is one or more of the following: phosphate ester compound, metal soap, silicone oil, and surfactant.

[0013] In the above technical solution, the amount of inorganic filler added is 1-5% of the total weight of the back coating resin; the amount of release agent added is 1-10% of the total weight of the back coating resin.

[0014] The white ink layer described in the above technical solution comprises white ink resin, pigment, dispersant, fluorescent whitening agent, antioxidant, and light stabilizer; the white ink resin is one or more of vinyl chloride-vinyl acetate copolymer, chloroether resin, polyester resin, and thermoplastic acrylic resin; the pigment is rutile titanium dioxide or anatase titanium dioxide; the dispersant is a cationic wetting and dispersing agent, anionic wetting and dispersing agent, nonionic wetting and dispersing agent, amphoteric wetting and dispersing agent, or polymeric superdispersant; and the fluorescent whitening agent is stilbene. The fluorescent whitening agent is one or more of the following: coumarin-type fluorescent whitening agent, pyrazoline-type fluorescent whitening agent, benzo[a]oxo[b]nitrile-type fluorescent whitening agent, and benzoimide-type fluorescent whitening agent; the antioxidant is one or more of the following: hindered phenolic antioxidants, phosphite antioxidants, thiolated antioxidants, complex antioxidants, and hindered amine antioxidants; the light stabilizer is one or more of the following: salicylate light stabilizers, benzophenone light stabilizers, benzo[a]triazole light stabilizers, substituted acrylonitrile light stabilizers, and triazine ultraviolet absorbers.

[0015] In the above technical solution, the mass ratio of white ink resin to pigment is 1:0.5-4; the amount of dispersant is 0.2-50% of the total weight of pigment; the amount of fluorescent whitening agent is 1-10% of the total weight of pigment; the amount of antioxidant is 0.3-0.5% of the total weight of white ink resin; and the amount of light stabilizer is 0.1-2% of the total weight of white ink resin.

[0016] In the above technical solution, the white ink resin material corresponding to the first white ink layer includes polyester resin and thermoplastic acrylic resin, and the mass ratio of the two is 4-1:2; the white ink resin corresponding to the second white ink layer includes polyester resin and vinyl chloride resin, and the mass ratio of the two is 4-1:2.

[0017] The second objective of this invention is to provide a method for preparing a white resin ribbon with strong adhesion, good resistance to yellowing, and good hiding power.

[0018] To achieve the above objectives, the technical solution of the present invention is as follows: a method for preparing white resin carbon ribbon as described above, characterized in that:

[0019] Step 1: Prepare materials:

[0020] Back coating liquid: Dissolve the raw materials of the back coating in an organic solvent, mix well to obtain the back coating liquid, and set aside for later use;

[0021] Primer coating: Dissolve the raw materials of the primer coating in an organic solvent, mix well and obtain the primer coating for later use;

[0022] White ink solution: Dissolve the raw material of the white ink layer in an organic solvent, mix well to obtain white ink solution, and set aside;

[0023] Step 2: Surface treatment of the substrate layer:

[0024] Take the substrate layer and perform an easy-to-adhere pretreatment on its surface;

[0025] Step 3: Coating:

[0026] The back coating liquid is applied to the back side of the substrate layer after step 2, and then dried to form a back coating layer;

[0027] Apply a primer coating to the front side of the substrate layer and then dry it to form the primer coating.

[0028] A white ink solution is applied to the side of the base layer that is away from the substrate layer, and then dried to form a first white ink layer;

[0029] Apply another layer of white ink to the side of the first white ink layer that is away from the base layer, and then dry it to form a second white ink layer.

[0030] Compared with the prior art, the beneficial effects of the embodiments of the present invention are as follows: The white resin ribbon provided by the present invention has very good opacity and yellowing resistance, which can effectively improve the color performance of transfer film printing, and at the same time significantly improve the color density of the final image. In addition, the function of the bonding ribbon is combined with the white ribbon, that is, the ribbon provided by the present invention can also significantly improve the substrate adaptability of the transfer film, and due to its good edge cutting properties, the white ribbon provided by the present invention can also be used to print labels, and has excellent yellowing resistance and alcohol abrasion resistance. Attached Figure Description

[0031] Figure 1 This is a cross-sectional view of the white resin ribbon described in an embodiment of the present invention.

[0032] In the diagram: 1 - Second white ink layer, 2 - First white ink layer, 3 - Base coating layer, 4 - Substrate layer, 5 - Back coating layer. Detailed Implementation

[0033] The principles and features of the present invention are described below. The examples given are only for explaining the present invention and are not intended to limit the scope of the present invention.

