PET mirror film and preparation method thereof

Abstract

The invention discloses a PET mirror film and a preparation method thereof, and belongs to the technical field of PET films, the preparation method of the PET mirror film comprises the following steps: (1) providing a first PET film and a second PET film; (2) performing plasma surface treatment on the first PET film, and electroplating the first PET film to form an electroplated layer; (3) coating coloring liquid on the surface of the electroplated layer to form a coloring layer; (4) plasma surface treatment is carried out on the coloring layer, a second PET film is placed on the surface of the coloring layer, and then plasma surface treatment is carried out on the second PET film; and (5) coating the surface of the second PET film with an anti-scraping coating to form an anti-scraping layer. The PET mirror surface film provided by the invention has excellent wear resistance, scratch resistance and aging resistance, and has a wide application prospect.

Description

Technical Field

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

[0002] In the early stage, the selection of substrates for mirror decorative films was limited and their performance was relatively ordinary. With the continuous progress of materials science, plastic films such as PET (polyethylene terephthalate) and PC (polycarbonate) have been widely used as substrates. Traditional mirrors usually use glass as the substrate, which has problems such as being fragile, heavy in weight, inconvenient for transportation and installation, and the cost of glass mirrors is relatively high. After being broken, it is easy to hurt people and there are safety hazards.

[0003] In terms of architectural decoration, people's requirements for the aesthetics and uniqueness of interior decoration are getting higher and higher. Mirror decorative films can simulate mirror effects and add a sense of brightness and spaciousness to the architectural space. In home decoration, mirror decorative films can be used for the decoration of the surfaces of furniture, cabinets, electrical appliances, etc., adding a sense of fashion and modernity to the furniture environment. The existing PET films have insufficient abrasion resistance and scratch resistance. During long-term use, due to frequent touching, wiping and other operations, the surface will gradually wear, resulting in a decrease in reflectivity and a deterioration of the mirror effect, and the service life is relatively short.

[0004] In view of this, this application is proposed. Summary of the Invention

[0005] The purpose of the present invention is to overcome the deficiencies of the prior art and provide a PET mirror film and a preparation method thereof. The PET mirror film of the present invention has excellent abrasion resistance, scratch resistance and aging resistance, and has broad application prospects.

[0006] To achieve the above purpose, the technical solution adopted by the present invention is as follows:

[0007] A preparation method of a PET mirror film includes the following steps:

[0008] (1) Provide a first PET film and a second PET film;

[0009] (2) Perform plasma surface treatment on the first PET film, and electroplate the first PET film to form an electroplated layer;

[0010] (3) Coat a coloring solution on the surface of the electroplated layer to form a coloring layer;

[0011] (4) Perform plasma surface treatment on the coloring layer, place the second PET film on the surface of the coloring layer, and then perform plasma surface treatment on the second PET film;

[0012] (5) Coat an anti-scratch coating on the surface of the second PET film to form an anti-scratch layer.

[0013] The PET mirror film of the present application is a multi-layer film, which has high gloss and reflectivity, can provide a high reflection effect like a mirror surface, endow the product surface with unique visual attraction, enhance the aesthetic degree of the product, and meet the requirements for high-end and fashionable appearances. It has excellent flatness and uniformity, ensuring that the product appearance is flat and smooth, without obvious unevenness or defects, making the reflection effect more uniform. At the same time, the PET mirror film described in the present invention has excellent wear resistance, scratch resistance and aging resistance, can effectively prevent the product surface from being scratched and worn, extend the service life of the product, has a certain resistance to common chemical substances, and can prevent the intrusion of moisture and humidity, protecting the interior of the product from damage.

[0014] Due to the characteristics of the PET material, the PET mirror film described in the present invention will not break into sharp fragments even when subjected to external force impact, thus avoiding the risk of injury.

[0015] As a preferred embodiment of the present invention, the power of the plasma surface treatment is 100 - 300W, and the time is 1 - 4min.

[0016] As a preferred embodiment of the present invention, the electroplated layer is aluminum, silver, copper, chromium or zinc; the thickness of the electroplated layer is 10 - 20nm.

[0017] As a preferred embodiment of the present invention, the thickness of the coloring layer is 0.5 - 1.2μm.

