A TPU high and low temperature film with hot stamping and perforation effect and its preparation method

Abstract

This invention specifically relates to a TPU high and low temperature film with a hot stamping and perforation effect and its preparation method. The TPU high and low temperature film includes a TPU film, a PU layer disposed on one surface of the TPU film, a hot stamping resin layer disposed sequentially on the other surface of the TPU film, a pattern layer disposed on the surface of the hot stamping resin layer away from the TPU film, a metal plating layer disposed on the surface of the pattern layer away from the hot stamping resin layer, and a hot melt adhesive film layer disposed on the surface of the metal plating layer away from the pattern layer. The resulting TPU high and low temperature film has good mechanical properties, adhesion, wear resistance, scratch resistance, and aging resistance. Its excellent antistatic ability also helps to broaden the application range of this TPU high and low temperature film.

Description

Technical Field

[0001] This invention relates to the field of TPU film materials and their manufacturing processes, specifically to a TPU high and low temperature film with a hot stamping and perforation effect and its preparation method. Background Technology

[0002] As people's demands for exquisite texture and design in product packaging continue to rise, the production of packaging materials is constantly innovating. Currently, the most common hot stamping film on the market refers to a type of hot stamping material made by laminating a layer of metal foil onto a base film through coating and vacuum evaporation. This hot stamping film has a strong metallic luster and a high-end feel, but its preparation process is lengthy, its quality is unstable, its efficiency is low, and its cost is high. The most commonly used base materials for hot stamping film are PE film, PP film, or PET film. The choice of base material is a crucial prerequisite for ensuring the hot stamping effect and quality stability of the film. Although PET film is widely used in hot stamping processes, its relatively high price, sensitivity to ultraviolet light, and difficulty in processing have, to some extent, limited the development and application of hot stamping film. TPU film is a new type of functional film with high strength, good toughness, and excellent temperature and weather resistance, and is widely used in various industries to replace PVC, PE, or PP film products. However, at present, there are very few reports on the research or development of applying hot stamping technology to TPU film. Summary of the Invention

[0003] The purpose of this invention is to overcome the shortcomings of the prior art by providing a TPU high and low temperature film with hot stamping and hollowing effect and its preparation method.

[0004] The objective of this invention is achieved through the following technical solution:

[0005] This invention provides a TPU high and low temperature film with hot stamping and hollowing effect, comprising a TPU film, a PU layer disposed on one surface of the TPU film, a hot stamping resin layer disposed sequentially on the other surface of the TPU film, a pattern layer disposed on the surface of the hot stamping resin layer away from the TPU film, a metal plating layer disposed on the surface of the pattern layer away from the hot stamping resin layer, and a hot melt adhesive film layer disposed on the surface of the metal plating layer away from the pattern layer.

[0006] Furthermore, the hot stamping resin layer is an acrylic resin layer.

[0007] Furthermore, the acrylic resin layer is formed by coating the surface of the TPU film with acrylic resin and then drying and curing it. The preparation method of the acrylic resin includes the following steps: adding butyl methacrylate, methyl acrylate, acrylic acid and silane coupling agent to butyl acetate and stirring thoroughly, raising the temperature to 65-75°C, adding an initiator diluent, refluxing for 8-10 hours, and then allowing it to cool naturally to obtain a transparent liquid. Transferring it to a rotary evaporator to remove some of the solvent, and then adding the remaining liquid dropwise to methanol in small amounts several times. Under stirring conditions, a white precipitate is generated, and after drying, the acrylic resin is obtained.

[0008] Furthermore, the mass ratio of butyl methacrylate, methyl acrylate, acrylic acid and silane coupling agent is 65-70:20-25:1-5:5-9.

[0009] Furthermore, the initiating diluent is a solution composed of 2',2-azobisisobutyronitrile and butyl acetate, wherein the amount of 2',2-azobisisobutyronitrile is 0.3-0.7% of the total mass of butyl methacrylate, methyl acrylate and acrylic acid.

[0010] Furthermore, the hot melt adhesive film layer is a TPU hot melt adhesive film layer, and the preparation method of the TPU hot melt adhesive film layer includes the following steps:

[0011] A1. Add polycarbonate diol and hexamethylene diisocyanate to the reactor for an addition reaction until the NCO content in the system reaches the theoretical value.