[0034] This invention discloses a white resin ribbon, comprising:

[0035] The substrate layer is a flexible, transparent plastic film;

[0036] A front layer disposed on the front side of the substrate layer; and

[0037] A back coating layer disposed on the back side of the substrate layer;

[0038] The front layer comprises a base coating and two white ink layers, wherein one of the white ink layers is sandwiched between the base coating and the other white ink layer, the middle white ink layer is the first white ink layer, and the other white ink layer is the second white ink layer, and the base coating is bonded to the front of the substrate layer.

[0039] The substrate layer described in the above technical solution is one of polypropylene film, polyethylene naphthalate film, polyethylene terephthalate film, polyethylene film, polyvinyl alcohol film, and polymethyl methacrylate film, preferably polyethylene terephthalate film or polyethylene naphthalate film (or a mixture of the two).

[0040] The thickness of the substrate layer is 3-12 μm (preferably 4-6 μm); the coating thickness of the base layer is 0.8-5 μm (preferably 0.8-2 μm); the coating thickness of the back layer is 0.4-1.2 μm (preferably 0.4-0.6 μm); and the coating thickness of the white ink layer is 1-5 μm (preferably 1-1.5 μm).

[0041] The raw materials for the primer layer in the above technical solution include primer resin one, primer resin two, and primer resin three; wherein, primer resin one is acrylic resin, vinyl chloride-vinyl acetate copolymer, vinyl chloride-acrylic copolymer, or EVA resin; primer resin two is one or two of polyester resin, polyurethane resin, and chloroether resin; and primer resin three is a crystalline polyester resin with a softening point of -70℃ to 10℃, a melting point below 110℃, and a melt viscosity not higher than 1000 dPa.s.

[0042] In this embodiment, the main function of the base coating is to provide a certain release force to the front layer when printing to the surface of the thermal sublimation transfer film, so as to ensure that the front layer can be easily peeled off from the substrate layer under high-speed printing, and at the same time, to provide adhesion between the entire transfer film and the target substrate when transferring to the target substrate.

[0043] Preferably, the first primer resin is an acrylic resin with a Tg value of 70-110℃ and a number-average molecular weight of 30,000-200,000. The purpose of adding the second primer resin is to improve the adhesion between the primer layer and the target substrate, as well as the interlayer adhesion with the white ink layer. Preferably, the second primer resin can be a chloroprene resin with a softening point temperature of 40-80℃. The purpose of adding the third primer resin is to enhance the fluidity of the coating resin when the re-transfer film is transferred to the surface of the target substrate (especially paper substrate), allowing the primer layer to penetrate into the pores of the substrate surface. Since both acrylic resin and chloroprene resin are relatively brittle and have poor curl resistance, to ensure the primer layer has good toughness, it is further preferred that a certain amount of polyurethane resin (TPU) be added to the second primer resin. More preferably, the polyurethane resin has a Tg value of -20℃ to 40℃, and the amount added is 0.02-0.05% of the total weight of the primer raw materials.

[0044] In the above technical solution, the mass ratio of primer resin material one to primer resin material two is 1:1-3 (too much primer resin material two will affect the release properties of the primer layer, and too little primer resin material will affect the high-speed printing effect of the front layer); the amount of primer resin material three added is 5-20 phr of the total weight of primer resin material one (preferably 10-20 phr).

[0045] The preparation method of the base coating is to dissolve a certain amount of resin in solvents such as methyl ethyl ketone, ethyl acetate, and toluene to obtain a base coating material, and then apply it to the surface of the substrate by gravure coating or slot coating and dry it. The drying temperature is 60-120℃ and the drying time is 0.5-2h.

[0046] The specific preparation method of the primer coating is as follows: Primer resin one, primer resin two, and primer resin three are mixed in proportion and added to an appropriate amount of organic solvent (butanone, ethyl acetate, or toluene). After being fully dissolved, the mixture is stirred evenly to obtain the primer coating. The coating method is as follows: The primer coating is applied to the surface of the substrate layer by gravure coating or slot coating and then dried. The drying temperature is 60-120℃, and the drying time is 0.5-2 hours.

