High-resistance metal mark and preparation method thereof

Abstract

The invention relates to a high-resistance metal mark and a preparation method thereof. The metal mark comprises a first base material layer and a second base material layer which are sequentially arranged from bottom to top. The first base material layer comprises a metal base material layer and a pretreatment layer which are sequentially arranged from bottom to top; the second base material layer comprises a transparent flexible plastic film, a stripping layer, a protective layer and a bonding layer which are sequentially arranged from bottom to top; the pretreatment layer is prepared from the following raw materials in parts by weight: 19 to 22 parts of first resin and 0.05 to 0.3 part of adhesion promoter; the stripping layer is prepared from the following raw materials in parts by weight: 11 to 15 parts of second resin, 0.2 to 0.4 part of adhesive and 0.4 to 0.7 part of lubricant; the protective layer is prepared from the following raw materials in parts by weight: 24 to 27 parts of third resin, 0.2 to 0.5 part of an isocyanate compound, 0.4 to 0.8 part of an ultraviolet absorbent and 0.3 to 1 part of an antioxidant; the bonding layer is prepared from the following raw materials in parts by weight: 18 to 21 parts of fourth resin. The metal mark is high in printing speed and excellent in performance, personalized customization can be achieved, the use scene is widened, and the metal mark is environmentally friendly.

Description

Technical Field

[0001] The invention relates to the technical field of metal marking, and in particular to a high-durability metal marking and a preparation method thereof. Background Art

[0002] There are many problems with metal logos on the market: ① The printing speed is relatively slow during the screen printing process, and each color needs to be printed separately; ② The operation process is relatively cumbersome, and it is necessary to prepare films and screens, adjust colors, and make proofs in advance; ③ The more colors a pattern has, the more plates are required, the longer the preparation time is, and the plate-making cost is high. Once the plate-making is completed, the layout cannot be changed quickly; ④ The final product cannot take into account all resistance properties, such as friction resistance, water resistance, corrosion resistance, weather resistance, etc.; ⑤ The pollution to the environment is serious, and the VOC emissions are relatively high; ⑥ It cannot meet the small-batch production needs of customers; ⑦ It cannot meet the personalized customization needs of customers and the market, reducing the scope of use and application scenarios of metal logos. Summary of the invention

[0003] In order to solve the above technical problems, the purpose of the present invention is to provide a high-durability metal label and a preparation method thereof. The metal label of the present invention has a fast printing speed, and has excellent properties such as friction resistance, water resistance, corrosion resistance, and weather resistance. It can meet the personalized customization requirements of customers, broaden the use scenarios of metal labels, and reduce conflicts with the environment during use, making it more green and environmentally friendly.

[0004] The technical solution of the present invention to solve the above technical problems is as follows:

[0005] The first object of the present invention is to provide a high-durability metal marker, the metal marker comprising a first substrate layer and a second substrate layer arranged in sequence from bottom to top;

[0006] The first substrate layer includes a metal substrate layer and a pretreatment layer arranged in sequence from bottom to top; the second substrate layer includes a plastic film layer, a peeling layer, a protective layer, and an adhesive layer arranged in sequence from bottom to top;

[0007] The pretreatment layer comprises the following raw materials in parts by weight: 19-22 parts of the first resin and 0.05-0.3 parts of the adhesion promoter;

[0008] The peeling layer comprises the following raw materials in parts by weight: 11-15 parts of the second resin, 0.2-0.4 parts of the adhesive, and 0.4-0.7 parts of the lubricant;

[0009] The protective layer comprises the following raw materials in parts by weight: 24-27 parts of a third resin, 0.2-0.5 parts of an isocyanate compound, 0.4-0.8 parts of an ultraviolet absorber, and 0.3-1 parts of an antioxidant;

[0010] The adhesive layer includes the following raw materials in parts by weight: 18-21 parts of the fourth resin.

[0011] The beneficial effects of the present invention are as follows: the metal label of the present invention comprises a first substrate layer and a second substrate layer; the first substrate layer comprises a metal substrate layer and a pretreatment layer, wherein the metal substrate layer plays a role in receiving patterns; the pretreatment layer plays a role in having good adhesion to the metal surface and can be well adhered to the transfer film. The second substrate layer comprises four layers: a transparent flexible plastic film, a peeling layer, a protective layer and an adhesive layer. The transparent flexible plastic film plays a role in supporting printing; the peeling layer plays a role in demoulding in the thermal transfer module; the protective layer plays a role in protecting the image in the thermal transfer module and improving the durability of the image; the adhesive layer plays a role in receiving the image in the thermal transfer module.

[0012] The metal label of the present invention has a fast printing speed and excellent properties such as friction resistance, water resistance, corrosion resistance, and weather resistance. It can meet the personalized customization requirements of customers, broaden the use scenarios of metal labels, and reduce conflicts with the environment during use, making it more green and environmentally friendly.

[0013] Based on the above technical solution, the present invention can also be improved as follows.

[0014] Furthermore, the metal substrate layer includes at least one of a steel plate, an aluminum plate, a zinc plate, a copper plate, a metal alloy plate, and a metal coating.

[0015] Further, the first resin includes at least one of water-based styrene acrylic resin, polyester resin, polyurethane resin, hydroxy acrylic resin, epoxy resin, polyvinyl butyral resin, and polyvinyl pyrrolidone resin;

[0016] The adhesion promoter includes at least one of a silane coupling agent, an organic silane adhesion promoter, an organic titanate adhesion promoter, a zircon adhesion promoter, a zirconium oxide aluminate adhesion promoter, an alkyl phosphate adhesion promoter, a chromium complex adhesion promoter, and an amine adhesion promoter.

[0017] The beneficial effects of adopting the above further scheme are: the role of the pretreatment layer in the metal marking is to improve the surface bonding performance of the pretreatment layer and the metal substrate layer by pre-coating the metal surface; second, to improve the adhesion between the pattern layer and the metal substrate layer after transfer by pre-coating the metal surface; third, the water resistance between the pattern layer and the metal substrate layer after transfer can be improved, and the coating will not have problems such as blistering, discoloration, shedding, and reduced adhesion.