[0012] A2. Take hydroxyethyl acrylate or pentaerythritol triacrylate, catalyst and hydroquinone and mix them thoroughly at 40-45°C under an inert atmosphere. Then add them to the reaction vessel of step A1 and continue the reaction under an inert gas atmosphere until the NCO groups in the system are completely reacted to obtain the polyurethane prepolymer.

[0013] A3. After thoroughly mixing the polyurethane prepolymer, antistatic agent, oxidant and solvent obtained in step A2, the adhesive is obtained. The adhesive is then coated onto the film-forming substrate. After drying and peeling, a polyurethane hot melt adhesive film is obtained.

[0014] Furthermore, the molar ratio of the polycarbonate diol, hexamethylene diisocyanate, and acrylate is 1:2:2, the mass of the catalyst is 0.05-0.2% of the mass of the acrylate, and the mass of the hydroquinone is 0.01-0.02% of the mass of the acrylate.

[0015] Furthermore, in step A3, the mass of the antistatic agent is 0.5-1.5% of the mass of the polyurethane prepolymer, and the mass of the oxidant is 0.1-1% of the mass of the polyurethane prepolymer.

[0016] Furthermore, the preparation method of the antistatic agent includes the following steps:

[0017] S1. Add methacrylic acid and a solution of dimethyl sulfoxide containing thionyl chloride to tetrahydrofuran and mix thoroughly. Add N,N-dimethylformamide and raise the temperature to 55-65℃. React for 2-4 hours. Then add 2,4,6-tris(dimethylaminomethyl)phenol and triethylamine and continue the reaction for 2-4 hours to obtain an intermediate product. Recrystallize the intermediate product with acetone and dry it.

[0018] S2. Place the dried intermediate product obtained in step S1 in anhydrous ethanol, add hydrochloric acid, react at room temperature for 0.5-1 h, then raise the temperature to 40-50℃, adjust the pH of the solution to 7.5-8, add epichlorohydrin, and continue the reaction for 8-10 h. Transfer to a rotary evaporator for rotary evaporation to evaporate the solvent, and then place the product in an oven to dry, thus obtaining the antistatic agent.

[0019] The present invention also provides a method for preparing the above-mentioned TPU high and low temperature film with hot stamping and hollowing effect, comprising the following preparation steps:

[0020] (1) Take a TPU film, coat one surface of the TPU film with PU coating, and dry to form a PU layer;

[0021] (2) Coat the other surface of the TPU film with hot stamping resin, and form a hot stamping resin layer after drying;

[0022] (3) A pattern layer with graphic information is formed by hot stamping on the surface of the hot stamping resin layer through a hot stamping process;

[0023] (4) A metal plating process is used to deposit a metal coating on the surface of the hot stamping resin layer by vacuum evaporation.

[0024] (5) Apply hot melt adhesive film to the surface of the metal coating, and after it is completely dried, it is laminated into a roll to obtain a TPU high and low temperature film with hot stamping effect.

[0025] Furthermore, the preparation method of the TPU high and low temperature film also includes step (6), which involves processing the TPU high and low temperature film with hot stamping effect by laser cutting, automatic vibrating knife or die cutting to form the required hollow shape, thereby obtaining the TPU high and low temperature film with hot stamping hollow effect.

[0026] The beneficial effects of this invention are as follows:

[0027] (1) The TPU high and low temperature film of the present invention has good mechanical properties, adhesion, wear resistance, scratch resistance and aging resistance. Among them, the acrylic resin layer is used as the hot stamping resin layer. The acrylic resin prepared by the combination of butyl methacrylate, methyl acrylate, acrylic acid and silane coupling agent has good mechanical properties, stability and temperature resistance. It has a fast curing speed and stable quality, and can better highlight the hot stamping effect of the TPU high and low temperature film. At the same time, it makes the hot stamping pattern layer and the TPU film substrate have a high adhesion and prevents delamination.

[0028] (2) The present invention uses TPU hot melt adhesive film as the protective layer of the TPU high and low temperature film, which greatly facilitates the storage and transportation of the TPU high and low temperature film, and makes the processing time of the TPU high and low temperature film short and the quality stable in application. Among them, the present invention modifies and synthesizes the TPU hot melt adhesive film by means of an antistatic agent during the preparation process, thereby significantly improving the antistatic ability of the TPU hot melt adhesive film.

