High-resistance metal color washing label thermal transfer ribbon, washing label and textile

Abstract

The invention discloses a high-resistance metal color washing label thermal transfer ribbon, a washing label and a textile, the high-resistance metal color washing label thermal transfer ribbon comprises a back coating layer, a base film layer, a stripping layer, a dye layer, an aluminum plating layer and a bonding layer which are sequentially laminated and compounded, and a protective layer is clamped between the stripping layer and the dye layer. And the resin component in the protective layer is thermoplastic resin containing reactive groups. The high-resistance metallic color washing label thermal transfer ribbon provided by the invention has the properties of high temperature resistance, scratch resistance, excellent water resistance, no fading and the like, has a printing effect with metallic luster texture, and has good applicability on different types of washing label base materials. Through the synergistic effect of all the layers, the comprehensive performance of the thermal transfer ribbon is comprehensively improved, it is ensured that printed patterns are always kept clear, complete and attractive under various complex use conditions of the washing label, the requirements of the market for the high-quality washing label thermal transfer ribbon are met, and the overall quality and brand image of textile products are improved.

Description

Technical Field

[0001] The invention belongs to the field of water-washing label carbon tapes, and in particular relates to a high-durability metallic color water-washing label carbon tape, a water-washing label and a textile. Background Art

[0002] As one of the important labels for textiles such as clothing and home textiles, the wash label needs to clearly and durably present key information such as washing instructions and ingredient labeling. However, in actual use, the wash label will frequently come into contact with water, detergents, friction and different temperature environments, which places extremely high requirements on the performance of the carbon ribbon. Traditional wash label carbon ribbons usually use simple structures and conventional materials, such as common ink coatings and ordinary plastic substrates. These carbon ribbons have the following defects: poor performance in high temperature resistance, and the pattern is prone to deformation and fading when dried at high temperature; poor scratch resistance, and daily friction may cause pattern wear; insufficient water resistance, and the information is blurred or even disappears after washing; no metallic luster texture, it is difficult to meet the product diversification and high-quality labeling needs.

[0003] Existing water-washable label ribbons mainly achieve label printing by coating ink or simple thermal transfer coating on ordinary plastic film substrates. For example, some ribbons use polyethylene or polypropylene film as the base film layer, and the ink layer is mainly composed of ordinary pigments and binders. During the preparation process, the ink is first evenly coated on the base film layer, and then cured by drying or a simple hot pressing process. However, this structure and process cannot give the ribbon sufficient high temperature resistance, scratch resistance and water resistance, and it is difficult to achieve a metallic luster effect. When combined with water-washable label substrates of different materials, it is easy to have problems such as insufficient adhesion and incomplete pattern transfer. Summary of the invention

[0004] In order to solve the above technical problems, one of the objectives of the present invention is to provide a water-washable label carbon ribbon with good transfer effect, metallic luster and high durability.

[0005] In order to achieve the above-mentioned purpose, the technical scheme of the present invention is as follows: a high-durability metallic color water-washed label carbon tape, comprising a back coating layer, a base film layer, a peeling layer, a dye layer, an aluminum plating layer and an adhesive layer which are laminated and composited in sequence, a protective layer is sandwiched between the peeling layer and the dye layer, and the resin component in the protective layer is a thermoplastic resin containing reactive groups.

[0006] The thickness of the base film layer in the above technical solution is 4-25 μm (can be any value among 4 μm, 10 μm, 15 μm, 20 μm and 25 μm or a range corresponding to any two values), and the coating thickness of the back coating layer is 0.2 The coating thickness of the peeling layer is 0.1-2μm (can be any value among 0.2μm, 0.5μm, 1μm and 1.2μm or a range corresponding to any two values), the coating thickness of the protective layer is 0.6-1.5μm (can be any value among 0.6μm, 0.8μm, 1μm, 1.2μm and 1.5μm or a range corresponding to any two values); the coating thickness of the dye layer is 0.2-5μm (can be any value among 0.6μm, 0.8μm, 1μm, 1.2μm and 1.5μm or a range corresponding to any two values); the vapor deposition thickness of the aluminum plating layer is (Can be and any value or a range corresponding to any two values); the coating thickness of the adhesive layer is 0.1-1 μm (can be any value among 0.1 μm, 0.2 μm, 0.4 μm, 0.6 μm, 0.8 μm and 1 μm or a range corresponding to any two values).

[0007] The base film layer in the above technical solution is a transparent flexible plastic film.

[0008] The preparation method of the back coating layer in the above technical scheme is to dissolve a first resin, an isocyanate compound, an inorganic filler and a release agent in a first solvent to obtain a back coating layer coating, apply the back coating layer coating on one side of the base film layer, and dry to obtain the back coating layer; the first resin is a thermoplastic resin, and the first solvent is at least one of acetone, 2-butanone, cyclohexanone, isophorone, tetrahydrofuran, ethyl acetate, butyl acetate, propyl acetate, toluene, xylene and DMF.

[0009] The preparation method of the peeling layer in the above technical scheme is to dissolve the second resin and the release agent in the second solvent to obtain a peeling layer coating, apply the peeling layer coating on the other side of the base film layer, and dry to obtain the peeling layer; the second resin is a water-based resin, and the second solvent is at least one of water, ethanol, isopropanol, methanol, ethyl ether, dipropylene glycol butyl ether, propylene glycol methyl ether and propylene carbonate.

[0010] The preparation method of the protective layer in the above technical solution is to dissolve a third resin, an isocyanate compound and an antioxidant in a third solvent to obtain a protective layer coating, apply the protective layer coating on the other side of the peeling layer, and dry to obtain the protective layer, wherein the third solvent is at least one of acetone, 2-butanone, cyclohexanone, isophorone, tetrahydrofuran, ethyl acetate, butyl acetate, propyl acetate, toluene, xylene and DMF.

[0011] The preparation method of the dye layer in the above technical scheme is to dissolve a fourth resin, an isocyanate compound, a dye, a wetting agent and a leveling agent in a fourth solvent to obtain a dye layer coating, apply the dye layer coating on the other side of the protective layer, and dry to obtain a dye layer; the fourth resin is a thermoplastic resin and / or a thermosetting resin, and the fourth solvent is at least one of acetone, 2-butanone, cyclohexanone, isophorone, tetrahydrofuran, ethyl acetate, butyl acetate, propyl acetate, toluene, xylene and DMF.