[0018] As a preferred embodiment of the present invention, the coloring solution comprises the following components in parts by weight: 50 - 70 parts of acrylic resin, 10 - 30 parts of the first solvent, 0.1 - 0.5 part of leveling agent, 0.1 - 0.3 part of antioxidant, 1 - 2 parts of isophorone diisocyanate, 3 - 5 parts of color paste.

[0019] As a preferred embodiment of the present invention, the antioxidant comprises at least one of antioxidant 1010, antioxidant 1086, and antioxidant 1076.

[0020] As a preferred embodiment of the present invention, the leveling agent comprises at least one of acrylated polysiloxane, polyether-modified polysiloxane, polysiloxane polyether copolymer, and polysiloxane.

[0021] As a preferred embodiment of the present invention, the first solvent comprises at least one of water, ethylene glycol monobutyl ether, ethyl acetate, butyl acetate, diethylene glycol monoethyl ether, methyl ethyl ketone, diisobutyl ketone, and N,N-dimethylformamide.

[0022] It should be noted that the present invention does not limit the preparation method of the coloring solution. Those skilled in the art can prepare it into a coloring solution according to the conventional technical means in the art and based on the formula of the present invention. For example, by mixing each raw material evenly according to the ratio, the coloring solution can be obtained.

[0023] As a preferred embodiment of the present invention, the scratch-resistant coating comprises the following components in parts by weight: 45 - 55 parts of hydroxy acrylic resin, 6 - 12 parts of cashew shell oil bio-based polyol, 9 - 12 parts of modified acicular wollastonite powder, 2 - 5 parts of polyvinyl alcohol, 2 - 4 parts of isophorone diisocyanate, 0.2 - 0.6 part of defoaming agent, 0.1 - 0.2 part of catalyst, 0.5 - 1.2 parts of titanium dioxide, and 15 - 25 parts of a second solvent.

[0024] The present invention creatively uses hydroxy acrylic resin as the matrix, which has excellent gloss and weather resistance. The cashew shell oil bio-based polyol, hydroxy acrylic resin, and isophorone diisocyanate form a three-dimensional cross-linked network structure. The introduction of the cashew shell oil bio-based polyol not only improves the scratch resistance of the coating but also prevents cracks in the coating when it is impacted or scratched by providing flexibility. At the same time, the natural phenolic components in the cashew shell oil can enhance the ultraviolet resistance of the coating, thereby improving the aging resistance of the coating. Among them, the modified acicular wollastonite powder has abundant functional groups, which can be evenly dispersed in the system and interpenetrate in the three-dimensional cross-linked network structure by using its special structure and participate in the formation of the cross-linked network structure, thus forming a unique filling network structure. By using the special cross-linked network structure and the unique filling network structure, the wear resistance, scratch resistance, and aging resistance of the PET mirror film are effectively improved.

[0025] As a preferred embodiment of the present invention, the second solvent comprises at least one of water, ethylene glycol monobutyl ether, ethyl acetate, butyl acetate, diethylene glycol monoethyl ether, methyl ethyl ketone, diisobutyl ketone, and N,N-dimethylformamide.

[0026] As a preferred embodiment of the present invention, the defoaming agent comprises at least one of tributyl phosphate, trimethylsiloxane, polyether, polyacrylate, and silicone resin.

[0027] As a preferred embodiment of the present invention, the catalyst comprises at least one of dibutyltin dilaurate, dibutyltin diacetate, and stannous octoate.

[0028] As a preferred embodiment of the present invention, the hydroxyl value of the cashew shell oil bio-based polyol is 224 - 256 mgKOH / g, and the viscosity at 25 °C is 1200 - 1710 mPa·s.

[0029] As a preferred embodiment of the present invention, the solid content of the hydroxy acrylic resin is 44-46 wt%, the viscosity at 25 °C is 1000-4000 mPa·s, the hydroxyl content is 2-2.5 wt%, and the glass transition temperature is 40-50 °C.

[0030] As a preferred embodiment of the present invention, the preparation method of the modified acicular wollastonite powder is as follows:

[0031] (1) Add 10 parts by weight of acicular wollastonite powder, 0.8-1.2 parts by weight of stearic acid, 0.4-0.8 parts by weight of oleic acid, and 6-12 parts by weight of absolute ethanol to 25-40 parts by weight of water, stir evenly at 70-85 °C, and then add 0.2-0.6 parts by weight of sorbitan monostearate, stir evenly to obtain a precursor solution;

[0032] (2) Add 10 parts by weight of amino silicone oil, 6-8 parts by weight of N-oleoyl-N-methyl taurine sodium salt, and 4-6 parts by weight of dopamine hydrochloride to 30-50 parts by weight of water, stir evenly, and then add 0.8-1.5 parts by weight of tris(hydroxymethyl)aminomethane hydrochloride buffer solution, stir evenly to obtain a modified solution;

[0033] (3) Drop 2-5 parts by weight of the modified solution into 10 parts by weight of the precursor solution, stir evenly at 70-85 °C, filter, and dry to obtain the modified acicular wollastonite powder.