[0029] (3) The preparation process of the TPU high and low temperature film of the present invention is clean and environmentally friendly, with fewer steps, shorter time, stable quality and lower production cost, and is suitable for large-scale production. Attached Figure Description

[0030] Figure 1 This is a product image of the TPU high and low temperature film with hot stamping and hollowing effect described in this invention. Detailed Implementation

[0031] To facilitate understanding by those skilled in the art, the present invention will be further described below with reference to embodiments. The content mentioned in the embodiments is not intended to limit the present invention.

[0032] In the following embodiments of the present invention, the TPU film used is a transparent TPU film of model ZD-135CM*85A from Guangdong Zhongding Technology Development Co., Ltd., with a thickness of 1.0mm.

[0033] Example 1

[0034] This embodiment provides a TPU high and low temperature film with hot stamping and hollowing effect, including a TPU film, a PU layer is disposed on one surface of the TPU film, a hot stamping resin layer is disposed sequentially on the other surface of the TPU film, a pattern layer is disposed on the surface of the hot stamping resin layer away from the TPU film, a metal plating layer is disposed on the surface of the pattern layer away from the hot stamping resin layer, and a hot melt adhesive film layer is disposed on the surface of the metal plating layer away from the pattern layer.

[0035] Furthermore, the hot stamping resin layer is an acrylic resin layer, which is formed by coating the surface of the TPU film with acrylic resin and then drying and curing it. The preparation method of the acrylic resin includes the following steps: butyl methacrylate, methyl acrylate, acrylic acid and silane coupling agent KH-570 are added to butyl acetate and stirred thoroughly. The temperature is raised to 65°C, an initiator diluent is added, and after reflux for 8 hours, the mixture is allowed to cool naturally to obtain a transparent liquid. This liquid is then transferred to a rotary evaporator to remove some of the solvent. The remaining liquid is then added dropwise to methanol in small amounts several times. A white precipitate is formed under stirring conditions. After drying, the acrylic resin is obtained.

[0036] Furthermore, the mass ratio of butyl methacrylate, methyl acrylate, acrylic acid, and silane coupling agent KH-570 is 65:25:1:9.

[0037] Furthermore, the initiating diluent is a solution composed of 2',2-azobisisobutyronitrile and butyl acetate, wherein the mass fraction of 2',2-azobisisobutyronitrile in the initiating diluent is 20%, and the amount of 2',2-azobisisobutyronitrile used is 0.3% of the total mass of butyl methacrylate, methyl acrylate and acrylic acid.

[0038] Furthermore, the hot melt adhesive film layer is a TPU hot melt adhesive film layer, and the preparation method of the TPU hot melt adhesive film layer includes the following steps:

[0039] A1. Add polycarbonate diol and hexamethylene diisocyanate to the reactor for an addition reaction until the NCO content in the system reaches the theoretical value.

[0040] A2. Take hydroxyethyl acrylate, catalyst DBTDL and hydroquinone and mix them thoroughly at 40°C under an inert atmosphere. Then add them to the reaction vessel of step A1 and continue the reaction under an inert gas atmosphere until the NCO groups in the system are completely reacted to obtain the polyurethane prepolymer.

[0041] A3. After thoroughly mixing the polyurethane prepolymer, antistatic agent, oxidant and solvent obtained in step A2, the adhesive is obtained. The adhesive is then coated onto the film-forming substrate. After drying and peeling, a polyurethane hot melt adhesive film is obtained.

[0042] Furthermore, the molar ratio of the polycarbonate diol, hexamethylene diisocyanate, and hydroxyethyl acrylate is 1:2:2, the mass of the catalyst is 0.05% of the mass of the acrylate, and the mass of the hydroquinone is 0.01% of the mass of the acrylate.

[0043] Furthermore, in step A3, the antistatic agent is 0.6% of the mass of the polyurethane prepolymer, and the oxidant is 0.1% of the mass of the polyurethane prepolymer.

[0044] The preparation method of the TPU high and low temperature film with hot stamping and hollowing effect described in this embodiment includes the following preparation steps:

[0045] (1) Take a TPU film, coat one surface of the TPU film with PU coating, and dry to form a PU layer;

[0046] (2) Coat the other surface of the TPU film with hot stamping resin, and form a hot stamping resin layer after drying;

[0047] (3) A pattern layer with graphic information is formed by hot stamping on the surface of the hot stamping resin layer through a hot stamping process;

[0048] (4) A metal plating process is used to deposit a metal coating on the surface of the hot stamping resin layer by vacuum evaporation.

