Metal wire-drawing decorative film and preparation method thereof

Abstract

The invention provides a metal wiredrawing decorative film and a preparation method thereof. The preparation method of the metal wiredrawing decorative film comprises the following steps that S1, a PET base material is sequentially subjected to pretreatment and surface activation, then the activated PET base material is subjected to dynamic wiredrawing, and a PET wiredrawing film is obtained; s2, vacuum gradient coating is conducted on the surface of the PET wiredrawing film, and a gradient alloy coating is obtained; and S3, the surface of the gradient alloy layer is coated with a self-repairing protective coating, a protective layer is obtained after curing, and the metal wiredrawing decorative film is obtained. The PET base material is pretreated, the surface of the PET base material is activated, then vacuum gradient coating is conducted, the metal layer can be tightly fixed to the surface of the PET base material, meanwhile, the corrosion resistance can be remarkably improved, the protective layer is coated on the gradient alloy gold plating surface, the self-repairing function is achieved, and the service life of the decorative film is remarkably prolonged.

Description

Technical Field

[0001] The present invention relates to the technical field of decorative films, and particularly to a metal wire drawing decorative film and a preparation method thereof. Background Art

[0002] The metal wire drawing decorative film is widely used in the shell decoration of furniture decoration, electronic products and automobile interiors. By combining the metallic luster with the wire drawing texture, it endows the product with a unique texture and visual effect, and at the same time has the advantages of light weight, corrosion resistance, easy processing, etc. With the continuous improvement of the requirements for the surface texture of materials in modern industrial design, the market demand for metal wire drawing decorative films continues to grow.

[0003] In the field of electronic products, high-end products of well-known brands such as mobile phones and laptop computers all use metal wire drawing decorative films as appearance decoration materials; in the field of furniture decoration, products such as refrigerators and washing machines use metal wire drawing decorative films as appearance panels to improve durability; in the field of automobile interiors, automobile instrument panels, consoles and door panels use metal wire drawing decorative films as decorations to enhance the sense of technology.

[0004] At present, the preparation process of metal wire drawing decorative films mainly includes steps such as base film treatment, wire drawing treatment, metal plating and protective layer coating. The base film usually uses polymer materials such as polyester or polycarbonate to endow the base film with good mechanical properties, transparency and processing properties; the wire drawing treatment mainly forms a uniform texture on the surface of the base film by mechanical or chemical methods to simulate the metal wire drawing effect; the metal plating usually uses vacuum evaporation or magnetron sputtering technology to deposit a layer of metal on the surface of the base film to endow the material with metallic luster; the protective layer coating is mainly to improve the wear resistance and corrosion resistance of the decorative film, and usually uses materials such as acrylic resin and polyurethane resin. Although the above-mentioned metal wire drawing decorative films have wide applications in the market, their technological development still has some challenges. For example, the adhesion between the metal plating and the base film is insufficient, resulting in the shedding of the plating; the wear resistance, heat resistance and self-repair performance of the protective layer all need to be improved. Summary of the Invention

[0005] (I) Technical Problems to be Solved

[0006] In view of the deficiencies of the prior art, the present invention provides a metal wire drawing decorative film and a preparation method thereof, which solve the problems raised in the above background art.

[0007] (II) Technical Solutions

[0008] To achieve the above objectives, the present invention is realized through the following technical solutions:

[0009] According to the first aspect of the present invention, a preparation method of a metal wire drawing decorative film is provided, including the following steps:

[0010] S1. First, pretreat the PET substrate in sequence to activate its surface, and then perform dynamic wire drawing on the activated PET substrate to obtain a PET drawn film;

[0011] S2. Perform vacuum gradient coating on the surface of the PET drawn film to obtain a gradient alloy coating;

[0012] S3. Coat a self - repairing protective coating on the surface of the gradient alloy layer, and after curing, obtain a protective layer, that is, a metal drawn decorative film.

[0013] By pretreating the PET substrate in the present invention, the surface of the PET substrate is activated, and then vacuum gradient coating is carried out, so that the metal layer can be tightly fixed on the surface of the PET substrate, and at the same time, the corrosion resistance can be significantly improved. Then, a protective layer with self - repairing function is coated on the surface of the gradient alloy plating, which can significantly extend the service life of the decorative film.

[0014] Preferably, in step S1, the pretreatment includes plasma activation and corona treatment carried out in sequence;

[0015] Among them, the process parameters of the plasma activation are: in an argon atmosphere, the power density is 0.6 - 1.0 W / cm 2 , and the treatment time is 30 - 50 s;

[0016] The process parameters of the corona treatment are: in an air atmosphere, the power density is 0.8 - 1.0 W / cm2, and the treatment speed is 20 - 50 m / min.