[0034] In the present invention, the acicular wollastonite powder is first treated with stearic acid and oleic acid in an absolute ethanol aqueous solution. Stearic acid and oleic acid have long-chain hydrocarbon groups, which can form a hydrophobic film layer on the surface of the acicular wollastonite powder, increasing its surface hydrophobicity. By reacting with the groups of the acicular wollastonite powder, the surface properties of wollastonite can be changed, making it have better wettability and lipophilicity, thus effectively improving its dispersion performance in the scratch-resistant coating and avoiding agglomeration. Sorbitan monostearate can further improve the dispersion of wollastonite powder and form a good interface in the coating, making the filler more compatible with the resin. Then, a mixed solution of amino silicone oil, N-oleoyl-N-methyl taurine sodium salt, dopamine hydrochloride, and tris(hydroxymethyl)aminomethane hydrochloride buffer solution is used as the modified solution. By enhancing the surface chemical activity and interfacial affinity of the acicular wollastonite powder, the dispersion of the modified wollastonite in the coating is greatly improved, and the modified wollastonite surface has better chemical affinity, which can better form a crosslinked network with the resin matrix and participate in the formation of the crosslinked network structure, thus forming a unique filling network structure. Using the special crosslinked network structure and unique filling network structure, the wear resistance, scratch resistance, and aging resistance of the PET mirror film are effectively improved.

[0035] As a preferred embodiment of the present invention, the particle size of the acicular wollastonite powder is 200-1000 mesh.

[0036] It should be noted that the present invention is not limited to the preparation method of the scratch-resistant coating. Those skilled in the art can prepare it into a scratch-resistant coating according to the conventional technical means in the art and the formula of the present invention. For example, by mixing each raw material evenly according to the ratio, the scratch-resistant coating can be obtained.

[0037] As a preferred embodiment of the present invention, the thickness of the scratch-resistant layer is 2-6 μm.

[0038] As a preferred embodiment of the present invention, the thickness of the first PET film is 8-50 μm.

[0039] As a preferred embodiment of the present invention, the thickness of the second PET film is 8-50 μm.

[0040] The beneficial effects of the present invention are as follows: The PET mirror film of the present application is a multi-layer film, having high gloss and reflectivity, and can provide a high reflection effect like a mirror, giving the product surface a unique visual attraction, enhancing the beauty of the product, and meeting the requirements for a high-end and fashionable appearance. It has excellent flatness and uniformity, ensuring that the product appearance is flat and smooth, without obvious unevenness or defects, making the reflection effect more uniform. At the same time, the PET mirror film described in the present invention has excellent wear resistance, scratch resistance and aging resistance, can effectively prevent the product surface from being scratched and worn, extend the service life of the product, has a certain resistance to common chemical substances, and can prevent the intrusion of moisture and humidity, protecting the interior of the product from damage. Detailed implementation manners

[0041] To make the objectives, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application will be clearly and completely described below. Obviously, the described embodiments are some, but not all, of the embodiments of the present application. All other embodiments obtained by those of ordinary skill in the art based on the embodiments in the present application without creative efforts shall fall within the scope of protection of the present application.

[0042] In the present application, among the technically characterized described in an open-ended manner, there are included closed technical solutions composed of the listed features, as well as open technical solutions including the listed features.

[0043] In this application, when it comes to numerical ranges, unless otherwise specified, the above numerical ranges are considered continuous and include the minimum and maximum values of the range, as well as every value between such minimum and maximum values. Further, when the range refers to integers, it includes every integer between the minimum and maximum values of the range. In addition, when multiple ranges are provided to describe features or characteristics, the ranges can be combined. In other words, unless otherwise specified, all ranges disclosed herein should be understood to include any and all sub-ranges subsumed therein.

[0044] In this application, there is no particular limitation on the specific dispersion and stirring treatment methods.

