An ultra-thin thermal sublimation reverse transfer printing film, a preparation method thereof and a transfer printing method

Abstract

The application belongs to the technical field of lining printing, and particularly relates to an ultrathin thermal sublimation lining printing retransfer film, a preparation method thereof and a transfer printing method. The ultrathin thermal sublimation lining printing retransfer film comprises a back coating layer, a base layer, a release layer, a white ink layer and a dye receiving layer arranged in sequence. The ultrathin thermal sublimation lining printing retransfer film provided by the application is applied to lining printing technology, can significantly improve the color density of an image and improve the image effect, can be printed on demand, can be directly transferred without the aid of other carbon ribbons, greatly saves production cost and simplifies the transfer printing process. The lining printing transfer printing object obtained by the application not only has a fine pattern of thermal sublimation printing, but also reduces production cost and simplifies the lining printing process.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of lining printing, and particularly relates to an ultrathin thermal sublimation lining printing retransfer film, a preparation method thereof, and a transfer printing method. BACKGROUND

[0002] The lining printing process on the market currently has the defects of complex pre-plate making technology, long cycle, high plate making cost, etc. The ultrathin thermal sublimation lining printing retransfer film provided by the present application can not only significantly improve the color density of the image and improve the image effect, but also can print on demand, directly transfer without the aid of other carbon bands, greatly saving the production cost and simplifying the transfer printing process.

[0003] Using the retransfer film as an intermediate medium, the image forming object can be formed on the transferred substrate without limitation. According to this method, the image needs to be formed on the intermediate medium retransfer film using thermal sublimation printing, and in the actual use process, the hardness of the substrate of the retransfer film is not enough, resulting in low printing color density. On the other hand, the thickness of the substrate used by the retransfer film is relatively thick, resulting in the need for a large amount of heat to achieve transfer printing, which not only causes loss of dye thermal sublimation and produces a large color difference, but also increases the production cost. In addition, the thermal sublimation retransfer film also has the defects of no special dye receiving coating, otherwise the color density is very low, the surface of the transferred object needs to be pretreated to realize thermal transfer printing, the substrate of the transfer film is relatively thick, resulting in high production cost, etc. In addition, other retransfer films may also need to be transferred with other carbon bands in the transfer printing process, which undoubtedly increases the production cost and the transfer printing process.

[0004] Lining printing and surface printing belong to intaglio printing, and the color order of the two printing is different. They have the defects of complex pre-plate making technology, long cycle, high plate making cost, etc. The application of thermal sublimation printing to the retransfer film as an intermediate medium can greatly simplify the lining printing process. However, the current retransfer film has the defects of insufficient color density of the image and high cost, which restricts its use in the market. SUMMARY

[0005] To solve the problems of the prior art, the present application provides an ultrathin thermal sublimation lining printing retransfer film, a preparation method thereof, and a transfer printing method. The ultrathin thermal sublimation lining printing retransfer film provided by the present application applied to the lining printing technology can not only significantly improve the color density of the image and improve the image effect, but also can print on demand, directly transfer without the aid of other carbon bands, greatly saving the production cost and simplifying the transfer printing process. The lining printing transferred object obtained by the present application not only has the exquisite pattern of thermal sublimation printing, but also reduces the production cost and simplifies the lining printing process.

[0006] The technical solutions provided by the present application are as follows:

[0007] The present application discloses a super-thin thermal dye sublimation transfer printing film, which comprises a back coating layer, a substrate layer, a release layer, a white ink layer and a dye receiving layer arranged in sequence.

[0008] <Substrate>:

[0009] The carbon tape comprises a substrate, a front layer coated on the surface of the substrate, the front layer comprising a release layer, a white ink layer and a dye receiving layer, and a back coating layer coated on the back of the substrate away from the protective layer.

[0010] The substrate is a transparent flexible plastic film, such as polypropylene (PP), polyethylene naphthalate (PEN), polyethylene terephthalate (PET), polyethylene (PE), polyvinyl alcohol (PVA), polymethyl methacrylate (PMMA) and the like. Preferably, PET and PEN are used.

[0011] Further, the thickness of the substrate is 2-5 μm, preferably 2-3 μm.

[0012] Generally, the PET film substrate can be pretreated before coating, and the treatment methods include corona discharge, plasma treatment, ozone treatment, flame treatment, primer (also known as anchor coating, adhesion promoter, easy-to-adhere agent) coating treatment, preheating treatment, dust removal treatment, evaporation treatment, alkali treatment, antistatic layer imparting and the like. The present application generally uses corona treatment. However, the inventors have proved by experiments that no treatment has no obvious effect on the performance of the final product.

