A kind of electroplated TPU film and its production process

Abstract

The present application relates to a plated TPU film and its production process, comprising the following steps: 1) laminating the side of the ABC plated film away from the electroplating layer with the TPU film, and then preheating, the preheating time is 5-10s, the preheating temperature is 70-80℃, and a semi-finished product is obtained; 3) the semi-finished product is hot pressed, wherein the temperature close to the TPU film is 110-130℃, the temperature close to the ABC plated film is 150-170℃, the pressing force is 2-10N, and the hot pressing time is 1-5s, to obtain the plated TPU film. The present application laminates the TPU film with the ABC plated film, and preheats it to make it stable. The obtained plated TPU film has the advantages of both the TPU film and the ABC plated film. When used in shoes, bags, etc., it is easy to stretch and stably heat-laminate on the surface of shoes or bags, and the electroplating effect is good. It is not easy to fall off after multiple washings and frictions, which improves its beauty and durability.

Description

Technical Field

[0001] The present application relates to the field of membrane materials, and more specifically, to an electroplated TPU membrane and a production process thereof. Background Art

[0002] TPU film has excellent properties of high tensile strength, high toughness, flexibility, wear resistance and aging resistance. The main use of TPU film is to be processed into various products, such as clothing, shoes, leather goods, etc. TPU film also has good transparency and glossiness, and has good aesthetics. And because it has good processability, it can be easily cut, stitched, embossed, printed and other processes to form various patterns, patterns and fonts. Therefore, it is widely used in clothing, bags, shoes and other fields, which can enhance the texture and grade of the product.

[0003] Electroplating is the process of plating a thin layer of other metals or alloys on certain metal surfaces using the principle of electrolysis, or the process of using electrolysis to make a layer of metal film adhere to the surface of metal or other material parts, thereby preventing metal oxidation (such as rust), improving wear resistance, conductivity, reflectivity, corrosion resistance (copper sulfate, etc.) and enhancing aesthetics.

[0004] After electroplating, the product surface forms various colorful patterns, which have high decorative beauty, but the surface of TPU film is difficult to electroplate. The commonly used substrates for electroplating are metals, alloys, and plastics. There are many kinds of plastics on the market, but not many kinds of plastics can be electroplated. Because each plastic has its own properties, the similarity between the plastic and metal layers needs to be considered during electroplating. If the difference is large, it is difficult to ensure its normal performance in the high temperature environment of electroplating.

[0005] Currently, the plastics that can be used for electroplating on the market include ABS, PP, PSF, PC, etc. Among them, ABS has the best electroplating effect and is widely used. After electroplating the ABS film, the colorful film formed is then used for the decoration of shoes, bags, stationery, etc. However, ABS has a relatively high hardness, and it is difficult to fit stably at the corners when attached, and the heating temperature is relatively high, which is not conducive to thermal bonding to the surface of shoes and bags.

[0006] To this end, the relevant technology blends and modifies ABS and TPU to form an ABS / TPU composite, combines the properties of the two, and then uses it for electroplating to form an ABS / TPU blend film. However, compared with TPU, the adhesion and softness of the film are reduced, so the adhesion on the surface of shoes, bags, stationery, etc. is reduced. In addition, the electroplating effect is lower than the electroplating effect of the ABS film. When the shoes and bags are washed many times, the electroplated layer on their surface is easy to fall off, thereby affecting the decorative appearance. Therefore, further research is needed. Summary of the invention

[0007] In order to obtain a coating that is not easy to fall off and a membrane material that is easy to adhere to the surface of shoes, bags, etc., the present application provides an electroplated TPU film and a production process thereof.

[0008] In a first aspect, a production process of an electroplated TPU film comprises the following steps:

[0009] 1) Lay the side of the ABC electroplated film away from the electroplated layer on the TPU film layer, and then preheat it for 5-10s at a preheating temperature of 70-80°C to obtain a semi-finished product;

[0010] 2) The semi-finished product is subjected to hot pressing, wherein the temperature near the TPU film is 110-130° C., the temperature near the ABC electroplated film is 150-170° C., the pressing force is 2-10N, and the hot pressing time is 1-5s to obtain an electroplated TPU film.