[0012] The preparation method of the bonding layer in the above technical scheme is to dissolve a fifth resin, an inorganic filler, a hyperdispersant and an antistatic agent in a fifth solvent to obtain a bonding layer coating, apply the bonding layer coating on the side of the aluminum-plated layer away from the dye layer, and dry it to obtain a bonding layer; the fifth resin is a thermoplastic resin, and the fifth solvent is at least one of acetone, 2-butanone, cyclohexanone, isophorone, tetrahydrofuran, ethyl acetate, butyl acetate, propyl acetate, toluene, xylene and DMF.

[0013] A second object of the present invention is to provide a wash label printed with the high-durability metallic wash label carbon ribbon as described above.

[0014] A third object of the present invention is to provide a textile product using the above-mentioned wash label.

[0015] The beneficial effects of the present invention are as follows: the high-durability metallic color wash label carbon ribbon provided by the present invention has the properties of high temperature resistance, scratch resistance, excellent water resistance and non-fading, and has a printing effect with a metallic luster texture, and has good applicability on different types of wash label substrates. Through the synergistic effect between the layers, the comprehensive performance of the carbon ribbon is comprehensively improved, ensuring that the wash label print pattern always remains clear, complete and beautiful under various complex use conditions, meeting the market demand for high-quality wash label carbon ribbons, and improving the overall quality and brand image of textile products. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 This is a schematic diagram of the structure of the high-durability metallic color wash label carbon ribbon provided by the present invention.

[0017] In the figure: 1, back coating layer; 2, base film layer; 3, peeling layer; 4, protective layer; 5, dye layer; 6, aluminum plating layer; 7, adhesive layer. DETAILED DESCRIPTION

[0018] The following will be combined with the embodiments to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative work are within the scope of protection of the present invention.

[0019] The present embodiment provides a high-durability metallic color water-washable label carbon ribbon, comprising a back coating layer 1, a base film layer 2, a peeling layer 3, a dye layer 5, an aluminum plating layer 6 and a bonding layer 7 which are laminated and composited in sequence, wherein a protective layer 4 is sandwiched between the peeling layer 3 and the dye layer 5, and the resin component in the protective layer 4 is a thermoplastic resin containing reactive groups. Among them, the back coating layer first provides smoothness at different printing temperatures to avoid undesirable phenomena such as lateral wrinkles or stickiness during printing; second, it cleans and protects the print head and ensures uniform heat transfer, effectively protects the print head from wear and heat accumulation, and extends the service life of the print head; the peeling layer first allows the transfer layer (dye layer, aluminum plating layer and adhesive layer) to be demolded smoothly after printing; second, it plays a certain protective role on the surface of the pattern after printing, improving the durability and appearance quality of the pattern; the functions of the protective layer are: first, it improves the adhesion between the peeling layer and the dye layer, and enhances the overall structural stability of the carbon ribbon; second, through its high temperature resistance, weather resistance and antioxidant properties, it effectively protects the dye layer and the aluminum plating layer from damage in harsh environments such as high temperature, light and chemical erosion, ensuring the high durability of the pattern after printing; third, it can isolate water vapor and other external substances to prevent them from penetrating into the transfer layer and affecting the performance of the carbon ribbon, further improving the water resistance of the carbon ribbon and the stability of the pattern; the functions of the dye layer are: first, it realizes that the pattern has different colors of metallic luster after transfer, and by selecting different dyes The first is to provide a metal deposition carrier for evaporation, and its surface characteristics can make the metal aluminum deposit evenly during the evaporation process to form a continuous and dense aluminum-plated layer, thereby ensuring the quality and stability of the hot stamping effect; the main functions of the aluminum-plated layer are: first, it provides a unique metallic luster and reflective performance, which greatly improves the decorativeness and visual impact of the pattern; second, the compactness and flatness of the metal aluminum layer are crucial to ensure the uniformity of gloss and reflective effects; third, the compact structure can prevent the aluminum layer from falling off or wearing during use, ensuring the durability of the hot stamping effect; fourth, the flat surface can make the light reflect evenly, avoiding the appearance of local bright spots or dark spots, making the pattern more beautiful and delicate; the role of the adhesive layer: first, it provides a strong bonding force, closely connecting the aluminum-plated layer with the wash label substrate, ensuring that the front layer can be completely transferred to the surface of the wash label substrate during printing, and maintaining a firm attachment during subsequent use to prevent the pattern from falling off; second, it effectively fills the tiny pores on the surface of the wash label substrate and significantly improves the flatness of the adhesive layer.

[0020] The base film layer in the above technical solution is a transparent flexible plastic film (which can be a polypropylene film, a polyethylene naphthalate film, a polyethylene terephthalate film, a polyethylene film, a polyvinyl alcohol film or a polymethyl methacrylate film, wherein polyethylene naphthalate film or polyethylene terephthalate film is preferred).