[0013] <Release layer>:

[0014] The main function of the release layer is to impart certain adhesion to the front layer during thermal dye sublimation printing, to ensure that the dye receiving layer does not peel off from the PET substrate under high-speed printing conditions, and to help the dye receiving layer smoothly separate from the PET substrate to the surface of the transfer substrate during transfer printing.

[0015] In order to ensure that the release layer can be smoothly demolded from the PET, the release layer can be selected from acrylic resin, chlorovinyl-vinyl acetate copolymer, chlorovinyl-acrylic copolymer, EVA resin and the like, preferably acrylic resin. The Tg of the acrylic resin is preferably 70-110℃, and the molecular weight is 30000-200000.

[0016] Further, in order to improve the adhesion of the release layer to the PET substrate and the interlayer adhesion of the white ink layer, one or two of polyester resin, polyurethane resin (TPU), chloroether resin and the like can be added to the release layer. Preferably, chloroether resin with a softening point temperature of 40-80℃ is added in an amount of 100 mass% to 300 mass% of the acrylic resin. Too much amount will affect the demolding property of the release layer, and too low amount will affect the high-speed printing effect of the front layer.

[0017] In order to ensure that the release layer has good toughness, the release layer generally adds a certain amount of polyurethane resin (TPU), further preferably the glass transition temperature (Tg) is above -20°C and below 40°C, and the amount added is 0.02% to 0.05% of the total resin.

[0018] The preparation method of the release layer is to dissolve a certain amount of resin in butanone, ethyl acetate, toluene or the like, then add a certain amount of additives to obtain a release layer coating, then coat it on the surface of the substrate by gravure coating or slot coating and dry it, the drying temperature is 60-120°C, and the drying time is 0.5-2h.

[0019] The recommended coating thickness of the primer layer is 0.8-5μm, and the preferred thickness is 0.8-2μm.

[0020] <White ink layer>:

[0021] The function of the white ink layer is to make a white base for the image layer of the retransfer film, so as to improve the color density of the image. The resin of this layer can be selected from chlorovinyl-vinyl acetate copolymer, chloroether resin, polyester resin, thermoplastic acrylic resin, etc. In order to ensure the interlayer adhesion between the white ink layer and the dye receiving layer and the release layer, a non-crystalline polyester resin is preferably selected, further preferably the glass transition temperature (Tg) of the non-crystalline polyester is above 50°C and below 80°C, and the molecular weight is preferably above 3000 and below 25000. At the same time, the main pigment selected for the white ink layer is titanium dioxide, preferably the particle size of the titanium dioxide is 0.2-0.4um, and the ratio of the resin to titanium dioxide is 1:0.5 to 1:4, preferably 1:1 to 1:2.

[0022] Further, in order to reduce the time and energy required for the dispersion process during the grinding of titanium dioxide and to stabilize the titanium dioxide dispersion after grinding, a certain amount of dispersant needs to be added. As such a dispersant, for example, cationic wet dispersant, anionic wet dispersant, non-ionic wet dispersant, amphoteric wet dispersant, high molecular weight super dispersant, etc. can be mentioned, and the high molecular weight super dispersant is preferably selected, the amount of the dispersant is 0.2% to 50% of the titanium dioxide, preferably 0.5% to 30%.

[0023] Further, in order to improve the whiteness of the white ink layer, a certain amount of fluorescent whitening agent needs to be added. The fluorescent whitening agent has the property of converting ultraviolet light into blue, blue-violet or red visible light, producing an optical whitening effect. The fluorescent whitening agent includes one or a combination of diphenylstyrene type, coumarin type, pyrazoline type, benzoxazin type and benzoyl imide type, and the amount used is 1% to 10% of the titanium dioxide, preferably 1% to 5%.

[0024] In order to reduce the yellowing of the product during the transfer and use, a certain amount of antioxidant, light stabilizer, ultraviolet absorber and other additives need to be added to the coating.

[0025] Further, the antioxidant includes one or more combinations of hindered phenol, phosphite, thio, complex and hindered amine (HALS), and the amount of the antioxidant is 0.3 mass% to 0.5 mass% of the total amount.

[0026] Further, the light stabilizer includes one or more combinations of salicylate, benzophenone, benzotriazole, substituted acrylonitrile, and triazine ultraviolet absorber, and the amount of the light stabilizer is 0.1 mass% to 2 mass% of the total amount.

[0027] The preparation method of the white ink layer is to dissolve a certain amount of resin in butanone, ethyl acetate, toluene and other solvents, then add a dispersant, and after uniform dispersion, add titanium dioxide and grind to a particle size of about 0.2-0.4um, then add a certain amount of auxiliary agent to obtain a white ink layer coating, and then coat it on the release layer surface by gravure coating or slot coating, and dry at a temperature of 60-120℃ for 0.5-2h.