[0011] The above scheme is simple to operate and has high production efficiency. Specifically, after the side of the ABC electroplated film away from the electroplated layer is bonded to the TPU film, it is preheated for 5-10 seconds at a temperature of 70-80°C to facilitate subsequent hot pressing and improve the structural stability of the electroplated TPU film after hot pressing.

[0012] In step 2), during the heat pressing process, the temperatures of the upper and lower surfaces are different. Based on the heating characteristics of the material, heat pressing is performed at a specific temperature and with pressure, so that the obtained electroplated TPU film has better layer structure stability.

[0013] In summary, the present application achieves stable bonding by bonding the TPU film layer with the ABC electroplated film, and presents the best performance of both. When used in footwear, bags, etc., it is easy to stretch and stably heat-bond to the shoe upper or bag surface. At the same time, the surface of the electroplated TPU film is good, and it is not easy to fall off after multiple washings, thereby improving its appearance and durability.

[0014] Preferably, the step (1) further comprises forming a protective layer on the surface of the ABC electroplated film. The specific process in the step (1) is:

[0015] The protective adhesive is coated on the surface of the electroplating layer of the ABC electroplating film, solidified, and a protective layer is formed on the surface of the electroplating layer. Then, the side of the ABC electroplating film with the protective layer away from the electroplating layer is laminated to the TPU film layer, and then preheated for 5-10s at a preheating temperature of 70-80°C to obtain a semi-finished product.

[0016] By forming a protective layer on the electroplating layer, the electroplating layer has a better protective effect, which can reduce the damage of the electroplating layer during the hot pressing process. When washing bags and shoes many times, the possibility of detachment of the electroplating layer is reduced, thereby making the electroplated TPU film have a better electroplating decorative effect.

[0017] When used to decorate bags, shoes and stationery, the electroplated TPU film needs to be heated to make the TPU film layer of the electroplated TPU film slightly melted. At this time, the TPU film layer of the electroplated TPU film can be attached to the surface of the shoe material or the surface of the bag, and after cooling, it can be stably attached to the surface of the shoe material or the bag. Especially in the bending area, due to the hardness of the ABS electroplated film, when it is used alone, it is easy to crack or crease during the bending process. The present application combines the TPU film layer with the ABC electroplated film, in which the TPU film layer has better flexibility, so it plays a buffering role during the bending process, reducing the phenomenon of creases or cracks on the ABS.

[0018] Furthermore, by providing a protective layer, the present application can further reduce the phenomenon of cracks on the surface of the ABS electroplated film during the bending process, and reduce scratches, wear and tear on the electroplated TPU film. It also reduces the phenomenon of wear on the electroplated layer of the electroplated TPU film after multiple washings.

[0019] In addition, the protective film obtained by the preparation process of the present application has a high light transmittance, and therefore has little impact on the colorful effect of the electroplated PUR film.

[0020] Preferably, the curing temperature is 130-150° C., and the curing time is 1-3 min.

[0021] By using the above curing temperature and curing time range, the applied protective adhesive is completely cured to form a protective layer, which has a good protective effect on the electroplating layer of the ABS electroplating film and reduces the deformation of the ABS electroplating film when the TPU film is pulled, thereby causing uneven distribution of the electroplating layer in the ABS electroplating film.

[0022] Preferably, the protective glue is composed of the following raw materials in parts by weight:

[0023] Polyester modified acrylic resin 5-10 parts

[0024] Wear-resistant agent 0.1-0.5 parts

[0025] Thickener 0.1-0.3 parts

[0026] 5-14 parts of diluent

[0027] Platinum catalyst 0.001-0.04 parts.

[0028] In the above scheme, the polyester modified acrylic resin contains hydroxyl groups and has good stretchability, scratch resistance, flexibility, heat resistance and adhesion, etc. The wear resistance of the protective glue is further enhanced by adding a wear-resistant agent, and the diluent can dilute its raw material system to improve the convenience of coating, and the platinum catalyst promotes curing and reaction. The tackifier can cooperate with the protective glue system to further improve the protective effect of the protective glue on the electroplating layer, reduce the phenomenon of wear, improve the appearance of the electroplated TPU film used in shoes and bags, and reduce the possibility of the electroplated TPU film falling off the surface of the shoe material. At the same time, the protective layer has high light transmittance, so that the electroplating layer maintains a good electroplating colorful effect.