[0018] At the same time, in order to ensure that the pretreatment layer has good adhesion to the metal surface, the pattern layer after transfer has good adhesion and water resistance to the pretreatment layer on the surface of the metal substrate layer. The first resin is added to the pretreatment layer to improve the adhesion between the metal surface and the pretreatment layer, and an adhesion promoter is also added to significantly improve the adhesion between the substrate and the coating layer, and improve the flexibility, ductility, corrosion resistance, and water immersion resistance of the coating.

[0019] Preferably, the first resin is a water-based styrene acrylic resin, which has excellent film-forming properties after drying, and the coating film has excellent water resistance and corrosion resistance and good adhesion to metals.

[0020] Further, the second resin includes at least one of acrylonitrile-butadiene-styrene copolymer resin, polystyrene resin, polycarbonate resin, polymethyl methacrylate resin, polyacrylic acid resin, and thermoplastic acrylic resin;

[0021] The adhesive comprises at least one of polyester resin, polyurethane resin and polycarbonate resin;

[0022] The lubricant includes at least one of wax powder, silicon dioxide, aluminum oxide, titanium dioxide, molybdenum disulfide, calcium carbonate, talcum powder, phosphate ester compound, metal soap, silicone oil and surfactant.

[0023] The beneficial effects of adopting the above further scheme are: the peeling layer has the following functions: first, the transfer layer can be demoulded smoothly after printing; second, it has a certain degree of protection for the bottom layer material, thereby improving the quality and durability of the product. In order to ensure that the peeling layer has good demoulding performance and a certain degree of protection after printing, a second resin is added to the peeling layer; at the same time, an adhesive is added to improve the flexibility of the peeling layer and the rubbing resistance of the coating. In order to improve the friction resistance of the peeling layer and the smoothness of the coating surface after transfer, a lubricant needs to be added to the peeling layer.

[0024] Preferably, the second resin is polyacrylic acid resin. In consideration of the excellent demoulding performance and weather resistance of the peeling layer, polyacrylic acid resin with a Tg of 80-130° C. and a molecular weight of 30,000-200,000 is further preferred.

[0025] Preferably, the adhesive is polyurethane resin, which can improve the adhesion between layers and improve the interlayer resin adhesion. Polyurethane has excellent high tension, high tensile strength, strong toughness and aging resistance. It is a mature environmentally friendly material with high strength, good toughness, wear resistance, cold resistance, oil resistance, aging resistance, weather resistance and other characteristics that other plastic materials cannot match.

[0026] Preferably, the lubricant is wax powder-PTFE modified polyethylene wax, which can improve surface hardness, slipperiness, and friction resistance, and has little effect on transparency and brightness.

[0027] Further, the third resin includes at least one of polyester resin, polyacrylate resin, styrene acrylate resin, polyurethane resin, polyethylene resin, polypropylene resin, polyolefin resin, polystyrene resin, polyvinyl chloride resin, polyvinyl butyral resin, amino resin, epoxy resin, hydroxyl acrylic resin, hydroxyl-modified vinyl chloride-acrylate resin, polyester-modified acrylic resin, and acrylic-modified polyester resin;

[0028] The isocyanate compound includes at least one of toluene diisocyanate (TDI), isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), dicyclohexylmethane diisocyanate (HMDI), hexamethylene diisocyanate (HDI), and lysine diisocyanate (LDI);

[0029] The ultraviolet absorber includes at least one of a salicylate ultraviolet absorber, a benzophenone ultraviolet absorber, a benzotriazole ultraviolet absorber, a substituted acrylonitrile ultraviolet absorber, a triazine ultraviolet absorber, a hindered amine ultraviolet absorber, a quencher, and a light shielding agent;

[0030] The antioxidant comprises at least one of hindered phenol antioxidants, phosphite antioxidants, thio antioxidants, composite antioxidants and hindered amine antioxidants.

[0031] The beneficial effects of adopting the above further scheme are: the role of the protective layer is to improve the direct adhesion between layers (i.e. adhesion); secondly, to improve the resistance of the coating after transfer (weather resistance, friction resistance, corrosion resistance, water resistance); in order to increase the adhesion of the coating, the protective layer is suitably selected from a third resin containing a reactive group. In addition, in order to improve the adhesion of the cured layer and the friction resistance of the coating, an isocyanate compound can be added to the above third resin. In order to improve the weather resistance of the coating, an ultraviolet absorber needs to be added. Finally, a certain amount of antioxidant needs to be added to the coating to extend the service life and thermal stability of the product.

[0032] Preferably, the third resin is one or more of hydroxyl-modified acrylic resin, hydroxyl-modified vinyl chloride-acrylate resin, polyester-modified acrylic resin, acrylic-modified polyester, etc., in consideration of interlayer adhesion and resistance.

[0033] Preferably, the third resin is a hydroxyl-modified acrylic resin, which provides excellent wear resistance, chemical corrosion resistance and adhesion properties, and the chemical structure of the secondary hydroxyl acrylic resin contains hydroxyl and acrylic groups. It has good solubility, high molecular weight and thermal stability, and is an ideal synthetic resin.

[0034] Preferably, the third resin is a hydroxyl-modified acrylic resin with a Tg of 70-95° C. and a molecular weight of 20,000-50,000.

[0035] Preferably, the isocyanate compound is an aromatic isocyanate, including at least one of 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, toluidine diisocyanate, and p-phenylene diisocyanate.

[0036] Preferably, the ultraviolet absorber is a benzophenone ultraviolet absorber, which has a slower absorption effect on UV-A, UV-B, and UV-C. The strength of the intrinsic hydrogen bond of the molecule is related to its light stabilization effect. The stronger the hydrogen bond, the greater the energy required to destroy it, and the better the effect. Its working principle is: the ketone group and the hydroxyl group in the molecule form a chelate ring due to the intrinsic hydrogen bond. After the chelate ring absorbs ultraviolet light energy, thermal vibration of the molecule occurs, and the intrinsic hydrogen bond is destroyed, causing the chelate ring to open, thereby converting light energy into heat energy and releasing it; in addition, light energy can also cause the carbonyl group in the molecule to produce tautomerism and generate an enol structure, which will also consume part of the energy. The benzophenone ultraviolet absorber has the characteristics of good compatibility, low volatility, good durability, low mobility, good thermal stability, high absorption efficiency, etc., and has the characteristics of blocking short-wave blue light and delaying physical loss, and is suitable for thick coatings.