[0047] The back coating layer mentioned in the above technical solution (the function of the back coating layer is to prevent adverse effects such as stickiness or wrinkles caused by heating of the thermal heating head during printing) includes back coating resin, isocyanate compound (the purpose of adding isocyanate compound is to improve the heat resistance of the back coating layer during printing), inorganic filler and release agent (the purpose of adding inorganic filler and release agent is to maintain the excellent sliding properties of the ribbon during high-speed printing). The back coating resin can be selected from existing known thermoplastic resins, such as polyester resins, polyacrylate resins, polyvinyl acetate resins, styrene acrylate resins, polyurethane resins, polyethylene resins, polypropylene resins, polyolefin resins, polystyrene resins, polyvinyl chloride resins, polyether resins, polyamide resins, polyimide resins, polyamide-imide resins, polycarbonate resins, polyacrylamide resins, polyvinyl chloride resins, polyvinyl butyral resins, etc. The resin comprises one or more of ethylene acetal resin and polyvinyl alcohol acetal resin and their silicone-modified derivatives (preferably, the back coating resin may be polyvinyl alcohol butyral resin); the isocyanate compound comprises one or more of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, bitoluidine diisocyanate and terephthalic diisocyanate (preferably aromatic isocyanate compounds of the class 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, bitoluidine diisocyanate and terephthalic diisocyanate); the inorganic filler comprises one or more of talc, kaolin, calcium carbonate, aluminum hydroxide, silicon dioxide, graphite and boron nitride; the release agent comprises one or more of phosphate ester compounds, metal soaps, silicone oil and surfactants.

[0048] The amount of inorganic filler added in the above technical solution is 1-5% (preferably 3-5%) of the total weight of the back coating resin; the amount of release agent added is 1-10% (preferably 3-5%) of the total weight of the back coating resin.

[0049] The preparation method of the back coating is as follows: First, the back coating resin is dissolved in an organic solvent (the type of organic solvent is not particularly limited, as long as the back coating resin can dissolve in the organic solvent and the viscosity at 25°C is 100-500 mPa·s; specifically, the organic solvent can be one or a mixture of acetone, 2-butanone, cyclohexanone, isophorone, tetrahydrofuran, ethyl acetate, butyl acetate, propyl acetate, toluene, xylene, and N,N-dimethylformamide, preferably 2-butanone and toluene are miscible, and the volume ratio of 2-butanone to toluene can be between 8 and 2:1). Then, an isocyanate compound, inorganic filler, and release agent are added and mixed evenly. The back coating is applied by gravure coating or slot coating to the surface of the other side of the substrate layer and then dried. The drying temperature is 60-120°C and the drying time is 60-120 seconds.

[0050] The white ink layer described in the above technical solution comprises white ink resin, pigment, dispersant, fluorescent whitening agent, antioxidant, and light stabilizer (the purpose of adding antioxidants and light stabilizers is to reduce yellowing of the product during transfer and use); the white ink resin is one or more of vinyl chloride-vinyl acetate copolymer, chloroether resin, polyester resin, and thermoplastic acrylic resin; the pigment is titanium dioxide, specifically rutile titanium dioxide or anatase titanium dioxide [preferably rutile titanium dioxide with higher refractive index and better stability]. The titanium dioxide powder has a refractive index of 2.71 (the higher the refractive index, the better the hiding power). The particle size D50 of the titanium dioxide at the factory should not exceed 0.5μm. After dispersion and grinding, the proportion of titanium dioxide particles with a particle size distribution of 0.2-0.4μm should not be less than 80% (the hiding power is best when the particle size of titanium dioxide is half the wavelength of visible light, which is 380nm-780nm). To ensure hiding power, theoretically, the content of titanium dioxide should be as high as possible, but the adhesion of the coating must also be ensured. Therefore, the ratio of white ink resin to pigment is 1: 0.5-4, preferably 1:1-2); the dispersant (added to reduce the time and energy required to complete the dispersion process during pigment grinding) is a cationic wetting and dispersing agent, anionic wetting and dispersing agent, nonionic wetting and dispersing agent, amphoteric wetting and dispersing agent, or a polymeric superdispersant (preferably a polymeric superdispersant); the fluorescent whitening agent (used to improve the whiteness of the white ink layer, its whitening principle is to convert ultraviolet light into blue, blue-violet, or red visible light, producing an optical whitening effect) is diphenylene oxide. The fluorescent whitening agent is one or more of the following: ethylene-type fluorescent whitening agent, coumarin-type fluorescent whitening agent, pyrazoline-type fluorescent whitening agent, benzo[a]oxo[b]nitrogen-type fluorescent whitening agent, and benzoimide-type fluorescent whitening agent; the antioxidant is one or more of the following: hindered phenolic antioxidants, phosphite antioxidants, thiolated antioxidants, complex antioxidants, and hindered amine antioxidants; the light stabilizer is one or more of the following: salicylate light stabilizers, benzophenone light stabilizers, benzo[a]triazole light stabilizers, substituted acrylonitrile light stabilizers, and triazine ultraviolet absorbers.

[0051] In the above technical solution, the mass ratio of white ink resin to pigment is 1:0.5-4; the amount of dispersant is 0.2-50% (preferably 0.5-30%) of the total weight of pigment; the amount of fluorescent whitening agent is 1-10% (preferably 1-5%) of the total weight of pigment; the amount of antioxidant is 0.3-0.5% of the total weight of white ink resin; and the amount of light stabilizer is 0.1-2% of the total weight of white ink resin.