[0029] Preferably, the wear-resistant agent is one or more of polyborosilazane, glycidyloxypropyl cyclotetrasiloxane, and organosilicon-modified polycarbonate polyurethane resin.

[0030] Polyborosilazane, glycidyloxypropyl cyclotetrasiloxane, and silicone-modified polycarbonate polyurethane resin all have good wear resistance and high temperature resistance. Therefore, using one or more of them in combination can further improve the wear resistance and high temperature resistance of the protective glue. Therefore, the cured protective layer is not only wear-resistant, reducing the wear and scratching of the electroplated TPU film, but also can further improve the high temperature resistance of the protective layer, avoiding the aesthetics of the electroplated layer being affected when the ABS electroplated film layer and the TPU film are pressed together.

[0031] Preferably, the wear-resistant agent is composed of polyborosilazane and glycidyloxypropyl cyclotetrasiloxane in a weight ratio of 1:(0.1-0.5), or polyborosilazane and silicone-modified polycarbonate polyurethane resin in a weight ratio of 1:(0.2-0.5), or polyborosilazane, glycidyloxypropyl cyclotetrasiloxane and silicone-modified polycarbonate polyurethane resin in a weight ratio of 1:(0.05-0.4):(0.1-0.4).

[0032] The wear resistance and high temperature resistance of the wear-resistant agent obtained by compounding at least two of the above materials are better than those of using only one material as the wear-resistant agent, and the obtained protective layer can have a good protective effect on the electroplated layer of the electroplated TPU film, reducing the wear of the electroplated layer.

[0033] Among them, when polyborosilazane, glycidyloxypropyl cyclotetrasiloxane, and silicone-modified polycarbonate polyurethane resin are compounded in a weight ratio of 1: (0.05-0.1): (0.2-0.3), the resulting protective adhesive solution is coated and cured, and the formed protective film has good toughness, high temperature resistance and wear resistance. Therefore, the electroplated TPU film has better wear resistance, high temperature resistance, etc., avoiding the possibility of wear after use in shoes and bags.

[0034] Furthermore, when the electroplated TPU film is bent and the corners are attached to shoes or bags, it can be stably attached to the surface thereof, and the electroplated layer of the electroplated TPU film is not prone to unstable adhesion.

[0035] Preferably, the viscosity enhancer is composed of one or more of bis(diethyl citrate)dipropoxy zirconium chelate, bis(dioctyloxypyrophosphate)ethylene titanate, γ-methacryloxypropyltrimethoxysilane, and aluminum triacetylacetonate.

[0036] Preferably, the tackifier is composed of bis(dioctyl pyrophosphate)ethylene titanate, γ-methacryloxypropyltrimethoxysilane, and aluminum triacetylacetonate in a weight ratio of 1:(1-3):(1-2); or is composed of bis(diethyl citrate)dipropoxy zirconium chelate and bis(dioctyl pyrophosphate)ethylene titanate in a weight ratio of 1:(2.5-3.5); or is composed of bis(diethyl citrate)dipropoxy zirconium chelate, γ-methacryloxypropyltrimethoxysilane, and aluminum triacetylacetonate in a weight ratio of 1:(1.5-2.5):(2-3).

[0037] The present application adopts two of the compositions of bis(diethyl citrate) dipropoxy zirconium chelate, bis(dioctyl pyrophosphate) ethylene titanate, γ-methacryloxypropyltrimethoxysilane, and triacetylacetonate aluminum to obtain a thickener with better thickening effect, thereby improving the wear resistance of the protective layer and reducing the wear of the electroplated layer of the electroplated TPU film.

[0038] Among them, aluminum triacetylacetonate is a white crystalline powder and will not cause discoloration in the protective glue solution.

[0039] Preferably, the protective colloid is prepared by the following method:

[0040] According to parts by weight, polyester modified acrylic resin, diluent, tackifier, anti-wear agent and platinum catalyst are weighed and mixed evenly to obtain a protective glue solution.