[0017] Preferably, in step S2, the process of the vacuum gradient coating is: use the magnetron sputtering process to perform primary vacuum aluminizing, vacuum copper plating, and secondary vacuum aluminizing on the surface of the PET drawn film in sequence.

[0018] Preferably, the sputtering power of the primary vacuum aluminizing is 2.5 - 3.0 kW, the working gas pressure is 0.3 - 0.5 Pa, and the deposition time is 60 - 80 s;

[0019] The sputtering power of the vacuum copper plating is 1.5 - 2.0 kW, the working gas pressure is 0.4 - 0.6 Pa, and the deposition time is 40 - 60 s;

[0020] The sputtering power of the secondary vacuum aluminizing is 2.0 - 2.5 kW, the working gas pressure is 0.3 - 0.5 Pa, and the deposition time is 50 - 70 s.

[0021] Preferably, in step S2, after the vacuum gradient coating, an annealing treatment is carried out;

[0022] The temperature of the annealing treatment is 145 - 155 °C, and the time of the annealing treatment is 20 - 40 min.

[0023] Preferably, in step S3, the preparation method of the self-healing protective coating is to dissolve graphene quantum dots in a solvent, then add polyurethane-acrylic resin and stir evenly, then add functional additives, and finally add microcapsule silicone prepolymer.

[0024] Preferably, the self-healing protective coating, by mass fraction, comprises 60-70% of polyurethane-acrylic resin, 5-8% of microcapsule silicone prepolymer, 0.5-1.0% of graphene quantum dots, 3.8-5.9% of functional additives, and 15-20% of solvent.

[0025] Preferably, in step S3, the curing temperature is 80-120 °C and the curing time is 10-20 min.

[0026] According to a second aspect of the present invention, there is provided a metal-drawn decorative film obtained by the above preparation method, comprising a PET drawn film, wherein a gradient alloy coating is provided on the surface of the PET drawn film, and a protective layer is provided on the surface of the gradient alloy coating.

[0027] Preferably, the thickness of the PET drawn film is 150-200 μm, the thickness of the gradient alloy coating is 1.2-1.7 μm, and the thickness of the protective layer is 3-5 μm.

[0028] (III) Beneficial effects

[0029] The present invention provides a metal-drawn decorative film and a preparation method thereof. The following beneficial effects are achieved:

[0030] The preparation method of the metal-drawn decorative film provided by this solution enhances the surface activity of the PET substrate through plasma activation and corona treatment. After generating texture by dynamic drawing, a gradient alloy coating is deposited by magnetron sputtering technology, significantly improving the metallic luster, adhesion, and corrosion resistance. And the wear resistance and self-healing function are improved by coating the self-healing protective coating. By optimizing the preparation process, the obtained metal-drawn decorative film has high surface quality, excellent mechanical properties, and durability. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Figure 1 is a schematic structural diagram of the metal-drawn decorative film in the present invention;

[0032] Figure 2 is a surface schematic diagram of the metal-drawn decorative film in the present invention;

[0033] Wherein, 1, PET drawn film; 2, gradient alloy coating; 3, protective layer; 21, first aluminum layer; 22, copper layer; 23, second aluminum layer. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0034] To better illustrate and elaborate on the content of the present invention, the following will be described in detail with specific embodiments.

[0035] Example 1

[0036] A method for preparing a metal-drawn decorative film includes the following steps:

[0037] Step 1: Use a PET substrate with a thickness of 150 μm. First, in an argon atmosphere, set the power density to 0.8 W / cm 2 , perform plasma activation treatment on the surface of the PET substrate for 40 s, and then in an air atmosphere, set the power density to 0.9 W / cm 2 , perform corona treatment on the surface of the PET substrate. The treatment speed of the PET substrate is 30 m / min. Finally, perform dynamic wire drawing on one side of the PET substrate to obtain a PET drawn film;

[0038] Step 2: First, use 99.999% Al as the target, adjust the sputtering power to 2.8 kW, the working pressure to 0.4 Pa, and deposit for 70 s to deposit a 700-nm aluminum layer on the surface of the PET drawn film. Then, use 99.999% Cu as the target, adjust the sputtering power to 1.8 kW, the working pressure to 0.5 Pa, and deposit for 50 s to deposit a 250-nm Cu layer on the surface of the aluminum layer. Finally, use 99.999% Al as the target again, adjust the sputtering power to 2.3 kW, the working pressure to 0.4 Pa, and deposit for 60 s to deposit a 450-nm layer on the surface of the Cu layer. After the deposition is completed, anneal at 150 °C for 30 min to obtain a vacuum gradient coating;

[0039] Step 3: Dissolve 0.8% graphene quantum dots in 23.7% ethyl acetate, then add 65% polyurethane-acrylic resin and stir evenly. Then add 3% hexamethylene diisocyanate trimer, 0.5% polyether-modified silicone, 0.2% mineral oil, 0.8% benzotriazole, and finally add 6% microcapsule silicone prepolymer and stir evenly to obtain a self-healing protective coating;

[0040] Step 4: Coat the self-healing protective coating on the surface of the vacuum gradient coating and cure at 100 °C for 15 min to obtain a 3-μm-thick protective layer, that is, the metal-drawn decorative film.