[0052] In the above technical solution, the white ink resin material corresponding to the first white ink layer (the function of the first white ink layer is to provide excellent hiding power and yellowing resistance) includes polyester resin (Tg of 50-80℃, molecular weight preferably 3000-25000, the purpose of which is to ensure the interlayer adhesion of the first white ink layer, the second white ink layer and the base layer) and thermoplastic acrylic resin (Tg of 70-115℃, number average molecular weight of 20000-200000, the purpose of which is to ensure the yellowing resistance of the first white ink layer and also to give the first white ink layer good edge cutting properties), and the mass ratio of the two is 4-1:2; the second white ink layer (the function of the second white ink layer is to provide excellent hiding power and yellowing resistance) includes polyester resin (Tg of 50-80℃, molecular weight preferably 3000-25 ...) includes polyester resin (Tg of 50-80℃, molecular weight preferably 3000-25000, the purpose of which is to ensure the yellowing resistance of the The white ink resins that provide a good white base color and excellent interlayer adhesion with the dye receiving layer of the retransfer film include polyester resin (which serves to ensure interlayer adhesion between the first white ink layer, the second white ink layer, and the base layer, with a Tg of 50-80℃ and a molecular weight preferably of 3000-25000) and vinyl chloride-vinyl acetate copolymer (which serves to ensure good interlayer adhesion with the dye receiving layer, with a Tg of 60-80℃, a VC:VAc ratio of 4-9:1, and a number average molecular weight of 10000-80000), and the mass ratio of the two is 1-4:2 (preferably 4-9:6).

[0053] The reason for designing two white ink layers in this embodiment is that acrylic resin and vinyl chloride resin have poor compatibility. To simultaneously meet the high standards of yellowing resistance, hiding power, and adhesion to the dye acceptor layer, both acrylic resin and vinyl chloride resin must be used. Therefore, considering all factors, it is necessary to separate the two. In addition, for good hiding power, the thickness of the white ink layer must reach 3μm. Therefore, the two layers are designed separately.

[0054] When the compositions of the first white ink layer and the second white ink layer are different, the first white ink layer coating and the second white ink layer coating need to be prepared separately.

[0055] The preparation method of the white ink layer coating is as follows: Dissolve white ink resin in an appropriate amount of organic solvent (butanone, ethyl acetate, or toluene), then add a dispersant. After uniform dispersion, add pigment and grind until the particle size is about 0.2-0.4 μm. After grinding, add fluorescent whitening agent, antioxidant, and light stabilizer, and mix well to obtain the white ink layer coating. The coating method is to apply the first white ink layer coating to the side of the base layer away from the substrate layer by gravure coating or slit coating, and then dry it at a temperature of 60-120℃ for 0.5-2 hours. Then, apply the second white ink layer coating to the side of the first white ink layer away from the base layer in the same way, and then dry it at a temperature of 60-120℃ for 0.5-2 hours.

[0056] The second objective of this invention is to provide a method for preparing a white resin ribbon with strong adhesion, good resistance to yellowing, and good hiding power.

[0057] To achieve the above objectives, the technical solution of the present invention is as follows: a method for preparing white resin carbon ribbon as described above.

[0058] Step 1: Prepare materials:

[0059] Back coating material: Dissolve the raw materials of the back coating material in an organic solvent, mix well and obtain the back coating material for later use;

[0060] Primer coating: Dissolve the raw materials of the primer coating in an organic solvent, mix well and obtain the primer coating for later use;

[0061] White ink layer coating: Dissolve the raw materials of white ink layer in an organic solvent, mix well to obtain white ink layer coating, and set aside;

[0062] Step 2: Surface treatment of the substrate layer:

[0063] Take the substrate layer and perform an easy-to-adhere pretreatment on its surface [the substrate layer can be pretreated before coating, and the treatment methods include corona discharge, plasma treatment, ozone treatment, flame treatment, primer (also known as anchoring coating, adhesion promoter, easy-to-adhere agent) coating treatment, preheating treatment, dust removal treatment, vapor deposition treatment, alkali treatment or antistatic layer application, etc. In this embodiment, corona treatment is selected for the substrate layer];

[0064] Step 3: Coating:

[0065] The back coating material is applied to the back side of the substrate layer after step 2, and then dried to form the back coating.

[0066] Apply a primer coating to the front side of the substrate layer and then dry it to form the primer coating.

[0067] A white ink layer is applied to the side of the base layer that is away from the substrate layer, and then dried to form the first white ink layer;

[0068] Apply another layer of white ink coating on the side of the first white ink layer that is away from the base layer, and then dry it to form a second white ink layer.