[0028] The recommended coating thickness of the white ink layer is 1-5um, and the preferred thickness is 2-2.5um.

[0029]

[0030] In addition to receiving heat transfer dye, the dye receiving layer should also have good adhesion to the surface of the transfer object. The main resin is preferably a halogenated resin such as polyvinyl chloride or polyvinylidene chloride, a vinyl chloride-vinyl acetate copolymer, and a chloroether resin, etc. The chloroether resin is preferred for its good adhesion to the target transfer substrate and good dye receiving capacity.

[0031] In order to further improve the adhesion of the dye receiving layer to the transfer object, a certain amount of auxiliary resin needs to be added. As such resins, for example, one or more of the following can be mentioned: thermoplastic polyurethane resin, polyester resin, acrylic modified polyolefin resin, etc. The preferred polyester resin has a glass transition temperature (Tg) of 60℃ or higher and 90℃ or lower, and a molecular weight of 7000 or higher and 25000 or lower. The content of the auxiliary resin is preferably 1 mass% or more and 15 mass% or less, and further preferably 3 mass% or more and 10 mass% or less, relative to the total mass of the dye receiving layer.

[0032] ​To prevent the problem of sticking between the printing layer and the ribbon due to the resin melting caused by heating during printing, a certain amount of anti-sticking agent is added to the printing layer for anti-sticking. Liquid or solid lubricants can be selected, such as polyethylene wax, amide wax, solid wax such as Teflon (registered trademark) powder, fluorine-based or phosphate-based surfactants, silicone oil, various modified silicone oils such as reactive silicone oil and curing silicone oil, etc., and modified silicone oil is preferred. The present application adopts the following scheme: a certain amount of aralkyl-modified silicone oil is added, which can provide good slipperiness during printing. The amount added is 1-10% of the total amount of resin.

[0033] In addition, a curing agent and polyethylene glycol can be added to the resin described above to improve the adhesion of the coating layer by crosslinking with the hydroxyl groups. The curing agent is not particularly limited and known substances can be used, and an aromatic polyisocyanate is preferred. The polyethylene glycol has a certain lubricity and dye wetting property in addition to providing hydroxyl crosslinking. The molecular weight of the polyethylene glycol is preferably 400-2000, and the hydroxyl value is in the range of 50-350 mgKOH / g. The amount of the curing agent and polyethylene glycol is controlled to be within the range of NCO / OH ratio of 0.3-0.8.

[0034] To reduce the yellowing of the product during transfer and use, a certain amount of antioxidant, light stabilizer, ultraviolet absorber and heat stabilizer and other additives need to be added to the coating layer.

[0035] Further, the antioxidant includes one or more combinations of hindered phenol, phosphite, thio, complex, and hindered amine (HALS), and the amount of the antioxidant is 0.3-0.5% of the total amount.

[0036] Further, the light stabilizer includes one or more combinations of salicylate, benzophenone, benzotriazole, substituted acrylonitrile, and triazine ultraviolet absorber, and the amount of the light stabilizer is 0.1-2% of the total amount.

[0037] Further, the heat stabilizer includes one or more combinations of metal soap, organotin, organoantimony, rare earth stabilizer, and liquid complex heat stabilizer, and the amount of the light stabilizer is 0.2-5% of the total amount.

[0038] The preparation method of the dye receiving layer is to dissolve a certain amount of resin in butanone, ethyl acetate, toluene and other solvents, then add a certain amount of additives to obtain a dye receiving layer coating, then coat it on the surface of the white ink layer by gravure coating or slot coating and dry it, the drying temperature is 60-120°C, and the drying time is 0.5-2h.

[0039] The recommended coating thickness of the dye receiving layer is 1-5μm, and the preferred thickness is 1-2.5μm.

[0040] <Back coating layer>

[0041] The back coating layer prevents the generation of stickiness or wrinkles due to the heating of the thermal head during printing. The back coating layer is preferably formed from a known thermoplastic resin. Examples of the thermoplastic resin include polyester resins, polyacrylate resins, polyvinyl acetate resins, styrene acrylate resins, polyurethane resins, polyethylene resins, polypropylene 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 silicone-modified products thereof. The polyvinyl butyral resin is preferred.

[0042] Further, to improve the heat resistance of the back coating layer during printing, an isocyanate compound can be added to the above-mentioned resin. The type of isocyanate compound is not particularly limited, and known compounds such as toluene diisocyanate (TDI), isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), dicyclohexylmethane diisocyanate (HMDI), hexamethylene diisocyanate (HDI), lysine diisocyanate (LDI), and the like can be used. An aromatic isocyanate compound is preferred, and examples of the aromatic isocyanate compound include 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, toluidine diisocyanate, p-phenylene diisocyanate, and the like. The amount of the isocyanate compound added is preferably 1 to 4% by weight of the thermoplastic resin.