[0041] The structural diagram and surface diagram of the metal-drawn decorative film prepared in this example are as shown in Figure 1 and Figure 2 . The surface of the metal-drawn decorative film has a unique metallic texture and can be applied to furniture decoration, electronic products, and automotive interiors.

[0042] Example 2

[0043] A preparation method of a metal wire-drawing decorative film, comprising the following steps:

[0044] Step 1: Use a PET substrate with a thickness of 200 μm. First, in an argon atmosphere, set the power density to 1.0 W / cm 2 , perform plasma activation treatment on the surface of the PET substrate for 30 s, then in an air atmosphere, set the power density to 1.0 W / cm 2 , perform corona treatment on the surface of the PET substrate. The treatment speed of the PET substrate is 20 m / min. Finally, perform dynamic wire drawing on one side of the PET substrate to obtain a PET wire-drawing film;

[0045] Step 2: First, use 99.999% Al as the target, adjust the sputtering power to 3.0 kW, the working pressure to 0.3 Pa, and deposit for 80 s to deposit an 800-nm aluminum layer on the surface of the PET wire-drawing film. Then, use 99.999% Cu as the target, adjust the sputtering power to 2.0 kW, the working pressure to 0.4 Pa, and deposit for 60 s to deposit a 300-nm Cu layer on the surface of the aluminum layer. Finally, use 99.999% Al as the target, adjust the sputtering power to 2.5 kW, the working pressure to 0.3 Pa, and deposit for 70 s to deposit a 550-nm layer on the surface of the Cu layer. After the deposition is completed, anneal at 155 °C for 20 min to obtain a vacuum gradient coating;

[0046] Step 3: Dissolve 1.0% graphene quantum dots in 15.1% methyl ethyl ketone, then add 70% polyurethane-acrylic resin and stir evenly. Then add 3.5% hexamethylene diisocyanate trimer, 0.8% polyether-modified silicone, 0.3% mineral oil, 1.3% benzotriazole, and finally add 8% microcapsule silicone pre-polymer and stir evenly to obtain a self-healing protective coating;

[0047] Step 4: Coat the self-healing protective coating on the surface of the vacuum gradient coating and cure at 120 °C for 10 min to obtain a protective layer with a thickness of 3.5 μm, that is, a metal wire-drawing decorative film.

[0048] Example 3

[0049] A preparation method of a metal wire-drawing decorative film, comprising the following steps:

[0050] Step 1: Use a PET substrate with a thickness of 180 μm. First, in an argon atmosphere, set the power density to 0.6 W / cm 2 , perform plasma activation treatment on the surface of the PET substrate for 50 s, then in an air atmosphere, set the power density to 0.8 W / cm 2, the surface of the PET substrate is corona-treated at a processing speed of 50 m / min for the PET substrate. Finally, dynamic wire drawing is performed on one side of the PET substrate to obtain a PET wire-drawn film;

[0051] Step 2: First, use 99.999% Al as the target, adjust the sputtering power to 2.5 kW, the working pressure to 0.5 Pa, and deposit for 60 s to deposit a 600-nm aluminum layer on the surface of the PET wire-drawn film. Then, use 99.999% Cu as the target, adjust the sputtering power to 1.5 kW, the working pressure to 0.6 Pa, and deposit for 40 s to deposit a 200-nm-thick Cu layer on the aluminum layer. Finally, use 99.999% Al as the target again, adjust the sputtering power to 2.0 kW, the working pressure to 0.5 Pa, and deposit for 50 s to deposit a 400-nm-thick layer on the Cu layer. After the deposition is completed, annealing treatment is carried out at 145 °C for 40 min to obtain a vacuum gradient coating;

[0052] Step 3: Dissolve 0.5% graphene quantum dots in 30.7% methyl ethyl ketone, then add 60% polyurethane-acrylic resin and stir evenly. Then add 3.0% hexamethylene diisocyanate trimer, 0.2% polyether-modified silicone, 0.3% mineral oil, 0.3% benzotriazole. Finally, add 5% microcapsule silicone oligomer prepolymer and stir evenly to obtain a self-healing protective coating;

[0053] Step 4: Coat the self-healing protective coating on the surface of the vacuum gradient coating and cure it at 80 °C for 20 min to obtain a 4.5-μm-thick protective layer, that is, a metal wire-drawn decorative film.