[0049] (5) Apply hot melt adhesive film to the surface of the metal coating, and after it is completely dried, it is laminated into a roll to obtain a TPU high and low temperature film with hot stamping effect.

[0050] Example 2

[0051] This embodiment provides a TPU high and low temperature film with hot stamping and hollowing effect, including a TPU film, a PU layer is disposed on one surface of the TPU film, a hot stamping resin layer is disposed sequentially on the other surface of the TPU film, a pattern layer is disposed on the surface of the hot stamping resin layer away from the TPU film, a metal plating layer is disposed on the surface of the pattern layer away from the hot stamping resin layer, and a hot melt adhesive film layer is disposed on the surface of the metal plating layer away from the pattern layer.

[0052] Furthermore, the hot stamping resin layer is an acrylic resin layer.

[0053] Furthermore, the acrylic resin layer is formed by coating the surface of the TPU film with acrylic resin and then drying and curing it. The preparation method of the acrylic resin includes the following steps: butyl methacrylate, methyl acrylate, acrylic acid and silane coupling agent KH-570 are added to butyl acetate and stirred thoroughly. The temperature is raised to 70°C, an initiator diluent is added, and after reflux for 9 hours, the mixture is allowed to cool naturally to obtain a transparent liquid. This liquid is then transferred to a rotary evaporator to remove some of the solvent. The remaining liquid is then added dropwise to methanol in small amounts several times. A white precipitate is formed under stirring conditions. After drying, the acrylic resin is obtained.

[0054] Furthermore, the mass ratio of butyl methacrylate, methyl acrylate, acrylic acid, and silane coupling agent KH-570 is 67.5:22.5:2:8.

[0055] Furthermore, the initiating diluent is a solution composed of 2',2-azobisisobutyronitrile and butyl acetate, wherein the mass fraction of 2',2-azobisisobutyronitrile in the initiating diluent is 20%, and the amount of 2',2-azobisisobutyronitrile used is 0.5% of the total mass of butyl methacrylate, methyl acrylate and acrylic acid.

[0056] Furthermore, the hot melt adhesive film layer is a TPU hot melt adhesive film layer, and the preparation method of the TPU hot melt adhesive film layer includes the following steps:

[0057] A1. Add polycarbonate diol and hexamethylene diisocyanate to the reactor for an addition reaction until the NCO content in the system reaches the theoretical value.

[0058] A2. Take pentaerythritol triacrylate, catalyst DBTDL and hydroquinone and mix them thoroughly at 45°C under an inert atmosphere. Then add them to the reaction vessel of step A1 and continue the reaction under an inert gas atmosphere until the NCO groups in the system are completely reacted to obtain the polyurethane prepolymer.

[0059] A3. After thoroughly mixing the polyurethane prepolymer, antistatic agent, oxidant and solvent obtained in step A2, the adhesive is obtained. The adhesive is then coated onto the film-forming substrate. After drying and peeling, a polyurethane hot melt adhesive film is obtained.

[0060] Furthermore, the molar ratio of the polycarbonate diol, hexamethylene diisocyanate, and acrylate is 1:2:2, the mass of the catalyst is 0.1% of the mass of the acrylate, and the mass of the hydroquinone is 0.015% of the mass of the acrylate.

[0061] Furthermore, in step A3, the antistatic agent is 1.0% of the mass of the polyurethane prepolymer, and the oxidant is 0.5% of the mass of the polyurethane prepolymer.

[0062] The preparation method of the TPU high and low temperature film with hot stamping and hollowing effect described in this embodiment includes the following preparation steps:

[0063] (1) Take a TPU film, coat one surface of the TPU film with PU coating, and dry to form a PU layer;

[0064] (2) Coat the other surface of the TPU film with hot stamping resin, and form a hot stamping resin layer after drying;

[0065] (3) A pattern layer with graphic information is formed by hot stamping on the surface of the hot stamping resin layer through a hot stamping process;

[0066] (4) A metal plating process is used to deposit a metal coating on the surface of the hot stamping resin layer by vacuum evaporation.

[0067] (5) Apply hot melt adhesive film to the surface of the metal coating, and after it is completely dried, it is laminated into a roll to obtain a TPU high and low temperature film with hot stamping effect.