[0043] Further, to maintain excellent sliding properties of the carbon ribbon during high-speed printing, an inorganic filler such as talc, kaolin, calcium carbonate, aluminum hydroxide, silicon dioxide, graphite, boron nitride, and a mold release agent such as a phosphate compound, a metal soap, silicone oil, and a surfactant can be added to the back coating layer. The inorganic filler is preferably talc or kaolin, and the amount of the inorganic filler added is preferably 1 to 5% by mass, and more preferably 3 to 5% by mass, of the resin. The mold release agent is preferably a phosphate compound, and the amount of the mold release agent added is preferably 1 to 10% by mass, and more preferably 3 to 5% by mass, of the resin.

[0044] The preparation method of the back coating layer is to dissolve a certain amount of resin in a conventional organic solvent. The type of the conventional organic solvent is not particularly limited, as long as the resin can be dissolved in the appropriate organic solvent and the viscosity at 25℃ is within 100-500 mPa·s. For example, the organic solvent can be selected from acetone, 2-butanone, cyclohexanone, isophorone, tetrahydrofuran, ethyl acetate, butyl acetate, propyl acetate, toluene, xylene, DMF, etc. 2-butanone and toluene are preferably miscible, and the ratio of 2-butanone to toluene is controlled between 8:2 and 1:1. The content is preferably more than 50% by mass and less than 80% by mass based on the total mass of the adhesive layer. Then a certain amount of additives is added to obtain a back coating paint, which is coated on the surface of the substrate by gravure coating or slot coating and dried at a temperature of 60-120℃ for 60-120S.

[0045] The coating thickness of the back coating layer is generally 0.4-1.2 μm, preferably 0.4-0.6 μm.

[0046] The present application also provides a preparation method of the ultra-thin thermal sublimation inner printing retransfer film, which is prepared in the order of the base layer, the back coating layer, the release layer, the white ink layer and the dye receiving layer.

[0047] The present application also provides a method for transferring using the ultra-thin thermal sublimation inner printing retransfer film, which is used for inner printing, and the specific steps are as follows:

[0048] 1) printing a pattern on the ultra-thin thermal sublimation inner printing retransfer film by thermal sublimation printing;

[0049] 2) transferring the dye receiving layer, the white ink layer and the release layer on the ultra-thin thermal sublimation inner printing retransfer film together to the surface of the transfer substrate by the first heat pressing at a temperature of 90-110℃;

[0050] 3) tightly bonding the dye receiving layer, the white ink layer and the release layer to the transfer substrate by the second heat pressing at a temperature of 90-110℃, so as to form a pattern on the inner surface of the transfer substrate.

[0051] The beneficial effects of the present application are as follows:

[0052] The ultra-thin thermal sublimation inner printing retransfer film provided by the present application not only can significantly improve the color density of the image and improve the image effect, but also can be printed on demand, directly transferred without the aid of other carbon tape, greatly saving the production cost and simplifying the transfer process.

[0053] The inner printing transfer object obtained by the present application not only has a fine pattern of thermal sublimation printing, but also reduces the production cost and simplifies the inner printing process. BRIEF DESCRIPTION OF DRAWINGS

[0054] Figure 1is a structural schematic diagram of the ultra-thin thermal sublimation inner printing retransfer film provided by the present application.

[0055] Figure 2 is a flow principle diagram of the method for performing transfer using the ultra-thin thermal sublimation inner printing retransfer film provided by the present application.

[0056] attached Figure 1 In the present application, the structures represented by each of the reference numerals are listed as follows:

[0057] 1, dye receiving layer, 2, white ink layer, 3, release layer, 4, base layer, 5, back coating layer. DETAILED DESCRIPTION

[0058] The principles and features of the present application are described below, and the examples are only used to explain the present application, and are not used to limit the scope of the present application.

[0059] In one embodiment, as shown in Figure 1 , the ultra-thin thermal sublimation inner printing retransfer film includes a back coating layer 5, a base layer 4, a release layer 3, a white ink layer 2, and a dye receiving layer 1 arranged in sequence.

[0060] In one embodiment, as shown in Figure 2 , the method for performing transfer using the ultra-thin thermal sublimation inner printing retransfer film includes the following steps:

[0061] 1) printing a pattern onto the retransfer film by thermal sublimation printing;

[0062] 2) transferring the front layer of the retransfer film (the front layer includes: dye receiving layer, white ink layer, release layer) to the surface of the transfer substrate by first heat pressing;

[0063] 3) tightly bonding the front layer and the transfer substrate by second heat pressing.

[0064] Example 1:

[0065] The substrate uses a 3μm PET film.