[0021] The preparation method of the back coating layer in the above technical scheme is to dissolve the first resin, isocyanate compound, inorganic filler and release agent in the first solvent to obtain the back coating layer (the viscosity of the back coating layer at 25°C is 100-500mPa·s, wherein the amount of the first solvent added to the back coating layer is 50-80wt%), apply the back coating layer on one side of the base film layer (by gravure coating or slit coating, the drying temperature is 60-100°C, the drying time is 60-120s), and dry to obtain the back coating layer; the first resin is a thermoplastic resin [for example: polyester resin, polyacrylate resin, polyvinyl acetate resin, styrene-acrylate resin, polyurethane resin, polyolefin resin (such as polyethylene resin or polypropylene resin), polystyrene resin, polyvinyl chloride resin, The first solvent is at least one of acetone, 2-butanone, cyclohexanone, isophorone, tetrahydrofuran, ethyl acetate, butyl acetate, propyl acetate, toluene, xylene and DMF (preferably 2-butanone and toluene are miscible, and the volume ratio of 2-butanone and toluene is 1-4:1); the purpose of adding the isocyanate compound to the back coating layer is to improve the heat resistance of the back coating layer during printing, improve the adhesion between the back coating layer and the base film layer and reduce the viscosity at high temperature, and the isocyanate compound can be toluene diisocyanate (TD I), isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), dicyclohexylmethane diisocyanate (HMD I), hexamethylene diisocyanate (HD I), lysine diisocyanate (LD I), etc., preferably, aromatic isocyanate compounds are used, such as 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, di-toluidine diisocyanate or p-phenylene diisocyanate, etc., and the amount of isocyanate compound in the back coating is 0.1-2wt% of the back coating coating; in order to maintain the excellent slipperiness of the carbon ribbon in high-speed printing, inorganic fillers (talc, kaolin, calcium carbonate, aluminum hydroxide, silicon dioxide, graphite or boron nitride) and release agents (phosphate compounds, metal soaps, silicone oils or surfactants, etc.) need to be added to the back coating.The inorganic filler is preferably talcum powder with a mesh size of 5000-11000, and the amount added is 1-5% (preferably 3-5%) of the weight of the first resin. The release agent is preferably phosphate ester, and the amount added is 1-10% (preferably 3-5%) of the first resin. In order to ensure that the inorganic filler is evenly dispersed in the resin, improve the good thermal conductivity of the back coating, improve the gloss after transfer, reduce the surface roughness, and improve the wear resistance, it is necessary to control the overall particle size and particle size distribution of the inorganic filler, and the filler D50 particle size is required to be 1.0-5μm, and the D90 particle size is 3-10μm. If the requirements cannot be met, grinding treatment is required.

[0022] The preparation method of the release layer in the above technical solution is to dissolve the second resin and the release agent in the second solvent to obtain a release layer coating (until the viscosity of the release layer coating at 25°C is 100-500mPa·s), apply the release layer coating on the other side of the base film layer (by gravure coating or slit coating, the drying temperature is 60-120°C, the drying time is 60-120s), and dry to obtain the release layer; the second resin is a water-based resin with high gloss (such as polyacrylic resin, polyurethane resin, polyester Resin or EVA resin, considering the release effect and durability of the peeling layer, preferably polyacrylic resin is used, and more preferably a resin with a Tg value of 50-120°C and a molecular weight of 1000-20000), the second solvent is at least one of water, ethanol, isopropanol, methanol, ethyl ether, dipropylene glycol butyl ether, propylene glycol methyl ether and propylene carbonate (preferably water, ethanol and propylene glycol methyl ether are miscible, the ratio is controlled at 1-3:1:1-1.5, and the amount of the second solvent added accounts for 50-95wt% of the total weight of the peeling layer). The purpose of adding a release agent to the peeling layer is to improve the glossiness of the peeling layer. The release agent can be a solid release agent or a liquid release agent. The solid release agent can be polyethylene wax, palmitamide, ethylene bislauric acid amide, behenic acid amide, ethylene bisoleic acid amide, stearic acid amide, ethylene bisstearic acid amide, oleic acid amide, erucic acid amide, oleyl palmitamide, octadecyl stearic acid amide, octadecyl erucic acid amide, pentaerythritol tetrastearate, glyceryl trihydroxystearate, zinc stearate, stearyl zinc phosphate, calcium stearate, magnesium stearate, talc or wax powder; the liquid release agent can be silicone oil, liquid paraffin, chlorinated paraffin, n-butyl stearate, etc. The preferred release agent is an aqueous wax emulsion, which can have The adhesive force between the peeling layer and the base film layer is effectively reduced. During the printing process, when the pattern needs to be transferred from the carbon ribbon to the washable label substrate, suitable demoulding performance is the key to ensure the complete and clear transfer of the pattern. The aqueous wax emulsion forms a low surface energy film in the peeling layer, so that the pattern can be smoothly separated from the carbon ribbon, avoiding problems such as pattern adhesion and incompleteness, thereby ensuring the integrity and clarity of the transfer, improving the printing quality, and at the same time improving the scratch resistance of the carbon ribbon and the smoothness of the film surface. It can also improve the surface smoothness of the peeling layer, thereby enhancing the gloss of the printed pattern. Further preferably, an aqueous wax emulsion with a melting point of 80-120°C can be used, and the addition amount is 1-10wt% of the peeling layer coating.

[0023] The preparation method of the protective layer in the above technical solution is to dissolve a third resin, an isocyanate compound and an antioxidant in a third solvent to obtain a protective layer coating (the viscosity at 25°C is 100-500mPa·s), apply the protective layer coating on the other side of the peeling layer, and dry it to obtain a protective layer (coating is performed by gravure coating or slit coating, the drying temperature is 60-120°C, and the drying time is 60-120s), the third resin is a thermoplastic resin containing a reactive group [such as polyester resin, polyacrylate resin, styrene-acrylate resin, polyurethane resin, polyolefin resin (such as polyethylene resin and polypropylene resin), polystyrene resin, polyvinyl chloride resin, polyvinyl butyral resin, amino resin or epoxy resin, etc., in view of interlayer adhesion and resistance, it is preferably a hydroxyl-modified acrylic resin. The invention relates to a coating comprising at least one of a resin, a hydroxyl-modified vinyl chloride-acrylate resin, a polyester-modified acrylic resin, an acrylic acid-modified polyester and the like, wherein the hydroxyl-modified acrylic resin provides excellent wear resistance, chemical corrosion resistance and adhesion properties, wherein the chemical structure of the hydroxyl-modified acrylic resin contains hydroxyl and acrylic acid groups, and it has good solubility, high molecular weight and thermal stability, and the Tg value of the selected hydroxyl-modified acrylic resin is preferably 70-95° C. and the molecular weight is preferably 20000-50000], wherein the third solvent is at least one of acetone, 2-butanone, cyclohexanone, isophorone, tetrahydrofuran, ethyl acetate, butyl acetate, propyl acetate, toluene, xylene and DMF (preferably 2-butanone and toluene are miscible, the ratio of 2-butanone to toluene is controlled between 1-4:1, and the amount of the third solvent added is 50-80wt% of the protective layer coating). The purpose of adding isocyanate compounds (similar in type to that in the back coating) to the protective layer is to improve the adhesion and friction resistance of the protective layer, and the amount thereof is 0.2-5wt% of the protective layer coating content; in order to extend the service life and thermal stability of the carbon ribbon, it is also possible to consider adding antioxidants to the protective layer coating, the antioxidants include at least one of hindered phenols, phosphites, thiols and hindered amines (HALS) (the antioxidants can be mixed with hindered phenols, phosphites and thiols), and the amount of the antioxidant is 0.05-0.5wt% of the total amount of the protective layer coating.