[0068] Example 3

[0069] This embodiment provides a TPU high and low temperature film with hot stamping and hollowing effect, including a TPU film, a PU layer is disposed on one surface of the TPU film, a hot stamping resin layer is disposed sequentially on the other surface of the TPU film, a pattern layer is disposed on the surface of the hot stamping resin layer away from the TPU film, a metal plating layer is disposed on the surface of the pattern layer away from the hot stamping resin layer, and a hot melt adhesive film layer is disposed on the surface of the metal plating layer away from the pattern layer.

[0070] Furthermore, the hot stamping resin layer is an acrylic resin layer.

[0071] Furthermore, the acrylic resin layer is formed by coating the surface of the TPU film with acrylic resin and then drying and curing it. The preparation method of the acrylic resin includes the following steps: butyl methacrylate, methyl acrylate, acrylic acid and silane coupling agent KH-570 are added to butyl acetate and stirred thoroughly. The temperature is raised to 75°C, an initiator diluent is added, and the mixture is refluxed for 8-10 hours. After natural cooling, a transparent liquid is obtained. The liquid is then transferred to a rotary evaporator to remove some of the solvent. The remaining liquid is then added dropwise to methanol in small amounts several times. A white precipitate is formed under stirring conditions. After drying, the acrylic resin is obtained.

[0072] Furthermore, the mass ratio of butyl methacrylate, methyl acrylate, acrylic acid, and silane coupling agent KH-570 is 70:20:4:6.

[0073] Furthermore, the initiating diluent is a solution composed of 2',2-azobisisobutyronitrile and butyl acetate, wherein the mass fraction of 2',2-azobisisobutyronitrile in the initiating diluent is 20%, and the amount of 2',2-azobisisobutyronitrile used is 0.6% of the total mass of butyl methacrylate, methyl acrylate and acrylic acid.

[0074] Furthermore, the hot melt adhesive film layer is a TPU hot melt adhesive film layer, and the preparation method of the TPU hot melt adhesive film layer includes the following steps:

[0075] A1. Add polycarbonate diol and hexamethylene diisocyanate to the reactor for an addition reaction until the NCO content in the system reaches the theoretical value.

[0076] A2. Take hydroxyethyl acrylate or pentaerythritol triacrylate, catalyst DBTDL and hydroquinone and mix them thoroughly at 45°C under an inert atmosphere. Then add them to the reaction vessel of step A1 and continue the reaction under an inert gas atmosphere until the NCO groups in the system are completely reacted to obtain the polyurethane prepolymer.

[0077] A3. After thoroughly mixing the polyurethane prepolymer, antistatic agent, oxidant and solvent obtained in step A2, the adhesive is obtained. The adhesive is then coated onto the film-forming substrate. After drying and peeling, a polyurethane hot melt adhesive film is obtained.

[0078] Furthermore, the molar ratio of the polycarbonate diol, hexamethylene diisocyanate, and acrylate is 1:2:2, the mass of the catalyst is 0.2% of the mass of the acrylate, and the mass of the hydroquinone is 0.02% of the mass of the acrylate.

[0079] Furthermore, in step A3, the antistatic agent is 1.5% of the mass of the polyurethane prepolymer, and the oxidant is 0.8% of the mass of the polyurethane prepolymer.

[0080] Furthermore, the preparation method of the antistatic agent includes the following steps:

[0081] S1. Add methacrylic acid and a dimethyl sulfoxide solution containing thionyl chloride in a mass ratio of 1:2 to tetrahydrofuran and mix thoroughly. Add N,N-dimethylformamide in an equimolar amount to methacrylic acid, raise the temperature to 60°C, and react for 3 hours. Then add 2,4,6-tris(dimethylaminomethyl)phenol and triethylamine in an equimolar amount to methacrylic acid, and continue the reaction for 2-4 hours to obtain an intermediate product. Recrystallize the intermediate product with acetone and dry it.

[0082] S2. Place the dried intermediate product obtained in step S1 in anhydrous ethanol, add hydrochloric acid to it, the molar ratio of hydrochloric acid to intermediate product is 3.3, react at room temperature for 0.5 h, then raise the temperature to 45 °C, adjust the pH of the solution to 7.5, add epichlorohydrin, and continue to react for 8 h. Transfer to a rotary evaporator for rotary evaporation to evaporate the solvent, and then place the product in an oven to dry, thus obtaining the antistatic agent.