[0069] Example 1

[0070] <Substrate Layer>

[0071] The substrate layer uses a 4.5μm PET film.

[0072] <Undercoat>

[0073] 10 parts of acrylic resin (BR-80, Tg: 104℃, Mn: 100000 Mitsubishi);

[0074] 10 parts of chlorinated ether resin (MP-25 BASF);

[0075] One part of crystalline polyester (GM920, Tg: -60℃, Mn: 30000 Toyobo);

[0076] One part of polyurethane resin (TPU-5778, Tg: 31.1 Lubrizol);

[0077] 39.5 parts of 2-butanone and 39.5 parts of toluene; wherein, 2-butanone and 3-toluene are used as organic solvents;

[0078] Gravure coating machine, coating thickness 1μm.

[0079] <First White Ink Layer>

[0080] 15 parts of polyester resin (220, Tg: 53℃, Mn: 3000 Toyobo);

[0081] 10 parts of acrylic resin (BR-83, Tg: 105℃, Mn: 40000 Mitsubishi);

[0082] 25 parts of titanium dioxide (R706 DuPont);

[0083] Dispersant (710S Eucalyptus) 3 parts;

[0084] Antioxidant 1 (BASF 1010) 0.5 parts, Antioxidant 2 (BASF 168) 0.5 parts, wherein Antioxidant 1 and Antioxidant 2 together constitute an antioxidant;

[0085] 0.5 parts of ultraviolet light absorber (Tinuvin 1130 BASF) and 0.5 parts of hindered amine light stabilizer (Tinuvin 123 BASF), wherein the ultraviolet light absorber and the hindered amine light stabilizer are combined to form a light stabilizer;

[0086] 0.3 parts of fluorescent whitening agent (OB-1 Lingrui Chemical);

[0087] 32.6 parts of 2-butanone and 32.6 parts of toluene, wherein 2-butanone and toluene are used as organic solvents;

[0088] Gravure coating machine is used for coating, with a coating thickness of 1.5μm.

[0089] The parentheses following each of the above-mentioned material components contain the corresponding material's brand name, specifications, and manufacturer's abbreviation.

[0090] <Second White Ink Layer>

[0091] 15 parts of chloroacetic acid resin (SOLBIN-CL VC:VAc=86:14, Tg=70℃, Mn=25000 nits);

[0092] 10 parts of polyester resin (226, Tg: 65℃, Mn: 8000 Toyobo);

[0093] 25 parts of titanium dioxide (R706 DuPont);

[0094] Dispersant (710S Eucalyptus) 3 parts;

[0095] Antioxidant 1 (BASF 1010) 0.5 parts, Antioxidant 2 (BASF 168) 0.5 parts, wherein Antioxidant 1 and Antioxidant 2 together constitute an antioxidant;

[0096] 0.5 parts of ultraviolet light absorber (Tinuvin 1130 BASF) and 0.5 parts of hindered amine light stabilizer (Tinuvin 123 BASF), wherein the ultraviolet light absorber and the hindered amine light stabilizer are combined to form a light stabilizer;

[0097] 0.3 parts of fluorescent whitening agent (OB-1 Lingrui Chemical).

[0098] 32.6 parts of 2-butanone and 32.6 parts of toluene, wherein 2-butanone and toluene are used as organic solvents;

[0099] Gravure coating machine is used for coating, with a coating thickness of 1.5μm.

[0100] <Back Coating>

[0101] 10 parts of polyvinyl butyral resin (S-LEC BH-6, Sekisui Chemicals, Japan);

[0102] 3 parts of polyisocyanate curing agent (TMHG-80B, Asahi Kasei, Japan);

[0103] 0.5 parts of silicone oil (KF-965-100cs Shin-Etsu silicone) and 0.6 parts of phosphate ester (MOA-3PK-70 Jiangsu Haian Petrochemical Plant), wherein the silicone oil and phosphate ester are combined as a mold release agent;

[0104] Talc powder (HY-TA05 Haiyang powder) 0.6 parts;

[0105] 42.65 parts of 2-butanone and 42.65 parts of toluene, wherein 2-butanone and toluene are used as organic solvents.

[0106] Gravure coating machine is used for coating, with a coating thickness of 0.4μm.

[0107] Example 2

[0108] <Substrate Layer>

[0109] The substrate layer uses a 4.5μm PET film.

[0110] The first white ink layer, the second white ink layer, and the back coating layer are consistent with those in Example 1.

[0111] <Undercoat>

[0112] 10 parts of acrylic resin (BR-80, Tg: 104℃, Mn: 100000 Mitsubishi);

[0113] 10 parts of chlorinated ether resin (VC-40 BASF);

[0114] One part of crystalline polyester (GA6400, Tg: -20℃, Mn: 30000 Toyobo);

[0115] One part of polyurethane resin (901H, Wanhua Chemical);

[0116] 39.5 parts of 2-butanone and 39.5 parts of toluene, wherein 2-butanone and toluene are used as organic solvents.