[0041] The above preparation method is simple to operate and has high production efficiency, and the obtained protective glue is easy to adhere to the surface of the electroplating layer. After curing, a highly transparent protective layer is formed. The protective layer not only has a good protective effect on the electroplating layer, but also can enable the electroplating layer to maintain a better colorful effect. When the electroplated TPU film is used on the surface of shoes, bags, etc., it can be stably attached to the surface and is not easy to fall off, and the electroplating layer is not easy to wear, so that the electroplating layer maintains a better electroplating colorful effect.

[0042] In the second aspect, the present application provides an electroplated TPU film using the following technical solution:

[0043] An ABS electroplated composite layer and a TPU film layer are sequentially arranged from the upper surface to the lower surface. The thickness of the electroplated TPU film is 0.1-2 mm, and the ratio of the thickness of the ABS electroplated film composite layer to the thickness of the TPU film layer is 1:(1-3.8). The electroplated TPU film is obtained by the production process of an electroplated TPU film.

[0044] After the ABS electroplated composite layer and the TPU film layer are bonded together, the electroplated TPU film formed has the advantages of both layers. The thickness of the electroplated TPU film and the thickness ratio between each film layer are the optimal thickness selection for this application, so that the obtained electroplated TPU film has better wear resistance and adhesion stability, reducing the possibility of detachment.

[0045] Preferably, the electroplated film composite layer further includes a protective layer, the protective layer is bonded to the electroplated layer, and the ratio of the thickness of the protective layer to the thickness of the ABS layer is (0.08-0.42):1.

[0046] By providing a protective layer, the electroplating layer is further protected, reducing the possibility of the electroplating layer being worn and exposed.

[0047] In summary, this application has the following beneficial effects:

[0048] The present application laminates the TPU film and the ABC electroplated film, and preheats the film to stabilize the laminate. The obtained electroplated TPU film has the advantages of both the TPU film and the ABC electroplated film. When used in shoes, bags, etc., it is easy to stretch and stably thermally laminated to the surface of shoes or bags, and has a good electroplating effect. It is not easy to fall off after multiple washings and frictions, thereby improving its appearance and durability. DETAILED DESCRIPTION

[0049] The present application is further described in detail below with reference to the embodiments.

[0050] The preferred TPU film manufacturer is Guangdong Jumao Plastic Industry Co., Ltd., brand R; thickness 0.15mm;

[0051] The ABS electroplated film in the embodiment is a laser fantasy color film, and the manufacturer is preferably Longgang Boda Laser Material Co., Ltd., and the model is customized, wherein the total thickness is 0.15mm, the thickness of the ABS layer is 0.1mm, and the thickness of the electroplated layer is 0.05mm;

[0052] The preferred brand of polyester modified acrylic resin manufacturer is Japan Asia / Japan, model SE-200;

[0053] Polyborosilazane, the manufacturer is preferably Anhui Mingyi Silicon Industry Co., Ltd., model MY9120;

[0054] Glycidyl ether oxypropyl cyclotetrasiloxane, refractive index 1.49, average molecular weight 797,

[0055] Silicone modified polycarbonate polyurethane resin, the preferred manufacturer is Jining Huakai Resin Co., Ltd., model 1091R.

[0056] Preparation example of protective glue

[0057] Preparation Example 1

[0058] A protective glue solution is prepared by the following method:

[0059] 5 kg of polyester modified acrylic resin, 5 kg of diluent, 0.2 kg of tackifier, 0.001 kg of platinum catalyst, and 0.2 kg of anti-wear agent were weighed and stirred at a speed of 50 r / min for 30 min to obtain a protective glue solution.

[0060] Wherein, the diluent is ethyl acetate, and the viscosity enhancer is γ-methacryloxypropyltrimethoxysilane.

[0061] The anti-wear agent is polyborosilazane.

[0062] Preparation Example 2-3

[0063] The difference between Preparation Example 2-3 and Preparation Example 1 is that the amount of raw materials used is different, as shown in Table 1;

[0064] Table 1 Raw material dosage of preparation examples 1-3 (kg)

[0065]

[0066] Preparation Example 4

[0067] The difference between Preparation Example 4 and Preparation Example 2 is that the viscosity enhancer is obtained by mixing 0.05 kg of bis(diethyl citrate)dipropoxy zirconium chelate and 0.15 kg of bis(dioctyloxypyrophosphate)ethylene titanate.