[0045] In addition, the terms "first" and "second" are used only for descriptive purposes and cannot be construed as indicating or implying relative importance or implicitly specifying the quantity of the indicated technical features. Thus, features defined with "first" and "second" may explicitly or implicitly include at least one such feature. In the description of the present invention, the meaning of "a plurality" is at least two, such as two, three, etc., unless otherwise specifically defined.

[0046] Unless otherwise specified, the component raw materials or instruments used in each embodiment and comparative example of the present invention are commercially available raw materials or instruments, and the component raw materials used in each parallel experiment are of the same kind.

[0047] The raw materials used in the examples and comparative examples are as follows:

[0048] Solvent: Diethylene glycol monobutyl ether.

[0049] Antioxidant: Antioxidant 1010.

[0050] Leveling agent: BYK347.

[0051] Defoaming agent: BYK028.

[0052] Catalyst: Dibutyltin dilaurate.

[0053] Acrylic resin: Dow AC-261P.

[0054] Hydroxy acrylic resin: The solid content is 45 wt%, the viscosity at 25 °C is 1000 - 4000 mPa·s, the hydroxyl content is 2.2 wt%, and the glass transition temperature is 45 °C.

[0055] Cashew shell oil bio-based polyol-1: FX-9011, the hydroxyl value is 224 mg KOH / g, and the viscosity at 25 °C is 1710 mPa·s.

[0056] Cardanol-based bio-polyol - 2: FX-9014, with a hydroxyl value of 256 mg KOH / g and a viscosity of 1200 mPa·s at 25°C.

[0057] Cardanol-based bio-polyol - 3: FX-9001LV, with a hydroxyl value of 175 mg KOH / g and a viscosity of 1000 mPa·s at 25°C.

[0058] Cardanol-based bio-polyol - 4: FX-9008, with a hydroxyl value of 320 mg KOH / g and a viscosity of 3000 mPa·s at 25°C.

[0059] Tris(hydroxymethyl)aminomethane hydrochloride buffer solution: pH 7.2.

[0060] Amino silicone oil: TP-585C, with a viscosity of 500 - 1000 mPa·s at 25°C.

[0061] Needle-shaped wollastonite powder: 600 mesh, Siyuan Mining.

[0062] Example 1

[0063] A method for preparing a PET mirror film, comprising the following steps:

[0064] (1) Provide two PET films with a thickness of 20 μm (divided into the first PET film and the second PET film);

[0065] (2) Place the first PET film in the reaction chamber of a low-temperature plasma processor, introduce nitrogen at a flow rate of 50 sccm, and treat it at a power of 200 W for 3 min;

[0066] Electroplate aluminum on the first PET film to form an electroplated aluminum layer with a thickness of 20 nm;

[0067] (3) Coat the surface of the electroplated layer with the coloring solution to form a coloring layer with a thickness of 1 μm;

[0068] The coloring solution comprises the following components in parts by weight: 60 parts of acrylic resin, 20 parts of solvent, 0.4 part of leveling agent, 0.2 part of antioxidant, 1.5 parts of isophorone diisocyanate, and 4 parts of color paste.

[0069] (4) Place it in the reaction chamber of a low-temperature plasma processor, introduce nitrogen at a flow rate of 50 sccm, and treat it at a power of 200 W for 3 min;

[0070] Place the second PET film on the surface of the coloring layer, then place it in the reaction chamber of a low-temperature plasma processor, introduce nitrogen at a flow rate of 50 sccm, and treat it at a power of 200 W for 3 min;

[0071] (5) Coat an anti-scratch coating on the surface of the second PET film to form an anti-scratch layer with a thickness of 5 μm.

[0072] The anti-scratch coating comprises the following components in parts by weight: 50 parts of hydroxyl acrylic resin, 10 parts of cashew shell oil bio-based polyol-1, 10 parts of modified acicular wollastonite powder, 4 parts of polyvinyl alcohol (PVA-1000), 3 parts of isophorone diisocyanate, 0.5 part of defoamer, 0.2 part of catalyst, 1 part of titanium dioxide, and 20 parts of solvent.