[0083] The preparation method of the TPU high and low temperature film with hot stamping and hollowing effect described in this embodiment includes the following preparation steps:

[0084] (1) Take a TPU film, coat one surface of the TPU film with PU coating, and dry to form a PU layer;

[0085] (2) Coat the other surface of the TPU film with hot stamping resin, and form a hot stamping resin layer after drying;

[0086] (3) A pattern layer with graphic information is formed by hot stamping on the surface of the hot stamping resin layer through a hot stamping process;

[0087] (4) A metal plating process is used to deposit a metal coating on the surface of the hot stamping resin layer by vacuum evaporation.

[0088] (5) Apply hot melt adhesive film to the surface of the metal coating, and after it is completely dried, it is laminated into a roll to obtain a TPU high and low temperature film with hot stamping effect.

[0089] Example 4

[0090] The difference between this embodiment and embodiment 3 is that the preparation method of the TPU high and low temperature film with hot stamping and hollowing effect described in this embodiment further includes step (6), which involves processing the TPU high and low temperature film with hot stamping effect by laser cutting to form the required hollowing shape, thereby obtaining the TPU high and low temperature film with hot stamping and hollowing effect.

[0091] Comparative Example 1

[0092] The difference between this comparative example and Example 2 is that the hot stamping resin layer in this comparative example is an acrylic resin layer. The acrylic resin layer is formed by coating the surface of a TPU film with acrylic resin and then drying and curing it. The preparation method of the acrylic resin includes the following steps: taking butyl methacrylate, methyl acrylate, and acrylic acid and adding them to butyl acetate and stirring thoroughly, raising the temperature to 70°C, adding an initiator diluent, refluxing for 9 hours, and then naturally cooling to obtain a transparent liquid. Transferring it to a rotary evaporator to remove part of the solvent, and then adding the remaining liquid dropwise to methanol in small amounts several times. A white precipitate is generated under stirring conditions, and after drying, the acrylic resin is obtained.

[0093] Furthermore, the mass ratio of butyl methacrylate, methyl acrylate, and acrylic acid is 67.5:22.5:10.

[0094] Furthermore, the initiating diluent is a solution composed of 2',2-azobisisobutyronitrile and butyl acetate, wherein the mass fraction of 2',2-azobisisobutyronitrile in the initiating diluent is 20%, and the amount of 2',2-azobisisobutyronitrile used is 0.5% of the total mass of butyl methacrylate, methyl acrylate and acrylic acid.

[0095] Comparative Example 2

[0096] The difference between this comparative example and Example 2 is that the hot stamping resin layer in this comparative example is an acrylic resin layer. The acrylic resin layer is formed by coating the surface of a TPU film with acrylic resin and then drying and curing it. The preparation method of the acrylic resin includes the following steps: adding butyl methacrylate, methyl acrylate and silane coupling agent KH-570 to butyl acetate and stirring thoroughly, raising the temperature to 70°C, adding an initiator diluent, refluxing for 9 hours, and then cooling naturally to obtain a transparent liquid. Transferring it to a rotary evaporator to remove part of the solvent, and then adding the remaining liquid dropwise to methanol in small amounts several times. A white precipitate is generated under stirring conditions, and after drying, the acrylic resin is obtained.

[0097] Furthermore, the mass ratio of butyl methacrylate, methyl acrylate, and silane coupling agent KH-570 is 67.5:22.5:10.

[0098] Furthermore, the initiating diluent is a solution composed of 2',2-azobisisobutyronitrile and butyl acetate, wherein the mass fraction of 2',2-azobisisobutyronitrile in the initiating diluent is 20%, and the amount of 2',2-azobisisobutyronitrile used is 0.5% of the total mass of butyl methacrylate, methyl acrylate and acrylic acid.

[0099] Comparative Example 3

[0100] The difference between this comparative example and Example 3 is that the hot melt adhesive film layer in this comparative example is a TPU hot melt adhesive film layer, and the preparation method of the TPU hot melt adhesive film layer includes the following steps:

[0101] A1. Add polycarbonate diol and hexamethylene diisocyanate to the reactor for an addition reaction until the NCO content in the system reaches the theoretical value.

[0102] A2. Take hydroxyethyl acrylate or pentaerythritol triacrylate, catalyst DBTDL and hydroquinone and mix them thoroughly at 45°C under an inert atmosphere. Then add them to the reaction vessel of step A1 and continue the reaction under an inert gas atmosphere until the NCO groups in the system are completely reacted to obtain the polyurethane prepolymer.