[0117] Gravure coating machine, coating thickness 1μm.

[0118] Example 3

[0119] <Substrate Layer>

[0120] The substrate layer uses a 4.5μm PET film.

[0121] The base coat, second white ink layer, and back coat are consistent with those in Example 1.

[0122] <First White Ink Layer>

[0123] Five parts of hydroxyl-modified acrylic resin (SGR-016A, Tg: 50℃, Mn: 80000, Changhao Trading);

[0124] 15 parts of polyester resin (220, Tg: 53℃, Mn: 3000 Toyobo);

[0125] 15 parts of titanium dioxide (R706 DuPont);

[0126] Dispersant (710S Eucalyptus) 3 parts;

[0127] Antioxidant (BASF B900) 0.5 parts;

[0128] 0.5 parts of ultraviolet light absorber (Tinuvin 1130 BASF) and 0.5 parts of hindered amine light stabilizer (Tinuvin 123 BASF), wherein the ultraviolet light absorber and the hindered amine light stabilizer are combined to form a light stabilizer;

[0129] 0.3 parts of fluorescent whitening agent (OB-1 Lingrui Chemical);

[0130] 32.6 parts of 2-butanone and 32.6 parts of toluene, wherein 2-butanone and toluene are used as organic solvents.

[0131] Gravure coating machine is used for coating, with a coating thickness of 1.5μm.

[0132] Example 4

[0133] <Substrate Layer>

[0134] The substrate layer uses a 4.5μm PET film.

[0135] The base coat, the first white ink layer, and the back coat are consistent with those in Example 1.

[0136] <Second White Ink Layer>

[0137] 15 parts of chloroacetic acid resin (H15 / 42, VC:VAc = 86:14, Tg = 70℃, MW = 25000WACKER);

[0138] 10 parts of polyester resin (226, Tg: 65℃, Mn: 8000 Toyobo);

[0139] 25 parts of titanium dioxide (R706 DuPont);

[0140] Dispersant (710S Eucalyptus) 3 parts;

[0141] Antioxidant 1 (BASF 1010) 0.5 parts, Antioxidant 2 (BASF 168) 0.5 parts, wherein Antioxidant 1 and Antioxidant 2 together constitute an antioxidant;

[0142] 0.5 parts of ultraviolet light absorber (Tinuvin 1130 BASF) and 0.5 parts of hindered amine light stabilizer (Tinuvin 123 BASF), wherein the ultraviolet light absorber and the hindered amine light stabilizer are combined to form a light stabilizer;

[0143] 0.3 parts of fluorescent whitening agent (OB-1 Lingrui Chemical);

[0144] 32.6 parts of 2-butanone and 32.6 parts of toluene, wherein 2-butanone and toluene are used as organic solvents.

[0145] Gravure coating machine is used for coating, with a coating thickness of 1.5μm.

[0146] Comparative Example 1

[0147] Same as Example 1, except that: the substrate layer uses a 4.5μm PET film and has no base coating.

[0148] Comparative Example 2

[0149] Same as Example 1, except that: the substrate layer uses a 4.5μm PET film and has no first white ink layer.

[0150] Comparative Example 3

[0151] Same as Example 1, except that: the substrate layer uses a 4.5μm PET film and there is no second white ink layer.

[0152] Comparative Example 4

[0153] <Substrate Layer>

[0154] Same as Example 1, except that:

[0155] <First White Ink Layer>

[0156] 15 parts of polyester resin (220, Tg: 53℃, Mn: 3000 Toyobo);

[0157] 10 parts of acrylic resin (BR-83, Tg: 105℃, Mn: 40000 Mitsubishi);

[0158] 25 parts of titanium dioxide (R706 DuPont);

[0159] Dispersant (710S Eucalyptus) 3 parts;

[0160] 32.6 parts of 2-butanone and 32.6 parts of toluene, wherein 2-butanone and toluene are used as organic solvents.

[0161] Gravure coating machine is used for coating, with a coating thickness of 1.5μm.

[0162] Comparative Example 5

[0163] Same as Example 1, except that: the substrate layer uses a 4.5μm PET film;

[0164] <Undercoat>

[0165] 10 parts of acrylic resin (BR-80, Tg: 104℃, Mn: 100000 Mitsubishi);

[0166] 10 parts of chlorinated ether resin (MP-25 BASF);

[0167] One part of polyurethane resin (TPU-5778, Tg: 31.1℃ Lubrizol);

[0168] 39.5 parts of 2-butanone and 39.5 parts of toluene, wherein 2-butanone and toluene are used as organic solvents.