[0066] <Release layer>:

[0067] Acrylic resin (MB-3015, Tg: 76, Mn: 70000 Mitsubishi) 10 parts

[0068] Chloroether resin (MP-25 BASF) 10 parts

[0069] Polyurethane resin (TPU-5778, Tg: 31.1 Lubrizol) 1 part

[0070] 2-Butanone 39.5 parts

[0071] Toluene 39.5 parts

[0072] Gravure coater, coating thickness 1 μm.

[0073] <White ink layer>:

[0074] Polyester resin (885, Tg: 79, Mn: 8000 Toyobo) 15 parts

[0075] Titanium dioxide (R706, DuPont) 15 parts

[0076] Dispersant (710S, Oka) 3 parts

[0077] Antioxidant (B900, BASF) 0.5 parts

[0078] Ultraviolet absorber (Tinuvin 1130, BASF) 0.5 parts

[0079] Hindered amine light stabilizer (Tinuvin 123, BASF) 0.5 parts

[0080] Fluorescent whitening agent (OB-1, Rui Chemical) 0.3 parts

[0081] 2-Butanone 32.6 parts Toluene 32.6 parts

[0082] Gravure coater, coating thickness 1.2 μm.

[0083] <Dye receiving layer>:

[0084] Chlorinated ether resin (VC-40, BASF) 20 parts

[0085] Polyester resin (226, Tg: 65, Mn: 8000 Toyobo) 1 part

[0086] Modified silicone oil (BYK-322, BYK-Chemie) 2 parts

[0087] Isocyanate (TFD-90SB, Asahi Denka) 0.5 parts

[0088] Polyethylene glycol (PEG-600, Haian Petrochemical) 1 part

[0089] Antioxidant (B215, BASF) 0.5 parts

[0090] Ultraviolet absorber (Tinuvin 1130, BASF) 0.5 parts

[0091] Hindered amine light stabilizer (Tinuvin 123, BASF) 0.5 parts

[0092] Thermal stabilizer (XJ-169 II T, Baohua) 0.3 parts

[0093] 2-Butanone 36.85 parts Toluene 36.85 parts

[0094] Gravure coater, coating thickness 2 μm.

[0095] <Back coating layer>:

[0096] Polyvinyl butyral resin (S-LEC BH-6, Nippon Eternity) 10 parts

[0097] Polyisocyanate curing agent (TMHG-80B, Asahi Kasei) 3 parts

[0098] Silicone oil (KF-965-100cs, Shin-Etsu Silicone) 0.5 parts

[0099] Phosphate ester (MOA-3PK-70, Jiangsu Hai'an Petrochemical Factory) 0.6 parts

[0100] Talc (HY-TA05, Haiyang Powder) 0.6 parts

[0101] 2-Butanone 42.65 parts Toluene 42.65 parts Gravure coater, coating thickness 0.4 μm.

[0102] Example 2:

[0103] The substrate used was a 3 μm PET film.

[0104] <White ink layer>: The protocol was identical to Example 1.

[0105] <Dye receiving layer>: The protocol was identical to Example 1.

[0106] <Back coating layer>: The protocol was identical to Example 1.

[0107] <Release layer>:

[0108] Acrylic resin (MB-3015, Tg: 76, Mn: 70000, Mitsubishi) 10 parts

[0109] Polyurethane resin (TPU-5778, Tg: 31.1, Lubrizol) 10 parts

[0110] 2-Butanone 40 parts Toluene 40 parts Gravure coater, coating thickness 1 μm.

[0111] Example 3:

[0112] The substrate used was a 3 μm PET film.

[0113] <Release layer>: The protocol was identical to Example 1.

[0114] <Dye receiving layer>: The protocol was identical to Example 1.

[0115] <Back coating layer>: The protocol was identical to Example 1.

[0116] <White ink layer>:

[0117] Hydroxyl modified acrylic resin (SGR-016A, Tg: 50, Mn: 80000, Nippon Shokubai) 5 parts

[0118] Dispersant (710S, UCB) 3 parts

[0119] Antioxidant (B900, BASF) 0.5 parts

[0120] Ultraviolet absorber (Tinuvin 1130, BASF) 0.5 parts

[0121] Hindered amine light stabilizer (Tinuvin 123, BASF) 0.5 parts Fluorescent whitening agent (OB-1, Lingrui Chemical) 0.3 parts 2-Butanone 32.6 parts Toluene 32.6 parts

[0122] Gravure coater coating, coating thickness 1.2 μm.

[0123] Example 4:

[0124] Substrate 3 μm PET film was used.

[0125] <Release layer>: The scheme was consistent with Example 1.

[0126] <White ink layer>: The scheme was consistent with Example 1.

[0127] <Back coating layer>: The scheme was consistent with Example 1.