[0024] The preparation method of the dye layer in the above technical scheme is to dissolve a fourth resin, an isocyanate compound (similar in type to that in the back coating layer), a dye, a wetting agent and a leveling agent in a fourth solvent to obtain a dye layer coating, apply the dye layer coating on the other side of the protective layer, and dry to obtain a dye layer (coating is performed by gravure coating or slit coating, the drying temperature is 60-100° C., and the drying time is 60-120s); the fourth resin is a thermoplastic resin and / or a thermosetting resin [such as a polyester resin, a polyacrylate resin, a polyvinyl acetate resin, a styrene acrylate resin, a polyurethane resin, a polyolefin resin (such as a polyethylene resin or a polypropylene resin) , polystyrene resin, polyvinyl chloride resin (such as polyvinyl chloride resin), polyether resin, polyamide resin, polyimide resin, polyamideimide resin, polycarbonate resin, polyacrylamide resin, polyvinyl acetal resin (such as polyvinyl butyral resin or polyvinyl acetal resin) or their silicone modified products. In order to ensure the transmittance of the dye layer and the affinity to the aluminum plating layer, the fourth resin is preferably a hydroxy polyacrylic resin with a Tg value of 80-130°C, a molecular weight of 10000-100000, and a hydroxyl value of 50-150. The fourth solvent is acetone, 2-butanone, cyclohexanone, isophorone, tetrahydrofuran, ethyl acetate, butyl acetate, propyl acetate , toluene, xylene and DMF (preferably a miscible substance of 2-butanone and toluene in a volume ratio of 1-4:1, and the addition amount of the fourth solvent is 50-80wt% of the total mass of the dye layer); in order to make the carbon ribbon have metallic luster of different colors after printing, it can be achieved by selecting different dyes, and as the dye, at least one of carbon black, acetylene black, lamp black, cadmium red, chrome red, vermilion, cobalt yellow, cadmium orange, chrome yellow, zinc yellow, Naples yellow, onion yellow, ultramarine, verdigris, cadmium green, chrome green, phthalocyanine, aluminum pigment and azo dye can be used, and the addition amount is 0-15wt% (preferably 5-15wt%) of the total weight of the dye layer coating, and when the silver metallic luster is achieved, it is not necessary to Add dye; The purpose of adding a wetting agent to the dye layer coating is to effectively reduce the surface tension of the dye layer, so that the aluminum atoms can better spread and adhere to its surface during the evaporation process, and improve the uniformity and density of the aluminum plating layer. Specifically, the wetting agent can be one or more combinations of organic silicon (such as polydimethylsiloxane and its derivatives, polydimethylsiloxane polyoxyethylene ether, modified polysiloxane or acetylene glycol modified organic silicon wetting agent), anionic (such as sodium dodecyl sulfate, sodium alkylbenzene sulfonate, alkyl phosphate salt or Solvay wetting penetrant) and nonionic (such as fatty alcohol polyoxyethylene ether, fatty acid polyoxyethylene ester or isooctyl glucoside). The amount of the wetting agent added is 0.5-2wt%; the addition of the leveling agent is to help the coating of the dye layer to level evenly during the coating process, eliminate surface defects, and ensure the flatness of the dye layer surface, thereby providing a good foundation for metal deposition, making the aluminum plating layer smoother and more uniform, and improving the gloss and texture of the hot stamping pattern. The leveling agent includes at least one of acrylic acid, silicone and fluorine-modified acrylic acid, and its addition amount is 0.5-2wt% of the total weight of the dye layer. .

[0025] The aluminum layer can be plated by vacuum aluminum plating, heating aluminum with resistance, high frequency, electron beam, or vacuum coating technology such as magnetron sputtering and ion sputtering. Further, from the perspective of cost and operation convenience, the resistance heating type vacuum aluminum plating method is preferred. To ensure the integrity of the surface of the aluminum layer after evaporation, the surface tension of the dye layer before evaporation needs to reach 38-42 dyne / cm. To ensure that the aluminum layer has high gloss, suitable folding resistance and toughness, the recommended aluminum layer evaporation thickness is (Angstroms), and a further preferred thickness is