[0068] Preparation Example 5

[0069] The difference between Preparation Example 5 and Preparation Example 2 is that the viscosity enhancer is obtained by mixing 0.04 kg of bis(dioctyloxypyrophosphate)ethylene titanate, 0.08 kg of γ-methacryloxypropyltrimethoxysilane, and 0.08 kg of aluminum triacetylacetonate.

[0070] Preparation Example 6

[0071] The difference between Preparation Example 6 and Preparation Example 2 is that the viscosity enhancer is obtained by mixing 0.04 kg of bis(diethyl citrate)dipropoxyzirconium chelate, 0.08 kg of γ-methacryloxypropyltrimethoxysilane, and 0.08 kg of aluminum triacetylacetonate.

[0072] Preparation Example 7

[0073] The difference between Preparation Example 7 and Preparation Example 5 is that the wear-resistant agent is obtained by mixing 0.4 kg of polyborosilazane and 0.1 kg of glycidyl ether oxypropyl cyclotetrasiloxane.

[0074] Preparation Example 8

[0075] The difference between Preparation Example 8 and Preparation Example 5 is that the wear-resistant agent is obtained by mixing 0.4 kg of polyborosilazane and 0.1 kg of organosilicon-modified polycarbonate polyurethane resin.

[0076] Preparation Example 9

[0077] The difference between Preparation Example 9 and Preparation Example 5 is that the wear-resistant agent is obtained by mixing 0.3 kg of polyborosilazane, 0.1 kg of glycidyloxypropyl cyclotetrasiloxane, and 0.1 kg of silicone-modified polycarbonate polyurethane resin.

[0078] Preparation Comparative Example

[0079] Preparation Comparative Example 1

[0080] The difference between Preparation Comparative Example 1 and Preparation Example 1 is that the wear-resistant agent is replaced by polyester-modified acrylic resin in equal amount.

[0081] Preparation Comparative Example 2

[0082] The difference between Preparation Comparative Example 2 and Preparation Example 1 is that an equal amount of the tackifier is replaced by a polyester-modified acrylic resin.

[0083] Example

[0084] Example 1

[0085] A plated TPU film, an ABS plated composite layer and a TPU film layer are sequentially arranged from the upper surface to the lower surface, the thickness of the electroplated TPU film can be 0.1mm, 0.2mm, 0.3mm, 0.4mm, 0.5mm, 0.6mm, 0.8mm, 1mm, 1.2mm, 1.5mm or 2mm, and the preferred thickness in this embodiment is 0.3mm, wherein the thickness of the ABS plated film composite is 0.15mm, the thickness ratio of the ABS plated film composite layer to the thickness of the TPU film layer is 1:1, the ABS plated composite layer includes an ABS layer and an electroplating layer, the ABS layer is bonded to the TPU film layer, and the thickness ratio of the ABS layer to the electroplating layer is 1:0.5.

[0086] The electroplated TPU film is obtained by the following process:

[0087] 1) Laminating the ABS layer of the ABC electroplated film with the TPU film layer, and then preheating the film for 5 seconds at a preheating temperature of 80° C. to obtain a semi-finished product;

[0088] 2) The semi-finished product is transferred to a laminating machine for hot pressing, wherein the mold temperature close to the TPU film is 110°C, the mold temperature close to the ABC electroplated film is 150°C, the pressing pressure is 2N, and the hot pressing time is 5s to obtain an electroplated TPU film.

[0089] Example 2

[0090] The difference between Example 2 and Example 1 is that the process parameters are different. The specific process is as follows:

[0091] 1) Laminating the ABS layer of the ABC electroplated film with the TPU film layer, and then preheating the film for 8 seconds at a preheating temperature of 75° C. to obtain a semi-finished product;

[0092] 2) The semi-finished product is transferred to a laminating machine for hot pressing, wherein the mold temperature close to the TPU film is 120°C, the mold temperature close to the ABC electroplated film is 160°C, the pressing pressure is 5N, and the hot pressing time is 3s to obtain an electroplated TPU film.