[0128] <Dye receiving layer>:

[0129] Chlorinated ether resin (VC-40, BASF) 20 parts

[0130] Acrylic modified polyolefin resin (350S, Sobi Chemical) 1 part Modified silicone oil (BYK-322, BYK-Chemie) 2 parts

[0131] Isocyanate (TFD-90SB, Asahi Kasei Polychem) 0.5 parts

[0132] Polyethylene glycol (PEG-600, Hai'an Petrochemical) 1 part

[0133] Antioxidant (B215, BASF) 0.5 parts

[0134] Ultraviolet absorber (Tinuvin 1130, BASF) 0.5 parts

[0135] Hindered amine light stabilizer (Tinuvin 123, BASF) 0.5 parts Heat stabilizer (XJ-169 II T, Baohua) 0.3 parts 2-Butanone 36.85 parts Toluene 36.85 parts

[0136] Gravure coater, coating thickness 2 μm.

[0137] Comparative Example 1:

[0138] The substrate used was a 3 μm PET film.

[0139] No release layer.

[0140] Comparative Example 2:

[0141] The substrate used was a 3 μm PET film.

[0142] No white ink layer.

[0143] Comparative Example 3:

[0144] The substrate used was a 3 μm PET film.

[0145] No dye receiving layer.

[0146] Comparative Example 4:

[0147] <Release layer>: The formulation was identical to Example 1.

[0148] <Dye receiving layer>: The formulation was identical to Example 1.

[0149] <Back coating layer>: The formulation was identical to Example 1.

[0150] <White ink layer>:

[0151] Pigment (R706, DuPont) 15 parts

[0152] Dispersant (Tego®710S, Tego) 3 parts

[0153] 2-Butanone 36.5 parts Toluene 36.5 parts

[0154] Gravure coater, coating thickness 1.2 μm.

[0155] Comparative Example 5:

[0156] The substrate used was a 3 μm PET film.

[0157] <White ink layer>: The formulation was identical to Example 1.

[0158] <Dye receiving layer>: The formulation was identical to Example 1.

[0159] <Back coating layer>: The formulation was identical to Example 1.

[0160] <Release layer>:

[0161] Acrylic resin (MB-3015, Tg: 76, Mn: 70000 Mitsubishi) 3 parts

[0162] Polyurethane resin (TPU-5778, Tg: 31.1 Lubrizol) 1 part

[0163] Comparative Example 6:

[0164] The substrate used was a 3 μm PET film.

[0165] <White ink layer>: The formulation was identical to Example 1.

[0166] <Dye receiving layer>: The formulation was identical to Example 1.

[0167] <Back coating layer>: The formulation was identical to Example 1.

[0168] <Release layer>:

[0169] Acrylic resin (MB-3015, Tg: 76, Mn: 70000 Mitsubishi) 19 parts

[0170] Polyurethane resin (TPU-5778, Tg: 31.1 Lubrizol) 1 part

[0171] Comparative Example 7:

[0172] The substrate used was a 3 μm PET film.

[0173] <White ink layer>: The formulation was identical to Example 1.

[0174] <Release layer>: The formulation was identical to Example 1.

[0175] <Back coating layer>: The formulation was identical to Example 1.

[0176] <Dye receiving layer>:

[0177] Chlorovinyl resin (SOLBIN-C Nisshin) 20 parts

[0178] Polyester resin (226, Tg: 65, Mn: 8000 Toyobo) 1 part

[0179] Modified silicone oil (BYK-322 BYK-Chemie) 2 parts

[0180] Isocyanate (TFD-90SB Asahi Denka) 0.5 part

[0181] Polyethylene glycol (PEG-600 Haean Petrochemical) 1 part

[0182] Antioxidant (Irganox 1076 BASF) 0.3 parts

[0183] UV absorber (Tinuvin 1130 BASF) 0.5 parts

[0184] Hindered amine light stabilizer (Tinuvin 123 BASF) 0.5 parts

[0185] Thermal stabilizer (XJ-169 II T Borchwar) 0.3 parts

[0186] 2-butanone 36.85 parts

[0187] Toluene 36.85 parts

[0188] Gravure coater coating, coating thickness 2 μm.

[0189] Performance test scheme:

[0190] The ultra-thin sublimation transfer printing film of Examples 1-4 and Comparative Examples 1-7 was tested, and the printing test was performed using a DTP330 sublimation soft label printer. The color bar was used with the original color bar, and the printing speed was 6 m / min. The transfer module used the DTP330 expansion module, and the transfer speed was 6 m / min. The first heat pressing temperature was 100°C, and the second heat pressing was 100°C.

[0191] Color density test:

[0192] The color density test pattern was a 255 gray scale pattern, and the printed sample size was 6x8 inches. After printing, the color density was tested using an X-Rite i1-PRO3 colorimeter, with a test point number of 256 (16x16), and the final color density was the average of 256 points.