[0169] Gravure coating machine, coating thickness 1μm.

[0170] Test results and analysis

[0171] Performance testing solution

[0172] Printing tests were conducted using a DTP330 dye-sublimation label printing press. Original ribbons were used, and the printing speed was 6 m / min. The transfer module used a DTP330 expansion module, with a transfer speed of 6 m / min and a temperature of 100°C. The re-pressing temperature was also 100°C. The test and evaluation methods for the following indicators are existing technologies and will not be elaborated upon here.

[0173] 1. Color density test

[0174] The color density test pattern is a 256-grayscale image. The 256th grayscale level color density test was performed using an X-Rite i1-PRO3 colorimeter. The evaluation criteria are as follows:

[0175] *A: OD≥2.4; *B: 2.0≤OD<2.4; *C: OD<2.0.

[0176] 2. Color difference test:

[0177] The color difference test pattern is a 1-256 grayscale image. The color difference before and after printing was tested using an X-Rite i 1-PRO3 colorimeter, with 256 test points (16×16). The evaluation criteria are as follows:

[0178] *A:△E ab ≤2; *B: 2>△E ab ≤4; *C: OD>4.

[0179] 3. Transfer adaptability test:

[0180] The printed image is a 256-color-level image, and the test substrate is a 25µm PET film. The evaluation criteria are as follows:

[0181] *A: Complete transfer; *B: Partial complete transfer; *C: No transfer.

[0182] 4. Adhesion test of the printed material:

[0183] After printing onto the transfer film, the image is transferred to the target substrate using a heat transfer machine. Adhesion is then tested using 3M tape at a 180° angle. The evaluation criteria are as follows:

[0184] *A: Coating retention ≥ 98%; *B: 98% > Coating retention ≥ 90%; *C: Coating retention < 90%.

[0185] 5. Barcode printing test:

[0186] The evaluation criteria for printing CODE-19 barcodes on PVC transparent label paper are as follows:

[0187] *A: Very clear, with no broken lines, trailing or other abnormalities;

[0188] *B: Clear, no broken lines, slight trailing;

[0189] *C: Unclear, with broken lines and trailing edges.

[0190] 6. Text printing test:

[0191] The evaluation criteria for printing 5-point Song typeface Chinese characters on PVC transparent label paper are as follows:

[0192] *A: Very clear, with no broken lines, trailing or other abnormalities;

[0193] *B: Clear, no broken lines, slight trailing;

[0194] *C: Unclear, with broken lines and trailing edges.

[0195] 7. Coverage test:

[0196] White blocks were printed on black PP synthetic paper, and color density was measured using an X-Rite i1-PRO3 colorimeter. The evaluation criteria are as follows:

[0197] *A: OD≤0.1; *B: 0.1<OD≤0.2; *C: OD>0.2.

[0198] 8. Alcohol resistance friction test:

[0199] A white patch was printed on black PP synthetic paper. An alcohol abrasion resistance tester was used, with a 500g weight applied back and forth 100 times. 0.5ml of 75% alcohol was added per 100 abrasions. The OD change before and after abrasion was measured. The evaluation criteria are as follows:

[0200] *A: OD 前 / OD 后 >90%; *B: 90% <OD 前 / OD 后 ≤80%; *C: OD 前 / OD 后 <80%.

[0201] The test results for each embodiment are shown in Table 1:

[0202] Table 1: Test Results

[0203]

[0204]

[0205] The above description is only a preferred embodiment of the present invention and is 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 within the protection scope of the present invention.