[0037] Preferably, the ultraviolet absorber is a solid benzophenone ultraviolet absorber with a melting point of 70-250°C.

[0038] Preferably, the antioxidant is a high molecular weight hindered phenol antioxidant, which can be used in combination with other additives, such as auxiliary stabilizers (thioethers, phosphites), and the synergistic effectiveness of the mixture is better.

[0039] Further, the fourth resin includes at least one of vinyl resin, vinyl chloride-acrylate resin, polyester resin, acrylic resin, hydroxy acrylic resin, polyurethane, cellulose resin, melamine resin, polyamide resin, polyolefin resin, styrene resin, hydroxy-modified acrylic resin, hydroxy-modified vinyl chloride-acrylate resin, polyester-modified acrylic resin, and acrylic-modified polyester resin.

[0040] The beneficial effects of adopting the above-mentioned further scheme are: the role of the bonding layer is, first, to serve as a substrate for receiving carbon ribbon during printing, and the phenomenon of carbon ribbon sticking will not occur when printing the carbon ribbon; second, the pattern layer and the bonding layer have good interlayer adhesion after printing; third, the protective layer and the bonding layer have good adhesion, and there will be no problem of interlayer adhesion; the fourth resin in the bonding layer composition can be the same as the third resin of the protective layer from the perspective of resin hardness, moldability, good solubility, thermal stability and adhesion. The advantage is that when printing, it will serve as a pattern receiving layer without any anti-sticking carbon ribbon, and the interlayer adhesion with the protective layer is good.

[0041] Preferably, the fourth resin is a hydroxyl-modified acrylic resin, more preferably a hydroxyl-modified acrylic resin with a Tg of 70-95° C. and a molecular weight of 20,000-50,000.

[0042] Furthermore, the transparent flexible plastic film includes at least one of polypropylene, polyethylene naphthalate, polyethylene terephthalate, polyethylene, polyvinyl alcohol, and polymethyl methacrylate.

[0043] Furthermore, the thickness of the pretreatment layer is 0.5-2 μm; the thickness of the plastic film layer is 4.5-50 μm; the thickness of the peeling layer is 0.6-4 μm; the thickness of the protective layer is 2-15 μm; and the thickness of the adhesive layer is 2-2.5 μm.

[0044] The second object of the present invention is to provide a method for preparing a high-resistance metal marker, the method for preparing the metal marker is as follows:

[0045] S1: Prepared liquid: Pretreatment liquid: The first resin and the adhesion promoter are mixed and dissolved to prepare the pretreatment liquid for standby use; Stripping liquid: The second resin is dissolved in a solvent, and then an adhesive and a lubricant are added and mixed and dissolved to prepare a stripping liquid for standby use; Protective liquid: The third resin is dissolved in a solvent, and then an isocyanate compound, an ultraviolet absorber, and an antioxidant are added and mixed and dissolved to prepare a protective liquid for standby use; Adhesive liquid: The fourth resin is dissolved in a solvent to prepare an adhesive liquid for standby use;

[0046] S2: Preparation of the first substrate layer: coating the pretreatment liquid on one side of the metal substrate layer, and then drying to form a pretreatment layer, thereby obtaining the first substrate layer for standby use;

[0047] S3: Preparation of the second substrate layer: coating a stripping liquid on one side of the plastic film layer, and then drying to form a stripping layer for standby use; coating a protective liquid on the side of the stripping layer away from the plastic film layer, and then drying to form a protective layer; coating an adhesive liquid on the side of the protective layer away from the plastic film layer, and then drying to form an adhesive layer; thus, the second substrate layer is obtained;

[0048] S4: Preparation of metal logo: The second substrate layer is transferred to the surface of the first substrate layer by hot lamination and hot pressing at 100° C.-110° C. and 10 MPa-20 MPa, thereby obtaining a high-durability metal logo.

[0049] Furthermore, the drying temperature of the pretreatment layer is 60-100°C, and the drying time is 0.5-2h; the drying temperature of the peeling layer is 60-100°C, and the drying time is 0.5-2h; the drying temperature of the protective layer is 60-100°C, and the drying time is 0.5-2h; the drying temperature of the bonding layer is 60-100°C, and the drying time is 0.5-2h. BRIEF DESCRIPTION OF THE DRAWINGS

[0050] Figure 1 This is a schematic diagram of the metal marking structure prepared in Example 1 of the present invention;

[0051] Figure 2 This is a schematic diagram of the structure of the first substrate layer prepared in Example 1 of the present invention;

[0052] Figure 3 This is a schematic diagram of the structure of the second substrate layer prepared in Example 1 of the present invention;

[0053] Figure 4 This is a schematic diagram of the process route of step S4 in Example 1 of the present invention;

[0054] In the accompanying drawings, the components represented by the reference numerals are listed as follows:

[0055] 1-metal substrate layer; 2-pretreatment layer; 3-plastic film layer; 4-peeling layer; 5-protective layer; 6-adhesive layer. DETAILED DESCRIPTION

[0056] The principles and features of the present invention are described below, and the examples are only used to explain the present invention and are not used to limit the scope of the present invention. If no specific technology or conditions are specified in the embodiments, the technology or conditions described in the literature in this field or the product instructions are used. If the manufacturer of the reagents or instruments used is not specified, they are all conventional products that can be purchased through regular channels.