[0054] Comparative Example 1

[0055] The preparation method of this comparative example is the same as that of Example 1, except that in Step 2, only aluminum plating is performed once, and copper plating and secondary aluminum plating are not carried out.

[0056] Comparative Example 2

[0057] The preparation method of this comparative example is the same as that of Example 1, except that the microcapsule silicone oligomer prepolymer is not added to the protective coating in Step 3.

[0058] Performance tests were carried out on the metal wire-drawn decorative films prepared in Examples 1 to 3 and Comparative Examples 1 and 2. Among them, the adhesion was measured according to ASTM D3359; a CS-10 grinding wheel was used with a load of 500 g and 1000 revolutions to measure the abrasion resistance of the metal wire-drawn decorative film; a scratch width of 50 μm was set, and the repair results were observed for 24 h, as shown in Table 1:

[0059] Table 1

[0060]

[0061] According to the data in Table 1, through plasma activation combined with corona treatment, the surface activity of the substrate is significantly improved, and the adhesion is improved. Through the gradient alloy coating, the corrosion resistance can be significantly improved. At the same time, a self-repairing protective layer is provided on the surface of the gradient alloy coating to achieve the self-repairing function.

[0062] Although the embodiments of the present invention have been shown and described, those of ordinary skill in the art can understand that various changes, modifications, substitutions, and variations can be made to these embodiments without departing from the principles and spirit of the present invention. The scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A method for preparing a metal brushed decorative film, characterized in that: The following steps are involved: S1, pre-treating the PET substrate in sequence to activate the surface, and then dynamically drawing the activated PET substrate to obtain a PET drawing film; S2, performing vacuum gradient coating on the surface of the PET drawing film to obtain a gradient alloy coating; S3, coating the surface of the gradient alloy layer with a self-repairing protective coating, and obtaining a protective layer after curing, that is, obtaining a metal brushed decorative film.

2. The method for preparing a brushed metal decorative film according to claim 1, characterized in that: In step S1, the pretreatment includes plasma activation and corona treatment performed sequentially; The process parameters of the plasma activation are: in an argon atmosphere, the power density is 0.6-1.0 W / cm 2 , the processing time is 30 to 50 seconds; The process parameters of the corona treatment are: in air atmosphere, the power density is 0.8-1.0 W / cm2, and the treatment speed is 20-50 m / min.

3. The method for preparing a metal brushed decorative film according to claim 1, characterized in that: In step S2, the process of vacuum gradient coating is: using a magnetron sputtering process to sequentially perform a first vacuum aluminum coating, a vacuum copper coating and a second vacuum aluminum coating on the surface of the PET drawing film.

4. The method for preparing a brushed metal decorative film according to claim 3, characterized in that: The sputtering power of the vacuum aluminum plating is 2.5-3.0 kW, the working gas pressure is 0.3-0.5 Pa, and the deposition time is 60-80 s; The sputtering power of the vacuum copper plating is 1.5-2.0 kW, the working gas pressure is 0.4-0.6 Pa, and the deposition time is 40-60 s; The sputtering power of the secondary vacuum aluminum plating is 2.0-2.5 kW, the working gas pressure is 0.3-0.5 Pa, and the deposition time is 50-70 s.

5. The method for preparing a brushed metal decorative film according to claim 1, characterized in that: In step S2, after vacuum gradient coating, annealing is performed; The temperature of the annealing treatment is 145-155° C., and the time of the annealing treatment is 20-40 minutes.

6. The method for preparing a brushed metal decorative film according to claim 1, characterized in that: In step S3, the preparation method of the self-healing protective coating is to dissolve graphene quantum dots in a solvent, add polyurethane-acrylic resin and stir evenly, then add functional additives, and finally add microcapsule siloxane prepolymer.

7. The method for preparing a brushed metal decorative film according to claim 6, characterized in that: The self-repairing protective coating comprises, by mass fraction, 60-70% of polyurethane-acrylic resin, 5-8% of microcapsule siloxane prepolymer, 0.5-1.0% of graphene quantum dots, 3.8-5.9% of functional additives and 15-20% of solvent.

8. The method for preparing a brushed metal decorative film according to claim 1, characterized in that: In step S3, the curing temperature is 80-120° C., and the curing time is 10-20 min.

9. The metal brushed decorative film obtained by the preparation method according to any one of claims 1 to 8, characterized in that: The invention comprises a PET drawing film, the surface of which is provided with a gradient alloy coating, and the surface of which is provided with a protective layer.

10. The metal brushed decorative film according to claim 9, characterized in that: The thickness of the PET wire drawing die is 150-200 μm, the thickness of the gradient alloy coating is 1.2-1.7 μm, and the thickness of the protective layer is 3-5 μm.

Images