[0103] A3. After thoroughly mixing the polyurethane prepolymer, antistatic agent, oxidant and solvent obtained in step A2, the adhesive is obtained. The adhesive is then coated onto the film-forming substrate. After drying and peeling, a polyurethane hot melt adhesive film is obtained.

[0104] Furthermore, the molar ratio of the polycarbonate diol, hexamethylene diisocyanate, and acrylate is 1:2:2, the mass of the catalyst is 0.2% of the mass of the acrylate, and the mass of the hydroquinone is 0.02% of the mass of the acrylate.

[0105] Furthermore, in step A3, the antistatic agent is 1.5% of the mass of the polyurethane prepolymer, and the oxidant is 0.8% of the mass of the polyurethane prepolymer.

[0106] Furthermore, the preparation method of the antistatic agent includes the following steps:

[0107] S1. Add methacrylic acid and a dimethyl sulfoxide solution containing thionyl chloride in a mass ratio of 1:2 to tetrahydrofuran and mix thoroughly. Add N,N-dimethylformamide in an equimolar amount to methacrylic acid, raise the temperature to 60°C, and react for 3 hours. Then add 2,4,6-tris(dimethylaminomethyl)phenol and triethylamine in an equimolar amount to methacrylic acid, and continue the reaction for 2-4 hours to obtain an intermediate product. Recrystallize the intermediate product with acetone and dry it.

[0108] S2. 2,4,6-Tris(dimethylaminomethyl)phenol was placed in anhydrous ethanol and stirred until homogeneous. Hydrochloric acid was added, and the reaction was carried out at room temperature for 0.5 h. The temperature was then increased to 45 °C, and the pH of the solution was adjusted to 7.5. Epichlorohydrin with an equimolar amount of 2,4,6-tris(dimethylaminomethyl)phenol was added, and the reaction was continued for 8 h. The mixture was then transferred to a rotary evaporator for rotary evaporation to evaporate the solvent. The product was then dried in an oven to obtain the antistatic agent.

[0109] This invention tests the TPU high and low temperature films with hot stamping and perforation effects prepared in Examples 1-3 and Comparative Examples 1-3. The performance tests include: an abrasion resistance test according to GB / T1768-2006 (note that the exposed substrate in the table below refers to the wear of the pattern layer, revealing the TPU film layer. The abrasion resistance test conditions are: CS-10 grinding wheel, set speed 72 r / min, surface load weight 1000g); an adhesion test according to GB / T286-1998; and an aging resistance test (irradiated with 340nm ultraviolet light for 1000h, light intensity 0.8W / cm²). 2 ); The surface resistivity was tested according to ASTM D4496, and the results are shown in Table 1 below.

[0110] Table 1

[0111]

[0112] As shown in Table 1 above, the TPU high and low temperature films with hot stamping and hollowing effects prepared by the present invention in Examples 1-3 have good mechanical properties and adhesion properties, and also exhibit long-lasting UV aging resistance in terms of photostability, while also having good antistatic ability. A comparison of Comparative Examples 1-2 with Example 2 shows that the hot stamping resin layer prepared using butyl methacrylate, methyl acrylate, acrylic acid, and silane coupling agent as the main raw materials has better abrasion resistance and adhesion. A comparison of Comparative Example 3 with Example 3 shows that the addition of a special antistatic agent during the preparation of the TPU hot melt adhesive film significantly improves the antistatic ability of the TPU high and low temperature film.

[0113] The specific embodiments described above are further illustrations of the technical solution and beneficial effects of the present invention, and are not intended to limit the implementation methods. For those skilled in the art, any obvious substitutions without departing from the concept of the present invention are within the protection scope of the present invention.