[0026] The preparation method of the bonding layer in the above technical scheme is to dissolve the fifth resin, inorganic filler, super dispersant and antistatic agent in the fifth solvent to obtain a bonding layer coating, apply the bonding layer coating on the side of the aluminum-plated layer away from the dye layer, and dry it to obtain the bonding layer (by gravure coating or slit coating, the drying temperature is 60-120°C, and the drying time is 60-120S); the fifth resin is a thermoplastic resin [the fifth resin can be polyester, (meth) acrylic resin, polyurethane, cellulose resin, melamine resin, polyamide, polyolefin resin (such as polyethylene resin or polypropylene resin), vinyl resin (such as polyvinyl chloride, styrene resin, polyvinyl acetate, vinyl chloride-vinyl acetate copolymer) or vinyl chloride-acrylate resin. Considering the hardness, film-forming property, good solubility, thermal stability and adhesion of the resin, it can be the same as the resin of the protective layer. The advantage is that when printing as a bonding layer, no anti-sticky carbon tape will appear, and the interlayer adhesion with the protective layer is good, so The fifth resin is preferably a hydroxyl-modified acrylic resin, and a resin having a Tg of 70-95° C. and a molecular weight of 20,000-50,000 is selected. The fifth solvent is at least one of acetone, 2-butanone, cyclohexanone, isophorone, tetrahydrofuran, ethyl acetate, butyl acetate, propyl acetate, toluene, xylene and DMF (preferably, the fifth solvent is a mixed solution of 2-butanone and toluene, and the ratio of 2-butanone to toluene is controlled at 1-4:1. Preferably, the fifth solvent is added The added amount accounts for 50-80wt% of the total amount of the bonding layer); the inorganic filler can provide flatness and adaptability of the carbon tape, and can use at least one of talcum powder, kaolin, calcium carbonate, aluminum hydroxide, silicon dioxide, graphite and boron nitride. Preferably, flaky kaolin is used, which can effectively fill the tiny pores on the surface of the water-washed label substrate and significantly improve the flatness of the bonding layer (this is very important for improving the uniformity of the transfer effect. In practical applications, the materials of the water-washed label substrate are diverse and the surface roughness is also different.On a rough substrate, if there is no leveling effect of the adhesive layer, it is difficult for the aluminum-plated layer and the dye layer to fully contact the substrate, which can easily lead to problems such as partial non-transfer or unclear transfer. By adding flaky kaolin, the adhesive layer can adapt to substrates of different roughness, ensuring high-quality printing effects on water-washable labels of various materials, making the pattern clearer and more complete. The amount of inorganic filler added is 1-3wt% of the total amount of the adhesive layer coating); and in order to make the kaolin well dispersed in the adhesive layer, it is also necessary to add a polymer-type superdispersant. The superdispersant can prevent kaolin from agglomerating in the resin through mechanisms such as steric hindrance and electrostatic stabilization. The anchoring group in its molecular structure can combine with the active site on the surface of kaolin, and the solvated chain extends in the resin solution, so that the kaolin particles remain in a stable dispersed state in the resin. In the process, it is necessary to control the type and amount of super dispersant added to achieve the best dispersion effect, ensure that kaolin can give full play to its advantages in improving bonding performance and improving surface flatness, thereby improving the comprehensive performance of the water-washable label adhesive layer, and ensure the reliability and stability of the water-washable label during long-term use. Preferably, the amount of super dispersant added is 0.5-1.5wt% of the total amount of the adhesive layer coating; in order to reduce the static electricity accumulation of the adhesive layer during printing, avoid the problem of static electricity adsorbing dust, affecting the printing quality or causing the print head to be blocked, and improve the reliability and stability of printing, a certain amount of antistatic agent is added to the adhesive layer, and the antistatic agent includes at least one of sulfuric acid derivatives, phosphoric acid derivatives, amines, quaternary ammonium salts, imidazoles and ethylene oxide derivatives, and the amount of the antistatic agent is 0.5-1wt% of the total amount of the adhesive layer coating.

[0027] Example 1

[0028] <Base film layer>:

[0029] The base film layer used a 4.5 μm PET film.

[0030] <Back coating>:

[0031] By weight, the formula is as follows:

[0032] 10 parts of polyvinyl butyral resin (Kuraray Chemical B-30HH, Japan);

[0033] 3 parts of polyisocyanate curing agent (Asahi Chemical TMHG-80B from Japan);

[0034] 0.5 parts of silicone oil (Shin-Etsu silicone KF-965-100cs);

[0035] Phosphate ester (MOA-3PK-70 from Jiangsu Haian Petrochemical Plant) 0.6 part;

[0036] 0.6 parts of talcum powder (Haiyang powder HY-TA05 D50 particle size 1.5um, D90 particle size 4.2um);

[0037] 2-butanone 42.65 parts;

[0038] Toluene 42.65 parts;

[0039] Coating was done by gravure coater, with a coating thickness of 0.4 μm.

[0040] <Peeling layer>:

[0041] By weight, the formula is as follows:

[0042] 15 parts of water-based acrylic resin (Baowei New Material 8503);

[0043] 10 parts of montan wax (Wengkel CT7093, Germany);

[0044] 1 part of hindered phenolic water-based antioxidant (Lowinox 1790 from SI Group Chemicals);

[0045] 20.5 parts of deionized water;

[0046] 40.5 parts of isopropyl alcohol;

[0047] Propylene glycol methyl ether 30.5 parts;

[0048] Coating was done by gravure coater, with a coating thickness of 0.3 μm.

[0049] <Protection layer>:

[0050] By weight, the formula is as follows:

[0051] 20 parts of hydroxy acrylic resin (SGR-015A Guangzhou Changhao);

[0052] Antioxidant (Irganox-1010 BASF Chemical, Germany) 0.3 parts;

[0053] Antioxidant (Irganox-168, BASF Chemical, Germany) 0.1 part;

[0054] Polyisocyanate curing agent (SBN-70D Polynaide) 0.3 parts;

[0055] 2-butanone 39.65 parts;

[0056] Toluene 39.65 parts;

[0057] Coating was done by gravure coater, with a coating thickness of 0.8 μm.

[0058] <Dye Layer>:

[0059] By weight, the formula is as follows:

[0060] Hydroxylated acrylic resin (Dongguan Yongyu Technology Chemical Y616C) 20 parts;

[0061] 5 parts of aliphatic isocyanate curing agent (Covestro Bayhydur 304);

[0062] 10 parts of gold dye (Y-20 yellow, a metal chromium dye produced by Mingru Chemical in Taiwan, China);

[0063] Wetting agent (Lida Chemical LD-8400) 0.1 part;

[0064] Leveling agent (Lida Chemical LD-9108) 0.1 part;

[0065] 2-butanone 28 parts;

[0066] 30 parts of butyl acetate;

[0067] Propylene glycol methyl ether acetate 5 parts;

[0068] Coating was done by gravure coater, with a coating thickness of 0.8 μm.

[0069] <Aluminum coating>:

[0070] The vacuum evaporation method was used with a vacuum degree of 5×10 -3 -1×10 -2 Under the conditions of Pa, evaporation rate of 0.3nm / s and substrate temperature of 60℃, metallic aluminum was evaporated and deposited on the surface of the dye layer, and the aluminum plating thickness was 0.05μm.