[0093] Example 3

[0094] The difference between Example 3 and Example 1 is that the process parameters are different, and the specific process is as follows:

[0095] 1) Laminating the ABS layer of the ABC electroplated film with the TPU film layer, and then preheating the film for 10 seconds at a preheating temperature of 70° C. to obtain a semi-finished product;

[0096] 2) The semi-finished product is transferred to a laminating machine for hot pressing, wherein the mold temperature close to the TPU film is 130°C, the mold temperature close to the ABC electroplated film is 170°C, the pressing pressure is 10N, and the hot pressing time is 1s to obtain an electroplated TPU film.

[0097] Example 4

[0098] The difference between Example 4 and Example 2 is that the electroplated film composite layer also includes a protective layer, the protective layer is bonded to the electroplated layer, and the ratio of the thickness of the protective layer to the thickness of the ABS layer is 0.3:1.

[0099] Wherein, step (1) also includes forming a protective layer on the surface of the electroplated layer of the ABC electroplated film, and the specific process is as follows:

[0100] The protective adhesive obtained in Preparation Example 1 was coated on the surface of the electroplated layer of the ABC electroplated film, heated to 140 minutes, and cured for 2 minutes to form a protective layer on the surface of the electroplated layer. The ABS layer of the ABC electroplated film with the protective layer was then laminated to the TPU film layer, and then transferred to an oven for preheating for 8 seconds at a preheating temperature of 75°C to obtain a semi-finished product.

[0101] Embodiment 5-14

[0102] The difference between Example 5-14 and Example 4 is that the source of the protective glue is different, as shown in Table 2;

[0103] Table 2 Sources of protective glue solutions of Examples 4-14

[0104] Example Source of protective glue Example 4 Preparation Example 1 Example 5 Preparation Example 2 Example 6 Preparation Example 3 Example 7 Preparation Example 4 Example 8 Preparation Example 5 Example 9 Preparation Example 6 Example 10 Preparation Example 7 Embodiment 11 Preparation Example 8 Example 12 Preparation Example 9 Embodiment 13 Preparation Comparative Example 1 Embodiment 14 Preparation Comparative Example 2

[0105] Comparative Example

[0106] Comparative Example 1

[0107] The difference between Comparative Example 1 and Example 1 is that the electroplated TPU film is a TPU / ABS electroplated film, wherein the thickness of the TPU / ABS layer in the TPU / ABS electroplated film is 0.25 mm, the thickness of the electroplated layer is 0.05 mm, and the raw material usage ratio of TPU and ABS in the TPU / ABS layer is 1:1.

[0108] Comparative Example 2

[0109] The difference between Comparative Example 2 and Example 1 is that the electroplated TPU film is an ABS electroplated film, wherein the thickness of the electroplated layer is 0.05 mm, and the thickness of the ABS layer is 0.25 mm.

[0110] Performance testing

[0111] Detection method / test method

[0112] (I) Preparation for the bonding stability experiment: TPU (brand and model: Risheng EMP-98A) was used to form a TPU square foam block after foaming through the sole process. The electroplated TPU film or TPU / ABS electroplated film or ABS electroplated film obtained in Examples 1-14 and Comparative Examples 1-2 was cut into 15 test strips of 2 cm*6 cm, and then the side of the 5 sample strips in Examples 1-3 and Comparative Examples 1-2 away from the electroplating layer was thermally bonded to the square foam block at 100°C for 5 seconds, so that the test strips were stably adhered to the surface of the TPU square foam block.

[0113] During the bonding process, the middle of the test strip was aligned with the edge of the TPU square foam block. After bonding, there were test strips of 3 cm in length on two adjacent sides of the TPU square foam block.

[0114] Then fix the bottom surface of the square foam block, cut a small opening of 1mm*1mm on the test strip on the top surface of the square foam block with a knife, and then clamp it with a clamp. Use forces of 1N, 2N, 3N, 4N, 5N, 6N, 7N, and 10N to peel off the test strip along the direction of the small opening. The peeling time is 5s. The force that can tear the entire test strip is recorded, and the average value of 5 test samples is taken. The specific values ​​are shown in Table 3.