[0057] Example 1: Preparation of Metal Marking

[0058] S1: Prepared solution: Pretreatment solution: 20 parts of water-based styrene acrylic resin emulsion (Joncryl-7256; BASF Chemical, Germany) and 0.1 parts of silane coupling agent (MP-200; Momentive Chemical, USA) are mixed and dissolved to prepare a pretreatment solution for standby use; Stripping solution: 8 parts of thermoplastic acrylic resin (MB-2; Shanghai Bolier Chemical) and 4 parts of thermoplastic acrylic resin (MB-12; Shanghai Bolier Chemical) are dissolved in 43.52 parts of 2-butanone and 43.52 parts of toluene, and then 0.36 parts of polyurethane resin (TPU-9307 solid; BASF Chemical, Germany) and 0.6 parts of modified polyethylene wax (PEW-0674F; Nanjing Tianshi wax powder) are added and dissolved to prepare a stripping solution for standby use; Protective solution : 25 parts of hydroxy acrylic resin (SGR-015A; Guangzhou Changhao) were dissolved in 36.9 parts of 2-butanone and 36.9 parts of toluene, and then 0.3 parts of hexamethylene diisocyanate curing agent (SBN-70D; Dornaide), 0.5 parts of ultraviolet absorber (UV-49 (BP-6) solid Nanjing Milan Chemical), 0.3 parts of antioxidant (Irganox-1010; German BASF Chemical), 0.1 parts of antioxidant (Irganox-168; German BASF Chemical) were added and mixed and dissolved to prepare a protective solution for standby use; Adhesive solution: 20 parts of hydroxy acrylic resin (SGR-015A; Guangzhou Changhao) were dissolved in 40 parts of 2-butanone and 40 parts of toluene to prepare an adhesive solution for standby use;

[0059] S2: Preparation of the first substrate layer: The pretreatment liquid is coated on one side of a 85 μm steel plate 1 (Hunan Hengxinwang Metal Materials Co., Ltd.), and then dried to form a pretreatment layer 2 to obtain a first substrate layer, such as Figure 2 As shown, standby;

[0060] S3: Preparation of the second substrate layer: Use a gravure coater to coat a stripping liquid on one side of a 25 μm PET film 3 (Anhui Tongai Electronic Materials Co., Ltd.) with a coating thickness of 1.5 μm, and then dry to form a stripping layer 4 for standby use; then use a gravure coater to coat a protective liquid on the side of the stripping layer away from the 25 μm PET film with a coating thickness of 6 μm, and then dry to form a protective layer 5; use a gravure coater to coat an adhesive liquid on the side of the protective layer away from the 25 μm PET film with a coating thickness of 2.5 μm, and then dry to form an adhesive layer 6; that is, a second substrate layer is obtained, such as Figure 1 As shown;

[0061] S4: Preparation of metal labels: Figure 3 As shown, the second substrate layer is transferred to the surface of the first substrate layer by heat lamination and heat pressing, thereby obtaining a highly resistant metal logo, such as Figure 4 shown.

[0062] Example 2: Preparation of Metal Marker II

[0063] The difference between this embodiment and embodiment 1 is that the raw materials used in preparing the solution in step S1 are different, and the other steps are the same. Step S1 is as follows:

[0064] S1: Prepared liquid: Pretreatment liquid: 20 parts of water-based styrene acrylic resin emulsion (Joncryl-8052; BASF Chemical, Germany) and 0.12 parts of silane coupling agent (LD-3147; Lida Chemical) were mixed and dissolved to prepare a pretreatment liquid for standby use; Stripping liquid: 12 parts of thermoplastic acrylic resin (MB-2; Shanghai Bolier Chemical) were dissolved in 43.52 parts of 2-butanone and 43.52 parts of toluene, and then 0.36 parts of polyurethane resin (TPU-9307 solid; BASF Chemical, Germany) and 0.6 parts of modified polyethylene wax (PEW-0674F; Nanjing Tianshi wax powder) were added and dissolved to prepare a stripping liquid for standby use; Protective liquid: 25 parts of hydroxyl acrylic resin (SGR-015A; Guangzhou Changhao) was dissolved in 36.9 parts of 2-butanone and 36.9 parts of toluene, and then 0.3 parts of hexamethylene diisocyanate curing agent (TLA-100; Dornaide), 0.5 parts of ultraviolet absorber (UV-49 (BP-6) solid Nanjing Milan Chemical), 0.3 parts of antioxidant (Irganox-1010; BASF Chemical, Germany), and 0.1 parts of antioxidant (Irganox-168; BASF Chemical, Germany) were added and mixed and dissolved to prepare a protective solution for use; bonding solution: 20 parts of hydroxyl acrylic resin (SGR-015A; Guangzhou Changhao) was dissolved in 40 parts of 2-butanone and 40 parts of toluene to prepare a bonding solution for use.

[0065] Example 3: Preparation of Metal Marking III

[0066] The difference between this embodiment and embodiment 1 is that the raw materials used in preparing the solution in step S1 are different, and the other steps are the same. Step S1 is as follows:

[0067] S1: Preparation of liquid: Pretreatment liquid: 20 parts of water-based styrene acrylic resin emulsion (Joncryl-8052; BASF Chemical, Germany) and 0.1 parts of silane coupling agent (MP-200; Momentive Chemical, USA) were mixed and dissolved to prepare a pretreatment liquid for standby use; Stripping liquid: 12 parts of thermoplastic acrylic resin (MB-2; Shanghai Bolier Chemical) were dissolved in 43.52 parts of 2-butanone and 43.52 parts of toluene, and then 0.36 parts of polyurethane resin (R-6835; Hunan Jinliyuan) and 0.6 parts of modified polyethylene wax (PEW-0674F; Nanjing Tianshi wax powder) were added and dissolved to prepare a stripping liquid for standby use; Protective liquid: 25 parts of hydroxyl acrylic resin (SG R-015A; Guangzhou Changhao) was dissolved in 36.9 parts of 2-butanone and 36.9 parts of toluene, and then 0.3 parts of hexamethylene diisocyanate curing agent (TLA-100; Dornaide), 0.5 parts of ultraviolet absorber (UV-49 (BP-6) solid Nanjing Milan Chemical), 0.3 parts of antioxidant (Irganox-1010; BASF Chemical, Germany), and 0.1 parts of antioxidant (Irganox-168; BASF Chemical, Germany) were added and mixed and dissolved to prepare a protective solution for use; bonding solution: 20 parts of hydroxyl acrylic resin (SGR-015A; Guangzhou Changhao) were dissolved in 40 parts of 2-butanone and 40 parts of toluene to prepare a bonding solution for use.