[0071] <Next layer>:

[0072] By weight, the formula is as follows:

[0073] 14 parts of hydroxy acrylic resin (Guangzhou Keding Chemical MR14896A);

[0074] 1 part of flake kaolin (BSKY-012 from Bushi Mining);

[0075] 0.4 parts of polymer hyperdispersant (BYK-163);

[0076] 0.8 parts of quaternary ammonium salt water-based antistatic agent (Milliken BNK-QQ);

[0077] 2-butanone 45.05 parts;

[0078] Toluene 45.05 parts;

[0079] Coating was done by gravure coater, with a coating thickness of 0.3 μm.

[0080] Example 2

[0081] Same as Example 1, except that:

[0082] <Peeling layer>:

[0083] By weight, the formula is as follows:

[0084] 10 parts of water-based acrylic resin (Covestro A2646);

[0085] 10 parts of water-based polyethylene wax (GA1050 from Germany);

[0086] 1 part of hindered phenolic water-based antioxidant (Lowinox 1790 from SI Group Chemicals);

[0087] 20 parts of deionized water;

[0088] 45.5 parts of isopropyl alcohol;

[0089] Propylene glycol methyl ether 25 parts;

[0090] Coating was done by gravure coater, with a coating thickness of 0.3 μm.

[0091] <Protection layer>:

[0092] By weight, the formula is as follows:

[0093] 20 parts of hydroxy acrylic resin (SGR-015A Guangzhou Changhao);

[0094] Antioxidant (Irganox-1010 BASF Chemical, Germany) 0.3 parts;

[0095] Antioxidant (Irganox-168, BASF Chemical, Germany) 0.1 part;

[0096] Polyisocyanate curing agent (SBN-70D Polynaide) 0.3 parts;

[0097] 2-butanone 39.65 parts;

[0098] Toluene 39.65 parts;

[0099] Coating was done by gravure coater, with a coating thickness of 0.8 μm.

[0100] <Dye Layer>:

[0101] By weight, the formula is as follows:

[0102] 20 parts of hydroxy acrylic resin (Changxing Chemical 601A-75);

[0103] 5 parts of aliphatic isocyanate curing agent (Covestro Bayhydur 304);

[0104] 10 parts of gold dye (Y-20 yellow, a metal chromium dye produced by Mingru Chemical in Taiwan, China);

[0105] Wetting agent (Lida Chemical LD-8400) 0.1 part;

[0106] Leveling agent (Lida Chemical LD-9108) 0.1 part;

[0107] 2-butanone 28 parts;

[0108] 30 parts of butyl acetate;

[0109] Propylene glycol methyl ether acetate 5 parts;

[0110] Coating was done by gravure coater, with a coating thickness of 0.8 μm.

[0111] Example 3

[0112] Same as Example 2, except that:

[0113] <Back coating>:

[0114] By weight, the formula is as follows:

[0115] Polyvinyl butyral resin (B17TX, Chang Chun Chemical Industry, Taiwan, China) 11 parts;

[0116] 2 parts of polyisocyanate curing agent (Asahi Chemical TMHG-80B from Japan);

[0117] 0.5 parts of silicone oil (Shin-Etsu silicone KF-965-100cs);

[0118] Phosphate ester (MOA-3PK-70 from Jiangsu Haian Petrochemical Plant) 0.6 part;

[0119] 0.6 parts of talcum powder (Haiyang powder HY-TA05 D50 particle size 1.5um, D90 particle size 4.2um);

[0120] 2-butanone 42.65 parts;

[0121] Toluene 42.65 parts;

[0122] Coating was done by gravure coater, with a coating thickness of 0.4 μm.

[0123] Example 4

[0124] Same as Example 3, except that:

[0125] <Peeling layer>:

[0126] By weight, the formula is as follows:

[0127] Water-based acrylic resin (Wuxi Honghui New Materials ACUST 3958) 10 parts;

[0128] 10 parts of water-based carnauba wax (BYK AQUACER 2650);

[0129] 1 part of hindered phenolic water-based antioxidant (Lowinox 1790 from SI Group Chemicals);

[0130] 25 parts of deionized water;

[0131] 45 parts of isopropyl alcohol;

[0132] Propylene glycol methyl ether 20 parts;

[0133] Coating was done by gravure coater, with a coating thickness of 0.3 μm.

[0134] Comparative Example 1

[0135] Same as Example 1, except that there is no peeling layer.

[0136] Comparative Example 2

[0137] Same as Example 1, except that there is no dye layer.

[0138] Comparative Example 3

[0139] Same as Example 1, except that there is no aluminum coating.

[0140] Comparative Example 4

[0141] Same as Example 1, except that there is no protective layer.

[0142] Comparative Example 5

[0143] The same as Example 1, except that there is no adhesive layer.

[0144] Comparative Example 6

[0145] Same as Example 1, except that:

[0146] <Back coating>:

[0147] By weight, the formula is as follows:

[0148] 10 parts of polyvinyl butyral resin (Kuraray Chemical B-30HH, Japan);

[0149] 3 parts of polyisocyanate curing agent (Asahi Chemical TMHG-80B from Japan);

[0150] 2-butanone 43.5 parts;

[0151] Toluene 43.5 parts;

[0152] Coating was done by gravure coater, with a coating thickness of 0.4 μm.

[0153] Comparative Example 7

[0154] Same as Example 1, except that:

[0155] <Dye Layer>:

[0156] By weight, the formula is as follows:

[0157] Hydroxylated acrylic resin (Dongguan Yongyu Technology Chemical Y616C) 20 parts;

[0158] 5 parts of aliphatic isocyanate curing agent (Covestro Bayhydur 304);

[0159] 5 parts of gold dye (Y-20 yellow, a metal chromium dye produced by Mingru Chemical in Taiwan, China);

[0160] Wetting agent (Lida Chemical LD-8400) 0.1 part;

[0161] Leveling agent (Lida Chemical LD-9108) 0.1 part;

[0162] 2-butanone 30 parts;

[0163] 33 parts of butyl acetate;

[0164] Propylene glycol methyl ether acetate 5 parts;

[0165] Coating was done by gravure coater, with a coating thickness of 0.4 μm.