[0115] (II) Water washing test

[0116] The 10 test samples of Examples 1-14 and Comparative Examples 1-2 obtained in (I) were placed in an oven at 50°C for drying for 20 min, and the weight was weighed and recorded as A. Then, they were placed in a stirring barrel of a MYP11-2 constant temperature magnetic stirrer. The solution in the stirring barrel (a phosphate-free laundry detergent solution with a mass fraction of 0.5% and a pH value of 8.2) was at a temperature of 30°C and stirred at a speed of 100 r / min for 24 h. The test samples were taken out and rinsed, and then placed in an oven at 50°C for drying for 20 min. The weight was then weighed and the mass loss was calculated. At the same time, it was observed whether whitening occurred on the surface of the electroplated layer or whether there was metal particle sedimentation after the solution was settled, and the records were made, as shown in Table 4.

[0117] (III) Wear resistance

[0118] The wear resistance of the electroplated layer of the electroplated PUR film obtained in Examples 1-14 and Comparative Examples 1-2 was tested with reference to GB / T 1768-2006. The rubber grinding wheel was loaded with 1 kg. After the friction coefficient was circulated for 200 times, the mass loss was calculated. The details are shown in Table 4.

[0119] Table 3 Experimental data of Examples 1-3 and Comparative Examples 1-2 (I)

[0120] Test items Peel force(N) Example 1 5.2 Example 2 5.4 Example 3 5.2 Comparative Example 1 3.0 Comparative Example 2 2.4

[0121] As can be seen from Table 3, the peeling force of Comparative Examples 1-2 is lower than that of Example 1, indicating that when the TPU / ABS electroplated film is thermally bonded to the sole material, the bonding is unstable, resulting in the TPU / ABS electroplated film being easily detached. The ABS electroplated film is also easily detached when thermally bonded to the sole material, reducing the decorative effect of the electroplated film on the surface of the shoe material. The electroplated TPU film prepared by the present application is stably bonded to the sole, and the electroplated TPU film can be stabilized on the sole surface, reducing the possibility of the electroplated TPU film falling off during use.

[0122] Table 4 Experimental data of Experiment (II) and Experiment (III) of Examples 1-14 and Comparative Examples 1-2

[0123]

[0124] It can be seen from Table 4 that the mass loss after the water washing test and the mass loss after the wear test of Comparative Example 1 are both higher than those of Example 1, indicating that the electroplated TPU prepared in the present application has good water washing resistance and wear resistance, and a large area of ​​whitening occurs in Comparative Example 1, indicating that a large amount of electroplated metal particles fall off, while a smaller area of ​​the electroplated TPU film in the present application has whitening, indicating that fewer electroplated metal particles fall off in the electroplated TPU film. It can be seen that the electroplated TPU film obtained in the present application has good durability.

[0125] Comparing Example 1 and Example 4, the mass loss after the water washing test and the mass loss after the wear resistance test of Example 4 are lower than those of Example 1, indicating that the electroplated TPU layer obtained in the present application has good wear resistance and water resistance, and further illustrates that the protective layer formed after coating the protective glue obtained by the production process of the present application has good wear resistance, and thus has a good protective effect on the electroplating layer, reduces the shedding of the electroplating layer, and improves the decorative effect on shoes, bags, etc.

[0126] By comparing Example 5 and Example 8, it can be seen that the mass loss after the water washing test and the mass loss after the wear resistance test of Example 8 are lower than those of Example 5, indicating that the thickener obtained by mixing bis(dioctyloxypyrophosphate)ethylene titanate, γ-methacryloxypropyltrimethoxysilane, and triacetylacetonate aluminum has a good thickening effect, further improves the wear resistance of the protective layer, reduces the wear of the electroplated layer, and thus improves the decorative effect and durability of the electroplated TPU film.

[0127] By comparing Example 8 and Example 12, it can be seen that the mass loss after the water washing test and the mass loss after the wear resistance test of Example 12 are lower than those of Example 8, indicating that the wear-resistant agent obtained by mixing polyborosilazane, glycidyl ether oxypropyl cyclotetrasiloxane, and silicone-modified polycarbonate polyurethane resin is used in the protective glue, which has a good wear-resistant effect, reduces the wear of the electroplated layer, and thus improves the decorative effect and durability of the electroplated TPU film.