Claims

1. A TPU high and low temperature film with a hot stamping and perforation effect, characterized in that: The TPU film includes a PU layer on one surface and a hot stamping resin layer on the other surface. A pattern layer is provided on the surface of the hot stamping resin layer away from the TPU film. A metal plating layer is provided on the surface of the pattern layer away from the hot stamping resin layer. A hot melt adhesive film layer is provided on the surface of the metal plating layer away from the pattern layer. The hot stamping resin layer is an acrylic resin layer, which is formed by coating the surface of a TPU film with acrylic resin and then drying and curing it. The preparation method of the acrylic resin includes the following steps: adding butyl methacrylate, methyl acrylate, acrylic acid and silane coupling agent to butyl acetate and stirring thoroughly, raising the temperature to 65-75℃, adding an initiator diluent, refluxing for 8-10 hours, and then cooling naturally to obtain a transparent liquid. Transferring it to a rotary evaporator to remove part of the solvent, and then adding the remaining liquid dropwise to methanol in small amounts several times. Under stirring conditions, a white precipitate is generated, and after drying, the acrylic resin is obtained. The mass ratio of butyl methacrylate, methyl acrylate, acrylic acid and silane coupling agent is 65-70: 20-25: 1-5: 5-9. The hot melt adhesive film layer is a TPU hot melt adhesive film layer, and the preparation method of the TPU hot melt adhesive film layer includes the following steps: A1. Add polycarbonate diol and hexamethylene diisocyanate to the reactor for an addition reaction until the NCO content in the system reaches the theoretical value. A2. Take hydroxyethyl acrylate or pentaerythritol triacrylate, catalyst DBTDL and hydroquinone and mix them thoroughly at 40-45°C under an inert atmosphere. Then add them to the reaction vessel of step A1 and continue the reaction under an inert gas atmosphere until the NCO groups in the system are completely reacted to obtain the polyurethane prepolymer. A3. After thoroughly mixing the polyurethane prepolymer, antistatic agent, oxidant and solvent obtained in step A2, the adhesive is obtained. The adhesive is then coated onto the film-forming substrate. After drying and peeling, a polyurethane hot melt adhesive film is obtained. In step A3, the mass of the antistatic agent is 0.5-1.5% of the mass of the polyurethane prepolymer. The method for preparing the antistatic agent includes the following steps: S1. Add methacrylic acid and a solution of dimethyl sulfoxide containing thionyl chloride to tetrahydrofuran and mix thoroughly. Add N,N-dimethylformamide and raise the temperature to 55-65℃. React for 2-4 hours. Then add 2,4,6-tris(dimethylaminomethyl)phenol and triethylamine and continue the reaction for 2-4 hours to obtain an intermediate product. Recrystallize the intermediate product with acetone and dry it. S2. Place the dried intermediate product obtained in step S1 in anhydrous ethanol, add hydrochloric acid, react at room temperature for 0.5-1 h, then raise the temperature to 40-50℃, adjust the pH of the solution to 7.5-8, add epichlorohydrin, and continue the reaction for 8-10 h. Transfer to a rotary evaporator for rotary evaporation to evaporate the solvent, and then place the product in an oven to dry, thus obtaining the antistatic agent.

2. The TPU high and low temperature film with hot stamping and hollowing effect according to claim 1, characterized in that: The initiating diluent is a solution composed of 2',2-azobisisobutyronitrile and butyl acetate, wherein the amount of 2',2-azobisisobutyronitrile is 0.3-0.7% of the total mass of butyl methacrylate, methyl acrylate and acrylic acid.

3. The TPU high and low temperature film with hot stamping and perforation effect according to claim 1, characterized in that: The molar ratio of polycarbonate diol, hexamethylene diisocyanate, and acrylate is 1:2:2, the mass of the catalyst is 0.05-0.2% of the mass of acrylate, and the mass of hydroquinone is 0.01-0.02% of the mass of acrylate.

4. The TPU high and low temperature film with hot stamping and hollowing effect according to claim 1, characterized in that: In step A3, the oxidant is 0.1-1% of the mass of the polyurethane prepolymer.

5. A TPU high and low temperature film with hot stamping and perforation effect as described in any one of claims 1-4, characterized in that: The preparation method of the TPU high and low temperature film includes the following preparation steps: (1) Take a TPU film, coat one surface of the TPU film with PU coating, and dry to form a PU layer; (2) Coat the other surface of the TPU film with hot stamping resin, and form a hot stamping resin layer after drying; (3) A pattern layer with graphic information is formed by hot stamping on the surface of the hot stamping resin layer through a hot stamping process; (4) A metal plating process is used to deposit a metal coating on the surface of the hot stamping resin layer by vacuum evaporation. (5) Apply hot melt adhesive film to the surface of the metal coating, and after it is completely dried, it is laminated into a roll to obtain a TPU high and low temperature film with hot stamping effect.

6. A TPU high and low temperature film with hot stamping and perforation effect according to claim 5, characterized in that: The preparation method of the TPU high and low temperature film also includes step (6), which involves processing the TPU high and low temperature film with hot stamping effect by laser cutting, automatic vibrating knife or die cutting to form the required hollow shape, thereby obtaining the TPU high and low temperature film with hot stamping hollow effect.

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