[0166] Performance Testing

[0167] The printing test was conducted using a Zebra 105SL PLUS TM printer. The ribbon used was a self-developed metallic washable label ribbon. The print sample size was 80*50mm, the printing speed was 10.1cm / s, and the concentration was 15-30. The specific test items are as follows:

[0168] ① Adhesion test and evaluation criteria

[0169] The wash label carbon ribbons obtained in the above embodiments and comparative examples were transferred onto polyester fiber fabric, cotton fabric and nylon fabric (wash label substrate), respectively, and the patterns were printed onto the substrates using a Zebra printer 105SL PLUS TM. After obtaining the test samples, they were tested using a German BYK-white grid knife. The grade was based on the ISO 2409 cross-cut test standard, and the standards are as follows (the results are shown in Table 1):

[0170] 0: The cutting edge is completely smooth; no grid is falling off;

[0171] 1: A small amount of coating falls off at the intersection of the cuts, and the cross-cut area affected cannot be greater than 5%;

[0172] 2: Coating peels off at the cutting edge and / or intersection, and the affected cutting area is greater than 5% but less than 15%;

[0173] 3: The coating falls off partially or completely in large pieces along the cut edge, and / or falls off partially or completely in different parts of the grid, and the affected cut area is greater than 15% but less than 35%;

[0174] 4: Large pieces of coating fall off along the cutting edge, and / or some grids fall off partially or completely, and the affected cutting area is greater than 35% but less than 65%;

[0175] 5: Any degree of shedding beyond Level 4.

[0176] Table 1 is the adhesion test results

[0177]

[0178]

[0179] ②Gloss test and evaluation standards

[0180] The washing mark carbon ribbons obtained in the above embodiments and comparative examples were respectively printed on polyester fiber fabrics, cotton fabrics, nylon fabrics, etc., using a Zebra printer 105SL PLUS TM to print patterns on substrates. After obtaining test samples, the 20° and 60° glossiness of part of the transferred pattern area was measured using a Sanens touch screen three-angle gloss meter NHG268, the average value was read, and the glossiness was evaluated based on the following evaluation criteria, the evaluation criteria are as follows (the results are shown in Table 2).

[0181] A+: Glossiness evaluation result is 1200 or more at 20° and 700 or more at 60°;

[0182] A-: Glossiness evaluation result is 1200 or more at 20° and 650 or more but less than 700 at 60°;

[0183] B+: The glossiness evaluation result is 1000 to 1200 at 20° and 600 to 650 at 60°;

[0184] B-: The glossiness evaluation result is 1000 to 1200 at 20° and 550 to 600 at 60°;

[0185] C+: Glossiness evaluation result is 800 to 1000 at 20° and 550 to 600 at 60°;

[0186] C-: Glossiness evaluation result is 800 to 1000 at 20° and 500 to 550 at 60°;

[0187] D: Glossiness evaluation results were 800 or less at 20° and 500 or less at 60°.

[0188] Table 2 is the gloss test results

[0189]

[0190] ③ Washability test and evaluation standards

[0191] The metallic wash label ribbons obtained in the above embodiments and comparative examples are respectively printed on polyester fiber fabrics, cotton fabrics and nylon fabrics (wash label substrates) using a Zebra printer 105SL PLUS TM. After obtaining the test samples, a certain amount of standard detergent is prepared under conditions simulating the actual washing environment. The composition and concentration of the detergent must be similar to those of common household or industrial detergents. Then, the wash label ribbon sample is placed in a container filled with detergent to ensure that the sample is completely immersed, and the appropriate water temperature is set, generally between 40-60°C. This temperature range covers the water temperature in most actual washing scenarios. Then, the stirring device is started to rotate or reciprocate the sample in the detergent at a certain speed (such as 100-150 rpm) to simulate the washing process of the washing machine. The washing is continued for a certain time, usually 30-60 minutes. After washing is completed, a rinsing step is performed to remove the detergent remaining on the surface of the sample. Generally, clean water is used for rinsing 2-3 times, and each rinsing time is about 5-10 minutes. Finally, the rinsed samples were taken out to air dry or dried at a specified temperature (such as 60-80°C). The evaluation criteria were as follows (the results are shown in Table 3).

[0192] 1: The pattern is basically not worn, the color has no obvious change, and the pattern is clearly discernible;

[0193] 2: The pattern is slightly worn and the color fades slightly. The pattern is basically recognizable, but some details are lost;

[0194] 3: The pattern is severely worn, the color has faded significantly, the pattern is difficult to recognize, and it is faded, blurred or falling off.

[0195] Table 3 is the results of the water washability test

[0196]

[0197]

[0198] ④Friction resistance test and evaluation standards

[0199] The wash label carbon ribbons obtained in the above embodiments and comparative examples are respectively used on polyester fiber fabrics, cotton fabrics and nylon fabrics (wash label substrates), and the patterns are printed onto the substrates using a Zebra printer 105SL PLUS TM to obtain test samples. A friction tester (such as DZ-204) is used to perform a simulated friction test: First, the metallic wash label sample with the pattern printed on it using the carbon ribbon is fixed on the test platform of the friction tester to ensure that the sample surface is flat and firmly fixed; then, a suitable friction medium is selected, and a common one is a standard friction cloth (such as cotton or polyester fiber material), whose roughness and fiber properties are standardized to ensure the consistency and comparability of the test results; the parameters of the friction tester are set, including friction pressure, friction speed and friction times, etc. The friction pressure is generally set according to the actual use. The friction head is set according to the pressure range that may be experienced during use (for example, 500-1000g); the friction speed is usually 30-60 times / minute, and this speed range can better simulate the friction frequency in daily use; the number of frictions is determined according to the expected use cycle and durability requirements of the product, generally between 500-2000 times. During the test, the friction head performs reciprocating friction operations on the water-washing label sample under the set parameters to simulate the friction between the water-washing label and other objects during the wearing and washing of clothes. The evaluation criteria are as follows (the results are shown in Table 4).

[0200] 1: The pattern is basically not worn, the color has no obvious change, and the pattern is clearly discernible;

[0201] 2: The pattern is slightly worn and the color fades slightly. The pattern is basically recognizable, but some details are lost;

[0202] 3: The pattern is severely worn, the color has faded significantly, the pattern is difficult to recognize, and it is faded, blurred or falling off.