[0128] Comparing Examples 13-14 with Example 4, the mass loss after the water washing test and the mass loss after the wear test of Example 4 are lower than those of Examples 13-14, indicating that when no wear-resistant agent or tackifier is added, the protective layer formed by curing the protective glue has a better wear-resistant effect.

[0129] This specific embodiment is merely an explanation of the present application and is not a limitation of the present application. After reading this specification, those skilled in the art may make modifications to the present embodiment without any creative contribution as needed, but such modifications are protected by the patent law as long as they are within the scope of the claims of the present application.

Claims

1. A production process for electroplating TPU film, characterized in that: The following steps are involved: 1) Lay the side of the ABS electroplated film away from the electroplated layer on the TPU film layer, and then preheat it for 5-10s at a temperature of 70-80°C to obtain a semi-finished product; 2) The semi-finished product is subjected to hot pressing, wherein the temperature near the TPU film is 110-130°C, the temperature near the ABS electroplated film is 150-170°C, the pressing force is 2-10N, and the hot pressing time is 1-5s to obtain the electroplated TPU film; The step 1) further includes forming a protective layer on the surface of the ABS electroplated film. The specific process in the step 1) is as follows: The protective glue is coated on the surface of the electroplated layer of the ABS electroplated film, solidified, and a protective layer is formed on the surface of the electroplated layer. Then, the ABS layer of the ABS electroplated film with the protective layer is laminated with the TPU film layer, and then preheated for 5-10s at a preheating temperature of 70-80°C to obtain a semi-finished product; The protective glue is composed of the following raw materials in parts by weight: Polyester modified acrylic resin 5-10 parts Wear-resistant agent 0.2-0.8 parts Thickener 0.1-0.3 parts 5-14 parts of diluent 0.001-0.04 parts of platinum catalyst; The tackifier is composed of one or more of bis(diethyl citrate)dipropoxy zirconium chelate, bis(dioctyloxypyrophosphate)ethylene titanate, γ-methacryloxypropyltrimethoxysilane, and aluminum triacetylacetonate; The wear-resistant agent is one or more of polyborosilazane, glycidyloxypropyl cyclotetrasiloxane, and organosilicon-modified polycarbonate polyurethane resin.

2. The production process of electroplated TPU film according to claim 1, characterized in that: The curing temperature is 130-150° C., and the curing time is 1-3 minutes.

3. The production process of electroplated TPU film according to claim 1, characterized in that: The wear-resistant agent is composed of polyborosilazane and glycidyloxypropyl cyclotetrasiloxane in a weight ratio of 1:(0.1-0.5), or polyborosilazane and organosilicon-modified polycarbonate polyurethane resin in a weight ratio of 1:(0.2-0.5), or polyborosilazane, glycidyloxypropyl cyclotetrasiloxane and organosilicon-modified polycarbonate polyurethane resin in a weight ratio of 1:(0.05-0.1):(0.2-0.3).

4. The production process of electroplated TPU film according to claim 1, characterized in that: The protective glue is prepared by the following method: According to parts by weight, polyester modified acrylic resin, diluent, tackifier, anti-wear agent and platinum catalyst are weighed and mixed evenly to obtain a protective glue solution.

5. An electroplated TPU film, characterized in that: An ABS electroplated composite layer and a TPU film layer are sequentially arranged from the upper surface to the lower surface, the thickness of the electroplated TPU film is 0.1-2 mm, the thickness ratio of the ABS electroplated film composite layer to the thickness of the TPU film layer is 1:(1-3.8), the ABS electroplated composite layer includes an ABS layer and an electroplated layer, the ABS layer is bonded to the TPU film layer, the thickness ratio of the ABS layer to the thickness of the electroplated layer is 1:(0.1-0.5), and the electroplated TPU film is obtained by a production process of an electroplated TPU film according to any one of claims 1 to 4.

6. The production process of electroplated TPU film according to claim 5, characterized in that: The electroplated film composite layer also includes a protective layer, which is bonded to the electroplated layer. The thickness of the protective layer and the thickness of the ABS layer have a ratio of (0.08-0.42):1.

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