[0068] Example 4: Preparation of Metal Marker IV

[0069] The difference between this embodiment and embodiment 1 is that the raw materials used in preparing the solution in step S1 are different, and the other steps are the same. Step S1 is as follows:

[0070] S1: Prepared liquid: Pretreatment liquid: 20 parts of water-based styrene acrylic resin emulsion (Joncryl-8052; BASF Chemical, Germany) and 0.12 parts of silane coupling agent (LD-3147; Lida Chemical) were mixed and dissolved to prepare a pretreatment liquid for standby use; Stripping liquid: 12 parts of thermoplastic acrylic resin (MB-250; Shanghai Bolier Chemical) were dissolved in 43.52 parts of 2-butanone and 43.52 parts of toluene, and then 0.36 parts of polyurethane resin (TPU-9307 solid; BASF Chemical, Germany) and 0.6 parts of modified polyethylene wax (PEW-0674F; Nanjing Tianshi wax powder) were added and dissolved to prepare a stripping liquid for standby use; Protective liquid: 25 parts of hydroxyl acrylic resin (E15 / 40A; Wacker Chemical, Germany) was dissolved in 36.9 parts of 2-butanone and 36.9 parts of toluene, and then 0.3 parts of hexamethylene diisocyanate curing agent (TLA-100; Dornaide), 0.5 parts of ultraviolet absorber (UV-49 (BP-6) solid Nanjing Milan Chemical), 0.3 parts of antioxidant (Irganox-1010; BASF Chemical, Germany), and 0.1 parts of antioxidant (Irganox-168; BASF Chemical, Germany) were added and mixed and dissolved to prepare a protective solution for use; bonding solution: 20 parts of hydroxyl acrylic resin (E15 / 40A; Wacker Chemical, Germany) were dissolved in 40 parts of 2-butanone and 40 parts of toluene to prepare a bonding solution for use.

[0071] Example 5: Preparation of Metal Markings

[0072] The difference between this embodiment and embodiment 1 is that the raw materials used in preparing the solution in step S1 are different, and the other steps are the same. Step S1 is as follows:

[0073] S1: Prepared solution: Pretreatment solution: 20 parts of water-based styrene acrylic resin emulsion (Joncryl-8052; BASF Chemical, Germany) and 0.1 parts of silane coupling agent (MP-200; Momentive Chemical, USA) were mixed and dissolved to prepare a pretreatment solution for standby use; Stripping solution: 8 parts of thermoplastic acrylic resin (MB-2; Shanghai Bolier Chemical) and 4 parts of thermoplastic acrylic resin (MB-12; Shanghai Bolier Chemical) were dissolved in 43.52 parts of 2-butanone and 43.52 parts of toluene, and then 0.36 parts of polyurethane resin (TPU-9307 solid; BASF Chemical, Germany) and 0.6 parts of modified polyethylene wax (PEW-0674F; Nanjing Tianshi wax powder) were added and mixed and dissolved to prepare a stripping solution for standby use; Protective solution: 25 parts of hydroxy acrylic resin (SGR-015A; Guangzhou Changhao) were dissolved in 36.9 parts of 2-butanone and 36.9 parts of toluene, and then 0.3 parts of hexamethylene diisocyanate curing agent (TLA-100; Dornaide), 0.5 parts of ultraviolet absorber (UV-49 (BP-6) solid; Nanjing Milan Chemical), 0.3 parts of antioxidant (Irganox-1010; BASF Chemical, Germany), and 0.1 parts of antioxidant (Irganox-168; BASF Chemical, Germany) were added and mixed and dissolved to prepare a protective solution for use; bonding solution: 20 parts of trivalent carboxyl chloroacetic acid resin (SOLBIN-M5; Nissin Chemical) were dissolved in 40 parts of 2-butanone and 40 parts of toluene to prepare a bonding solution for use.

[0074] Comparative Example 1: Preparation of Metal Marking

[0075] Compared with Example 1, the difference between this comparative example is that no stripping solution, protective solution, adhesive solution and corresponding coating are prepared (no step S3), and the remaining steps are the same as those of Example 1. Specifically, step S1 is as follows:

[0076] S1: prepared solution: pretreatment solution: the same as in Example 1;

[0077] S2: Preparation of the first substrate layer: the same as in Example 1;

[0078] S4: Preparation of metal logo: Use heat mounting (temperature: 100°C-110°C) and hot pressing (10MPa-20MPa) to transfer the 25μm PET film 3 to the surface of the metal substrate layer 1, thereby obtaining a high-durability metal logo.

[0079] Comparative Example 2: Preparation of Metal Marking

[0080] Compared with Example 1, the difference between this comparative example is that no pretreatment liquid and corresponding coating are prepared (no step S2), and the remaining steps are the same as those in Example 1. The specific steps are as follows:

[0081] S1: preparation liquid: stripping liquid: the same as in Example 1; protection liquid: the same as in Example 1; bonding liquid: the same as in Example 1;

[0082] S3: Preparation of the second substrate layer: the same as in Example 1;

[0083] S4: Preparation of metal logo: The second substrate layer is transferred to the surface of the metal substrate layer by heat lamination (temperature: 100°C-110°C) and hot pressing (10MPa-20MPa), thereby obtaining a highly durable metal logo.

[0084] Comparative Example 3: Preparation of Metal Marking

[0085] Compared with Example 1, the difference between this comparative example is that the composition of the protective solution in step S1 is different, and the remaining steps are the same as those in Example 1. Specifically, step S1 is as follows:

[0086] S1: Prepared liquid: Pretreatment liquid: the same as in Example 1; Stripping liquid: the same as in Example 1; Protective liquid: 25 parts of hydroxyl acrylic resin (SGR-015A; Guangzhou Changhao) were dissolved in 37.05 parts of 2-butanone and 37.05 parts of toluene, and then 0.5 parts of ultraviolet absorber (UV-49 (BP-6) solid Nanjing Milan Chemical), 0.3 parts of antioxidant (Irganox-1010; BASF Chemical, Germany), 0.1 parts of antioxidant (Irganox-168; BASF Chemical, Germany) were added and mixed and dissolved to prepare a protective liquid for use; Adhesive liquid: the same as in Example 1.