[0203] Table 4 is the friction test results

[0204]

[0205] ⑤Alcohol friction resistance test and evaluation standards

[0206] The metallic wash label ribbons obtained in the above embodiments and comparative examples were respectively printed on polyester fiber fabric, cotton fabric and nylon fabric (wash label substrate) using a Zebra printer 105SL PLUS TM to print patterns on the wash label materials. After obtaining the test samples, the color density before friction was tested using an X-Rite i 1-PRO3 colorimeter. The alcohol friction tester DZ-204 was used with a WIP-1009D friction cloth to perform a friction test 1000 times at a weight load of 1000g and a friction speed of 60 times / min. After the test was completed, the color density after friction was tested using an X-Rite i 1-PRO3 colorimeter, the ratio of the color density after friction to the color density before friction was calculated, and the glossiness was evaluated based on the following evaluation criteria, the evaluation criteria are as follows (the results are shown in Table 5):

[0207] A: Color density ratio is greater than or equal to 95%;

[0208] B: Color density ratio is greater than or equal to 80% and less than 95%;

[0209] C: Color density ratio is greater than or equal to 60% and less than 80%;

[0210] D: The color density ratio is less than 60%.

[0211] Table 5 is the alcohol resistance test results

[0212]

[0213] Among them, since the thermal transfer effects of Comparative Examples 1 and 6 in Tables 1 to 5 are not good, no performance test was performed.

[0214] In this embodiment, the back coating layer, base film layer, peeling layer, protective layer, dye layer, aluminum plating layer and adhesive layer are combined in sequence, so that the layers work closely together, achieving significant improvements in the carbon ribbon's performance in terms of friction resistance, water resistance, chemical resistance, non-fading, and metallic luster texture, while ensuring good applicability on different types of water-washable label substrates.

[0215] The embodiments of the present invention are described in detail above. Specific examples are used herein to illustrate the principles and implementation methods of the present invention. The description of the above embodiments is only used to help understand the method of the present invention and its core idea. At the same time, for those skilled in the art, according to the idea of ​​the present invention, there will be changes in the specific implementation methods and application scope. In summary, the content of this specification should not be understood as a limitation on the present invention.

Claims

1. A high-durability metallic color washable label carbon ribbon, comprising a back coating layer (1), a base film layer (2), a peeling layer (3), a dye layer (5), an aluminum plating layer (6) and an adhesive layer (7) which are laminated and composited in sequence, characterized in that: A protective layer (4) is sandwiched between the peeling layer (3) and the dye layer (5), and the resin component in the protective layer (4) is a thermoplastic resin containing reactive groups.

2. The high-durability metallic color wash label carbon ribbon according to claim 1, characterized in that: The thickness of the base film layer is 4-25 μm, the coating thickness of the back coating layer is 0.2-1.2 μm, the coating thickness of the peeling layer is 0.1-2 μm, the coating thickness of the protective layer is 0.6-1.5 μm; the coating thickness of the dye layer is 0.2-5 μm; the vapor deposition thickness of the aluminum plating layer is The coating thickness of the adhesive layer is 0.1-1 μm.

3. The high-durability metallic color wash label carbon ribbon according to claim 1, characterized in that: The base film layer is a transparent flexible plastic film.

4. The high-durability metallic color wash label carbon ribbon according to claim 1, characterized in that: The preparation method of the back coating layer is as follows: a first resin, an isocyanate compound, an inorganic filler and a release agent are dissolved in a first solvent to obtain a back coating layer coating, the back coating layer coating is applied on one side of a base film layer, and the back coating layer is obtained by drying; the first resin is a thermoplastic resin, and the first solvent is at least one of acetone, 2-butanone, cyclohexanone, isophorone, tetrahydrofuran, ethyl acetate, butyl acetate, propyl acetate, toluene, xylene and DMF.

5. The high-durability metallic color wash label carbon ribbon according to claim 1, characterized in that: The preparation method of the peeling layer is to dissolve the second resin and the release agent in the second solvent to obtain a peeling layer coating, apply the peeling layer coating on the other side of the base film layer, and dry to obtain the peeling layer; the second resin is a water-based resin, and the second solvent is at least one of water, ethanol, isopropanol, methanol, ethyl ether, dipropylene glycol butyl ether, propylene glycol methyl ether and propylene carbonate.

6. The high-durability metallic color wash label carbon ribbon according to claim 1, characterized in that: The protective layer is prepared by dissolving a third resin, an isocyanate compound and an antioxidant in a third solvent to obtain a protective layer coating, coating the protective layer coating on the other side of the stripping layer, and drying to obtain the protective layer, wherein the third solvent is at least one of acetone, 2-butanone, cyclohexanone, isophorone, tetrahydrofuran, ethyl acetate, butyl acetate, propyl acetate, toluene, xylene and DMF.

7. The high-durability metallic color wash label carbon ribbon according to claim 1, characterized in that: The preparation method of the dye layer is to dissolve a fourth resin, an isocyanate compound, a dye, a wetting agent and a leveling agent in a fourth solvent to obtain a dye layer coating, apply the dye layer coating on the other side of the protective layer, and dry to obtain the dye layer; the fourth resin is a thermoplastic resin and / or a thermosetting resin, and the fourth solvent is at least one of acetone, 2-butanone, cyclohexanone, isophorone, tetrahydrofuran, ethyl acetate, butyl acetate, propyl acetate, toluene, xylene and DMF.

8. The high-durability metallic color wash label carbon ribbon according to claim 1, characterized in that: The preparation method of the bonding layer is to dissolve a fifth resin, an inorganic filler, a hyperdispersant and an antistatic agent in a fifth solvent to obtain a bonding layer coating, apply the bonding layer coating on the side of the aluminum-plated layer away from the dye layer, and dry to obtain the bonding layer; the fifth resin is a thermoplastic resin, and the fifth solvent is at least one of acetone, 2-butanone, cyclohexanone, isophorone, tetrahydrofuran, ethyl acetate, butyl acetate, propyl acetate, toluene, xylene and DMF.

9. A washing label, characterized in that: The product is printed and dyed using the high-durability metallic color wash label carbon ribbon as described in any one of claims 1 to 8.

10. A textile, characterized in that: Including the washing label as claimed in claim 9.

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