Claims

1. A white resin ribbon, characterized in that, include: The substrate layer is a flexible, transparent plastic film; A front layer disposed on the front side of the substrate layer; and A back coating layer disposed on the back side of the substrate layer; The front layer comprises a base coating layer and two white ink layers, wherein one of the white ink layers is sandwiched between the base coating layer and the other white ink layer, the white ink layer in the middle is the first white ink layer, and the other white ink layer is the second white ink layer, and the base coating layer is bonded to the front of the substrate layer. The raw materials for the base coating include base coating resin one, base coating resin two, and base coating resin three; wherein, base coating resin one is acrylic resin, vinyl chloride-vinyl acetate copolymer, vinyl chloride-acrylic copolymer, or EVA resin; base coating resin two is one or two of polyester resin, polyurethane resin, and chloroether resin; and base coating resin three is a crystalline polyester resin with a softening point of -70°C to 10°C, a melting point below 110°C, and a melt viscosity not higher than 1000 dPa.s. The white ink layer includes white ink resin, pigment, dispersant, fluorescent whitening agent, antioxidant and light stabilizer; The white ink resin material is one or more of vinyl chloride-vinyl acetate copolymer, chloroether resin, polyester resin and thermoplastic acrylic resin; The pigment is rutile titanium dioxide or anatase titanium dioxide; the dispersant is a cationic wetting and dispersing agent, anionic wetting and dispersing agent, nonionic wetting and dispersing agent, amphoteric wetting and dispersing agent, or a polymeric superdispersant. The fluorescent whitening agent is one or more of the following: stilbene-type fluorescent whitening agent, coumarin-type fluorescent whitening agent, pyrazoline-type fluorescent whitening agent, benzo[a]oxonitrile-type fluorescent whitening agent, and benzoimide-type fluorescent whitening agent; The antioxidant is one or more of the following: hindered phenolic antioxidants, phosphite antioxidants, thiolated antioxidants, compound antioxidants, and hindered amine antioxidants; the light stabilizer is one or more of the following: salicylate light stabilizers, benzophenone light stabilizers, benzotriazole light stabilizers, substituted acrylonitrile light stabilizers, and triazine ultraviolet absorbers. The white ink resin material corresponding to the first white ink layer includes polyester resin and thermoplastic acrylic resin, and the mass ratio of the two is 4-1:2; The white ink resin corresponding to the second white ink layer includes polyester resin and chloroacetic acid resin, and the mass ratio of the two is 4-1:

2.

2. The white resin ribbon according to claim 1, characterized in that, The substrate layer is one of the following: polypropylene film, polyethylene naphthalate film, polyethylene terephthalate film, polyethylene film, polyvinyl alcohol film, and polymethyl methacrylate film. And / or the thickness of the substrate layer is 3-12 μm; the coating thickness of the base layer is 0.8-5 μm; the coating thickness of the back layer is 0.4-1.2 μm; and the coating thickness of the white ink layer is 1-5 μm.

3. The white resin ribbon according to claim 1, characterized in that, The mass ratio of primer resin material one to primer resin material two is 1:1-3; And / or the amount of the third primer resin added is 5-20 phr of the total weight of the first primer resin.

4. The white resin ribbon according to claim 1, characterized in that, The raw materials for the back coating include a back coating resin, an isocyanate compound, inorganic fillers, and a release agent. The back coating resin is one or more of the following: polyester resin, polyacrylate resin, polyvinyl acetate resin, styrene acrylate resin, polyurethane resin, polyethylene resin, polypropylene resin, polyolefin resin, polystyrene resin, polyvinyl chloride resin, polyether resin, polyamide resin, polyimide resin, polyamide-imide resin, polycarbonate resin, polyacrylamide resin, polyvinyl chloride resin, polyvinyl butyral resin, polyvinyl acetal resin, and polyvinyl alcohol acetal resin, and their silicone-modified products. The isocyanate compound is one or more selected from toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, benzylamine diisocyanate, and terephthalic diisocyanate. The inorganic filler is one or more of the following: talc, kaolin, calcium carbonate, aluminum hydroxide, silicon dioxide, graphite, and boron nitride. The release agent is one or more of the following: phosphate ester compound, metal soap, silicone oil, and surfactant.

5. The white resin ribbon according to claim 4, characterized in that, The amount of inorganic filler added is 1-5% of the total weight of the back coating resin; The amount of the release agent added is 1-10% of the total weight of the back coating resin.

6. The white resin ribbon according to claim 1, characterized in that, The mass ratio of the white ink resin to the pigment is 1:0.5-4; The amount of the dispersant used is 0.2-50% of the total weight of the pigment; The amount of the fluorescent whitening agent used is 1-10% of the total weight of the pigment; The amount of antioxidant used is 0.3-0.5% of the total weight of the white ink resin; The amount of light stabilizer used is 0.1-2% of the total weight of the white ink resin.

7. A method for preparing a white resin ribbon as described in any one of claims 1-6, characterized in that: Step 1: Prepare materials: Back coating liquid: Dissolve the raw materials of the back coating in an organic solvent, mix well to obtain the back coating liquid, and set aside for later use; Primer coating: Dissolve the raw materials of the primer coating in an organic solvent, mix well and obtain the primer coating for later use; White ink solution: Dissolve the raw material of the white ink layer in an organic solvent, mix well to obtain white ink solution, and set aside; Step 2: Surface treatment of the substrate layer: Take the substrate layer and perform an easy-to-adhere pretreatment on its surface; Step 3: Coating: The back coating liquid is applied to the back side of the substrate layer after step 2, and then dried to form a back coating layer; Apply a primer coating to the front side of the substrate layer and then dry it to form the primer coating. White ink is applied to the side of the base layer that is away from the substrate layer, and then dried to form the first white ink layer; Apply another layer of white ink to the side of the first white ink layer that is away from the base layer, and then dry it to form a second white ink layer.

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