[0087] Comparative Example 4: Preparation of Metal Marking

[0088] Compared with Example 1, the difference between this comparative example is that the composition of the bonding liquid in step S1 is different, and the remaining steps are the same as those in Example 1. Specifically, step S1 is as follows:

[0089] S1: Prepared liquid: Pretreatment liquid: the same as in Example 1; Stripping liquid: the same as in Example 1; Protective liquid: the same as in Example 1; Adhesive liquid: 20 parts of polyester (220; Toyobo, Japan) are dissolved in 40 parts of 2-butanone and 40 parts of toluene to prepare an adhesive liquid for use.

[0090] Comparative Example 5: Preparation of Metal Marking

[0091] The difference between this comparative example and Example 1 is that no pretreatment liquid is prepared in step S1, and the composition of the stripping liquid is different. The remaining steps are the same as those in Example 1. Specifically, step S1 is as follows:

[0092] S1: Prepare the solution: Stripping solution: dissolve 8 parts of thermoplastic acrylic resin (MB-2; Shanghai Bolier Chemical) and 4 parts of thermoplastic acrylic resin (MB-12; Shanghai Bolier Chemical) into 44 parts of 2-butanone and 44 parts of toluene, mix and dissolve to prepare a stripping solution for use; Protective solution: the same as in Example 1; Adhesive solution: the same as in Example 1.

[0093] Comparative Example 6: Preparation of Metal Marking

[0094] Compared with Example 1, the difference between this comparative example is that the composition of the protective solution in step S1 is different, and the remaining steps are the same as those in Example 1. Specifically, step S1 is as follows:

[0095] S1: Prepared liquid: Pretreatment liquid: the same as in Example 1; Stripping liquid: the same as in Example 1; Protective liquid: dissolve 25 parts of hydroxyl acrylic resin (SGR-015A; Guangzhou Changhao) in 37.15 parts of 2-butanone and 37.15 parts of toluene, then add 0.3 parts of hexamethylene diisocyanate curing agent (SBN-70D; Dornaide), 0.3 parts of antioxidant (Irganox-1010; BASF Chemical, Germany), 0.1 parts of antioxidant (Irganox-168; BASF Chemical, Germany) and mix and dissolve them together to prepare a protective liquid for use; Adhesive liquid: the same as in Example 1.

[0096] Comparative Example 7: Preparation of Metal Marking

[0097] Compared with Example 1, the difference between this comparative example is that the composition of the protective solution in step S1 is different, and the remaining steps are the same as those in Example 1. Specifically, step S1 is as follows:

[0098] S1: Prepared liquid: Pretreatment liquid: the same as in Example 1; Stripping liquid: the same as in Example 1; Protective liquid: 25 parts of hydroxy acrylic resin (SGR-015A; Guangzhou Changhao) were dissolved in 40.9 parts of 2-butanone and 40.9 parts of toluene, and then 0.3 parts of antioxidant (Irganox-1010; BASF Chemical, Germany) and 0.1 parts of antioxidant (Irganox-168; BASF Chemical, Germany) were added and mixed and dissolved to prepare a protective liquid for use; Adhesive liquid: the same as in Example 1.

[0099] Test example: performance test

[0100] The metal labels prepared in Examples 1-5 and Comparative Examples 1-7 were respectively tested for printing using a DTP-500X / DTP-265E printer. The original ribbon was used. The print sample size was 6×6 inches. The printing speed was 51 mm / s. The specific test items were as follows:

[0101] ①Adhesion test

[0102] The German BYK-white grid knife test was used, and the grade was tested for adhesion according to the ISO 2409 grid method. The evaluation criteria are shown in Table 1 below:

[0103] Table 1: Evaluation criteria

[0104]

[0105]

[0106] ②Alcohol friction resistance test

[0107] The color density of the metal logos prepared in Examples 1-5 and Comparative Examples 1-7 before rubbing was tested using an X-Rite i1-PRO3 colorimeter, and the color density after rubbing was tested 2000 times with an alcohol friction tester DZ-204 and a WIP-1009D friction cloth at a weight of 1000g and a friction speed of 60 times / min. After the test was completed, the color density after rubbing was tested again with an X-Rite i1-PRO3 colorimeter, the ratio of the color density after rubbing to that before rubbing was calculated, and the glossiness was evaluated based on the following evaluation criteria. The evaluation results are shown in Table 2.

[0108] Table 2: Evaluation criteria

[0109] A OD ≥ 95% B 80%≤OD<95% C 60%≤OD<80% D OD<60%

[0110] ③ Gasoline friction resistance test

[0111] The metal labels prepared in Examples 1-5 and Comparative Examples 1-7 were subjected to gasoline friction resistance tests using an experimental instrument (DZ-204; Dongguan Zhonghao Testing Equipment Co., Ltd.). The steps were the same as those for the alcohol friction resistance test, and the evaluation criteria were as shown in Table 2.

[0112] ④Bending resistance test

[0113] The backs of the metal labels prepared in Examples 1-5 and Comparative Examples 1-7 were respectively placed close to a round steel bar with a diameter of 20 mm, and slowly bent along the steel bar by 90° within 30 seconds. The evaluation results are shown in Table 3.