[0193] Average color difference (△E*ab) test:

[0194] The color difference test pattern was a 150 gray scale pattern, and the printed sample size was 6x6 inches. After printing, the Lab test was performed using an X-Rite i1-PRO3 colorimeter, and the color difference △E * ab The color difference between the remaining 149 points and the first point was calculated based on the first point, and the final average color difference was the average of 149 points.

[0195] Transferability test:

[0196] The printed image was a 256 color scale pattern, and the test substrate was a 25 μm PET film. The evaluation criteria were as follows:

[0197] *A: complete transfer.

[0198] B: partially complete transfer.

[0199] C: no transfer.

[0200] The test results are as follows:

[0201]

[0202] The above description is merely the preferred embodiments of the present application, and is not used to limit the present application. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. An ultra-thin heat transfer sublimation retransfer print film, characterized in that: The back coating layer, the base layer, the release layer, the white ink layer and the dye receiving layer are sequentially arranged; The main resin material of the release layer is selected from acrylic resin with Tg of 70-110℃ and molecular weight of 30000-200000; The release layer further adds chloro-ether resin with softening point temperature of 40-80℃, and the addition amount is 100%-300% of the weight of the main resin of the release layer; The release layer further adds polyurethane resin with glass transition temperature of above-20℃ and below 40℃, and the addition amount is 0.02%-0.05% of the total resin weight in the release layer; The material of the white ink layer includes main resin and white pigment with weight ratio of (1:0.5)-(1:4): The main resin is selected from any one or mixture of more than one of chloro-vinyl acetate copolymer, chloro-ether resin, polyester resin or thermoplastic acrylic resin; The white pigment is selected from titanium white powder with particle size of 0.2μm-0.4μm; The white ink layer further adds any one or mixture of more than one of dispersant, fluorescent whitening agent, antioxidant or light stabilizer, wherein: The amount of the dispersant is 0.2%-50% of the weight of the white pigment; The amount of the fluorescent whitening agent is 1%-10% of the weight of the white pigment; The amount of the antioxidant is 0.3%-0.5% of the total weight of the white ink layer; The amount of the light stabilizer is 0.1%-2% of the total weight of the white ink layer; The thickness of the white ink layer is 1-5μm; The main resin is non-crystalline polyester resin with glass transition temperature of above 50℃ and below 80℃, and molecular weight of above 3000 and below 25000; The dispersant is selected from any one or mixture of more than one of cationic wet dispersant, anionic wet dispersant, non-ionic wet dispersant, amphoteric wet dispersant or high molecular super dispersant; The fluorescent whitening agent is selected from any one or mixture of more than one of stilbene type, coumarin type, pyrazoline type, benzoxazin type or benzimidazole type; The antioxidant is selected from any one or mixture of more than one of hindered phenol, phosphite, sulfide, complex or hindered amine; The light stabilizer is selected from any one or mixture of more than one of salicylate, benzophenone, benzotriazole, substituted acrylonitrile or triazine ultraviolet absorber; The main resin material of the dye receiving layer is selected from any one or mixture of more than one of polyvinyl chloride, polyvinylidene chloride, chloro-vinyl acetate copolymer or chloro-ether resin; The dye receiving layer further includes auxiliary resin selected from non-crystalline polyester resin with glass transition temperature of above 60℃ and below 90℃ and molecular weight of above 7000 and below 25000, and the amount of the auxiliary resin is 1%-15% or 3%-10% of the total weight of the dye receiving layer.

2. The ultra-thin dye-sublimation retransfer print film according to claim 1, characterized in that: The material of the back coating layer is selected from any one or a mixture of more than one of the following thermoplastic resins modified or unmodified by silicone: polyester-based thermoplastic resin, polyacrylate-based thermoplastic resin, polyvinyl acetate-based thermoplastic resin, styrene-acrylate-based thermoplastic resin, polyurethane-based thermoplastic resin, polyethylene-based thermoplastic resin, polypropylene-based thermoplastic resin, polystyrene-based thermoplastic resin, polyvinyl chloride-based thermoplastic resin, polyether-based thermoplastic resin, polyamide-based thermoplastic resin, polyimide-based thermoplastic resin, polyamide-imide-based thermoplastic resin, polycarbonate-based thermoplastic resin, polyacrylamide thermoplastic resin, polyvinyl chloride thermoplastic resin, polyvinyl butyral thermoplastic resin, or polyvinyl acetal thermoplastic resin.