[0114] Table 3: Evaluation criteria

[0115] OK There is no damage such as cracks, peeling, interlayer separation, etc. on the surface NG There are cracks, peeling, interlayer separation and other damage on the surface

[0116] ⑤Water resistance test

[0117] The metal labels prepared in Examples 1-5 and Comparative Examples 1-7 were placed in the tank, and sufficient deionized water was added to the tank to keep three-quarters of the metal label immersed in the water. Then the water in the tank was circulated or ventilated, and the water temperature was adjusted to 40±1°C, and this temperature was maintained throughout the test. The conductivity of the water in the tank was sampled and checked to be ≤2μs / cm. The test duration was 12h. The sample coating had no blistering, wrinkling, rust, loss of gloss, discoloration, shedding, reduced adhesion, and rust on the substrate after paint stripping. The evaluation results are also shown in Table 3.

[0118] ⑥Salt spray resistance test

[0119] The metal labels prepared in Examples 1-5 and Comparative Examples 1-7 were placed in a sodium chloride solution with a mass fraction of (5±1)% at room temperature for 48 hours. After the test, the samples were taken out, wiped dry and placed for 1 hour. The surface and the substrate should not show signs of fading, discoloration, fading, softening, wrinkling, blistering, cracking, delamination, curling or corrosion. The evaluation results are also shown in Table 3.

[0120] ⑦Impact resistance test

[0121] The metal labels prepared in Examples 1-5 and Comparative Examples 1-7 were placed in an environment of -20℃±3℃ for 1h, taken out and subjected to impact test within 5min, and placed face up on a steel plate with a thickness of 20mm. A solid steel ball with a diameter of 25mm was dropped freely from 2m above the sample, and the landing point was as close as possible to the flat part of the test sample. The sample surface should not have cracks, interlayer detachment, etc. outside the circular area with the impact point as the center and a radius of 6mm. The evaluation results are also shown in Table 3.

[0122] ⑧Pencil hardness performance test

[0123] The Zhonghua brand 101 drawing pencil produced by Shanghai China First Pencil Co., Ltd. was used to test the metal logos prepared in Examples 1-5 and Comparative Examples 1-7 using GB / T6739-2022.

[0124] ⑨Weather resistance test

[0125] The color density of the metal labels prepared in Examples 1-5 and Comparative Examples 1-7 before weathering was tested using an X-Rite i1-PRO3 colorimeter. A xenon lamp was used as the light source, which had a continuous spectrum at wavelengths between 300nm and 1200nm. The illumination on the sample surface should be between 30klx and 100klx. A standard window glass filter was placed between the xenon light source and the sample. The blackboard temperature in the box was selected to be 40℃±3℃, the relative humidity was selected to be 50%±5%, the exposure period was 24h drying, and the artificial accelerated aging test time was 1200h. After the test was completed, the color density of the metal labels prepared in Examples 1-5 and Comparative Examples 1-7 after weathering was tested using an X-Rite i1-PRO3 colorimeter, and the ratio of the color density after weathering to the color density before weathering was calculated.

[0126] The calculation results are shown in Table 4.

[0127] Table 4

[0128]

[0129]

[0130] From Table 4, we can get:

[0131] (1) The comprehensive performance of the metal labels of Examples 1-5 is better than the comprehensive performance of the metal labels of Comparative Examples 1-7. The metal labels of Comparative Examples 1 and 4 cannot be transferred. The reason is that in the process of preparing the metal label of Comparative Example 1, the second substrate layer lacks a peeling layer, a protective layer, and an adhesive layer; the first substrate layer of the metal label of Comparative Example 2 lacks a pretreatment layer; in the process of preparing the metal label of Comparative Example 4, the hydroxy acrylic resin in the adhesive layer of the second substrate layer is replaced with a polyester resin. It can be seen that the pretreatment layer and the peeling layer, the protective layer, and the adhesive layer in the embodiments of the present invention can better improve the adhesion between the metal label layers, and can improve the water resistance between the pattern layer and the metal substrate layer after transfer, and the coating will not have problems such as blistering, discoloration, shedding, and reduced adhesion.

[0132] (2) In the process of preparing the metal logo in Comparative Example 3, the protective layer of the second substrate layer did not add polyisocyanate curing agent, and was not resistant to alcohol and gasoline friction. It was also not resistant to water, salt spray, impact, pencil hardness and weather resistance, and had poor performance. It can be seen that adding polyisocyanate curing agent to the protective layer can improve the adhesion of the cured layer and improve the friction resistance of the coating. The metal logo of Comparative Example 5 has no pretreatment layer in its first substrate layer; modified polyethylene wax and polyurethane are not added to the peeling layer of the second substrate layer. Modified polyethylene wax can improve the adhesion between layers and improve the adhesion of interlayer resins; polyurethane can improve the adhesion between layers and improve the adhesion of interlayer resins, so all performances are poor.

[0133] (3) In the process of preparing the metal logo in Comparative Example 6, no ultraviolet absorber was added to the protective layer of the second substrate layer, and the various properties were equivalent to those of Examples 1-5. However, due to the lack of ultraviolet absorber, the weather resistance of the metal logo in Comparative Example 6 was only 48.2%, far lower than the 94.8%-98.4% of Examples 1-5. Compared with Comparative Example 6, the protective layer of Comparative Example 7 did not add polyisocyanate curing agent, and the weather resistance was only 28.5%. In addition, it was not resistant to alcohol and gasoline friction, and the pencil hardness performance was less than 2B.

[0134] In summary, the metal label provided by the present invention has strong adhesion, resistance to alcohol and gasoline friction, bending, water, salt spray, impact, pencil hardness> 2B, and good weather resistance through the design of the first substrate layer and the second substrate layer.

[0135] Although the embodiments of the present invention have been shown and described above, it is to be understood that the above embodiments are exemplary and are not to be construed as limitations of the present invention. A person skilled in the art may change, modify, replace and vary the above embodiments within the scope of the present invention.

Claims

1. A high-resistance metal marker, characterized in that: The metal logo comprises a first substrate layer and a second substrate layer which are arranged in sequence from bottom to top; The first substrate layer includes a metal substrate layer and a pretreatment layer arranged in sequence from bottom to top; the second substrate layer includes a plastic film layer, a peeling layer, a protective layer, and an adhesive layer arranged in sequence from top to bottom; the pretreatment layer is bonded to the adhesive layer; The pretreatment layer comprises the following raw materials in parts by weight: 19-22 parts of the first resin and 0.05-0.3 parts of the adhesion promoter; The peeling layer comprises the following raw materials in parts by weight: 11-15 parts of the second resin, 0.2-0.4 parts of the adhesive, and 0.4-0.7 parts of the lubricant; The protective layer comprises the following raw materials in parts by weight: 24-27 parts of a third resin, 0.2-0.5 parts of an isocyanate compound, 0.4-0.8 parts of an ultraviolet absorber, and 0.3-1 parts of an antioxidant; The adhesive layer includes the following raw materials in parts by weight: 18-21 parts of the fourth resin.

2. A high-resistance metal marker according to claim 1, characterized in that: The metal substrate layer includes at least one of a steel plate, an aluminum plate, a zinc plate, a copper plate, a metal alloy plate, and a metal coating.

3. A high-resistance metal marker according to claim 1, characterized in that: The first resin includes at least one of water-based styrene acrylic resin, polyester resin, polyurethane resin, hydroxy acrylic resin, epoxy resin, polyvinyl butyral resin, and polyvinyl pyrrolidone resin; The adhesion promoter includes at least one of a silane coupling agent, an organic silane adhesion promoter, an organic titanate adhesion promoter, a zircon adhesion promoter, a zirconium oxide aluminate adhesion promoter, an alkyl phosphate adhesion promoter, a chromium complex adhesion promoter, and an amine adhesion promoter.

4. A high-resistance metal marker according to claim 1, characterized in that: The second resin includes at least one of acrylonitrile-butadiene-styrene copolymer resin, polystyrene resin, polycarbonate resin, polymethyl methacrylate resin, and thermoplastic acrylic resin; The adhesive comprises at least one of polyester resin, polyurethane resin and polycarbonate resin; The lubricant includes at least one of wax powder, silicon dioxide, aluminum oxide, titanium dioxide, molybdenum disulfide, calcium carbonate, talcum powder, phosphate ester compound, metal soap, silicone oil and surfactant.

5. A high-resistance metal marker according to claim 1, characterized in that: The third resin includes at least one of polyester resin, polyacrylate resin, styrene acrylate resin, polyurethane resin, polyethylene resin, polypropylene resin, polyolefin resin, polystyrene resin, polyvinyl chloride resin, polyvinyl butyral resin, amino resin, epoxy resin, hydroxyl acrylic resin, hydroxyl-modified vinyl chloride-acrylate resin, polyester-modified acrylic resin, and acrylic-modified polyester resin; The isocyanate compound includes at least one of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, and lysine diisocyanate; The ultraviolet absorber includes at least one of a salicylate ultraviolet absorber, a benzophenone ultraviolet absorber, a benzotriazole ultraviolet absorber, a substituted acrylonitrile ultraviolet absorber, a triazine ultraviolet absorber, a hindered amine ultraviolet absorber, a quencher, and a light shielding agent; The antioxidant comprises at least one of hindered phenol antioxidants, phosphite antioxidants, thio antioxidants, composite antioxidants and hindered amine antioxidants.

6. A high-resistance metal marker according to claim 1, characterized in that: The fourth resin includes at least one of vinyl resin, vinyl chloride-acrylate resin, polyester resin, acrylic resin, hydroxy acrylic resin, polyurethane, cellulose resin, melamine resin, polyamide resin, polyolefin resin, styrene resin, hydroxyl-modified acrylic resin, hydroxyl-modified vinyl chloride-acrylate resin, polyester-modified acrylic resin, and acrylic-modified polyester resin.

7. A high-resistance metal marker according to claim 1, characterized in that: The plastic film layer is a transparent flexible plastic film, including at least one of polypropylene, polyethylene naphthalate, polyethylene terephthalate, polyethylene, polyvinyl alcohol, and polymethyl methacrylate.

8. A high-resistance metal marker according to claim 1, characterized in that: The thickness of the pretreatment layer is 0.5-2 μm; the thickness of the plastic film layer is 4.5-50 μm; the thickness of the peeling layer is 0.6-4 μm; the thickness of the protective layer is 2-15 μm; and the thickness of the bonding layer is 2-2.5 μm.

9. A method for preparing a high-durability metal marker according to any one of claims 1 to 8, characterized in that: The preparation method of the metal marker is as follows: S1: Preparation liquid: Pretreatment liquid: The first resin and the adhesion promoter are mixed and dissolved together to prepare the pretreatment liquid for standby use; Stripping liquid: The second resin is dissolved in a solvent, and then the adhesive and the lubricant are added and mixed and dissolved together to prepare the stripping liquid for standby use; Protective liquid: dissolve the third resin in a solvent, then add an isocyanate compound, an ultraviolet absorber, and an antioxidant to mix and dissolve to prepare a protective liquid for standby use; Adhesive liquid: dissolve the fourth resin in a solvent to prepare an adhesive liquid for standby use; S2: Preparation of the first substrate layer: coating the pretreatment liquid on one side of the metal substrate layer, and then drying to form a pretreatment layer, thereby obtaining the first substrate layer for standby use; S3: Preparation of the second substrate layer: coating a stripping liquid on one side of the plastic film layer, and then drying to form a stripping layer for standby use; coating a protective liquid on the side of the stripping layer away from the plastic film layer, and then drying to form a protective layer; coating an adhesive liquid on the side of the protective layer away from the plastic film layer, and then drying to form an adhesive layer; thus, the second substrate layer is obtained; S4: Preparation of metal logo: The second substrate layer is transferred to the surface of the first substrate layer by hot lamination and hot pressing at 100° C.-110° C. and 10 MPa-20 MPa, thereby obtaining a high-durability metal logo.

10. The method for preparing a metal marker according to claim 9, characterized in that: The drying temperature of the pretreatment layer is 60-100°C, and the drying time is 0.5-2h; the drying temperature of the peeling layer is 60-100°C, and the drying time is 0.5-2h; the drying temperature of the protective layer is 60-100°C, and the drying time is 0.5-2h; the drying temperature of the bonding layer is 60-100°C, and the drying time is 0.5-2h.

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