3. The ultra-thin dye-sublimation retransfer print film according to claim 2, wherein, One or more of the following conditions are met: The back coating layer further comprises an isocyanate compound, which is added in an amount of 1-4% by weight of the thermoplastic resin, the isocyanate compound being selected from any one or a mixture of more than one of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, or lysine diisocyanate; The back coating layer further comprises an inorganic filler, which is added in an amount of 1-5% by weight of the resin, or 3-5%, the inorganic filler being selected from any one or a mixture of more than one of talc, kaolin, calcium carbonate, aluminum hydroxide, silicon dioxide, graphite, or boron nitride; The back coating layer further comprises a release agent, which is added in an amount of 1-10% by weight of the resin, or 3-5%, the release agent being selected from any one or a mixture of more than one of phosphate ester compound, metal soap, silicone oil, or surfactant; The thickness of the back coating layer is 0.4-1.2 μm, or 0.4-0.6 μm.

4. The ultra-thin thermal sublimation reverse printing transfer film according to claim 1, wherein: The base layer is a transparent flexible plastic film, which is selected from any one of polypropylene, polyethylene naphthalate, polyethylene terephthalate, polyethylene, polyvinyl alcohol, or polymethyl methacrylate; The thickness of the base layer is 2-5 μm, or 2-3 μm.

5. The ultra-thin dye-sublimation retransfer print film according to claim 1, wherein: The thickness of the release layer is 0.8-5 μm, or 0.8-2 μm.

6. The ultra-thin thermal sublimation reverse printing transfer film according to any one of claims 1-5, wherein: The dye-receiving layer further comprises a release agent, which is selected from a liquid release agent or a solid release agent, the solid release agent being selected from any one or a mixture of more than one of polyethylene wax, amide wax, or Teflon powder, the liquid release agent being selected from any one or a mixture of more than one of fluorine-based or phosphate-based surfactant, silicone oil, reactive silicone oil, or curable silicone oil; the release agent being used in an amount of 1-10% by weight of the total weight of the resin in the dye-receiving layer. The dye receiving layer further comprises a curing agent selected from aromatic polyisocyanate and polyethylene glycol with a molecular weight of 400-2000 and a hydroxyl value ranging from 50 mgKOH / g to 350 mgKOH / g, and the polyethylene glycol is added in an amount of 1% to 5% of the total weight of the dye receiving layer; the NCO / OH ratio of the added curing agent and the added polyethylene glycol is within 0.3-0.8; The dye receiving layer further comprises an antioxidant selected from any one or combination of hindered phenols, phosphites, sulfides, complexes, or hindered amines; the antioxidant is added in an amount of 0.3% to 0.5% of the total weight of the dye receiving layer; The dye receiving layer further comprises a light stabilizer selected from any one or combination of hindered phenols, phosphites, sulfides, complexes, or hindered amines; the light stabilizer is added in an amount of 0.1% to 2% of the total weight of the dye receiving layer; The dye receiving layer further comprises a heat stabilizer selected from any one or combination of metal soaps, organic tin, organic antimony, rare earth stabilizers, or liquid complex heat stabilizers; the heat stabilizer is added in an amount of 0.2% to 5% of the total weight of the dye receiving layer; The thickness of the dye receiving layer is 1 μm to 5 μm, or 1 μm to 2.5 μm.

7. A method of producing the ultra-thin dye sublimation transfer film according to any one of claims 1 to 6, characterized by, The method comprises the following steps: 1) Obtain a base layer material and calibrate both sides; 2) Prepare the back coating layer material into a coating according to the amount of the formula, coat it on one surface of the substrate by gravure coating or slot coating, and dry it at a drying temperature of 60-120°C for 60-120 seconds; 3) Prepare the release layer material into a coating according to the amount of the formula, then coat it on the other surface of the substrate by gravure coating or slot coating, and dry it at a drying temperature of 60-120°C for 0.5-2 hours; 4) Prepare the white ink layer material into a coating according to the amount of the formula, then coat it on the surface of the release layer by gravure coating or slot coating, and dry it at a drying temperature of 60-120°C for 0.5-2 hours; 5) Prepare the dye receiving layer material into a coating according to the amount of the formula, then coat it on the surface of the white ink layer by gravure coating or slot coating, and dry it at a drying temperature of 60-120°C for 0.5-2 hours.

8. A transfer method characterized by, The method for printing the inner print of the ultra-thin thermal sublimation inner print retransfer film according to any one of claims 1 to 6 comprises the following steps: 1) Print a pattern on the ultra-thin thermal sublimation inner print retransfer film by thermal sublimation printing; 2) Transfer the dye receiving layer, the white ink layer, and the release layer on the ultra-thin thermal sublimation inner print retransfer film together to the surface of a transfer substrate by first heat pressing at a temperature of 90-110°C; 3) Make the dye receiving layer, the white ink layer, and the release layer tightly adhere to the transfer substrate by second heat pressing at a temperature of 90-110°C.

Images