[0073] The preparation method of the modified acicular wollastonite powder is as follows:

[0074] (1) Add 10 parts by weight of acicular wollastonite powder with a particle size of 600 mesh, 1 part by weight of stearic acid, 0.5 part by weight of oleic acid, and 10 parts by weight of absolute ethanol to 28.5 parts by weight of water. Stir evenly at 80 °C at a rotation speed of 100 rpm, then add 0.5 part by weight of sorbitan monostearate, and stir evenly at a rotation speed of 100 rpm to obtain a precursor solution;

[0075] (2) Add 10 parts by weight of amino silicone oil, 6 parts by weight of N-oleoyl-N-methyl taurine sodium salt, and 6 parts by weight of dopamine hydrochloride to 38 parts by weight of water. Stir evenly at a rotation speed of 100 rpm, then add 1 part by weight of tris(hydroxymethyl)aminomethane hydrochloride buffer solution, and stir evenly to obtain a modified solution;

[0076] (3) Drop 4 parts by weight of the modified solution into 10 parts by weight of the precursor solution, stir evenly at 80 °C at a rotation speed of 100 rpm, filter, and dry at 90 °C to obtain the modified acicular wollastonite powder.

[0077] Example 2

[0078] A preparation method of a PET mirror film comprises the following steps:

[0079] (1) Provide two PET films with a thickness of 20 μm (divided into a first PET film and a second PET film);

[0080] (2) Place the first PET film in the reaction chamber of a low-temperature plasma processor, introduce nitrogen at a flow rate of 50 sccm, and treat it at a power of 200 W for 3 min;

[0081] Perform electroplating aluminum on the first PET film to form an electroplated aluminum layer with a thickness of 20 nm;

[0082] (3) Coat the coloring solution on the surface of the electroplated layer to form a coloring layer with a thickness of 1 μm;

[0083] The coloring solution comprises the following components in parts by weight: 60 parts of acrylic resin, 20 parts of solvent, 0.4 part of leveling agent, 0.2 part of antioxidant, 1.5 parts of isophorone diisocyanate, and 4 parts of color paste.

[0084] (4) Place it in the reaction chamber of a low-temperature plasma processor, introduce nitrogen at a flow rate of 50 sccm, and treat it at a power of 200 W for 3 min;

[0085] Place the second PET film on the surface of the coloring layer, then place it in the reaction chamber of a low-temperature plasma processor, introduce nitrogen at a flow rate of 50 sccm, and treat it at a power of 200 W for 3 min;

[0086] (5) Coat an anti-scratch coating on the surface of the second PET film to form an anti-scratch layer with a thickness of 5 μm.

[0087] The anti-scratch coating comprises the following components in parts by weight: 45 parts of hydroxy acrylic resin, 12 parts of cashew shell oil bio-based polyol-1, 9 parts of modified acicular wollastonite powder, 5 parts of polyvinyl alcohol (PVA-1000), 2 parts of isophorone diisocyanate, 0.6 part of defoaming agent, 0.1 part of catalyst, 1.2 parts of titanium dioxide, and 15 parts of solvent.

[0088] The preparation method of the modified acicular wollastonite powder is as follows:

[0089] (1) Add 10 parts by weight of acicular wollastonite powder with a particle size of 600 mesh, 1 part by weight of stearic acid, 0.5 part by weight of oleic acid, and 10 parts by weight of absolute ethanol to 28.5 parts by weight of water, stir evenly at 80 °C at a rotation speed of 100 rpm, then add 0.5 part by weight of sorbitan monostearate, and stir evenly at a rotation speed of 100 rpm to obtain a precursor solution;

[0090] (2) Add 10 parts by weight of amino silicone oil, 6 parts by weight of N-oleoyl-N-methyl taurine sodium salt, and 6 parts by weight of dopamine hydrochloride to 38 parts by weight of water, stir evenly at a rotation speed of 100 rpm, then add 1 part by weight of tris(hydroxymethyl)aminomethane hydrochloride buffer solution, and stir evenly to obtain a modified solution;

[0091] (3) Drop 4 parts by weight of the modified solution into 10 parts by weight of the precursor solution, stir evenly at 80 °C at a rotation speed of 100 rpm, filter, and dry at 90 °C to obtain the modified acicular wollastonite powder.

[0092] Example 3

[0093] A preparation method of a PET mirror film, comprising the following steps:

[0094] (1) Provide two PET films with a thickness of 20 μm (divided into a first PET film and a second PET film);

[0095] (2) Place the first PET film in the reaction chamber of a low-temperature plasma processor, introduce nitrogen at a flow rate of 50 sccm, and treat it at a power of 200 W for 3 min;

[0096] Electroplate aluminum on the first PET film to form an electroplated aluminum layer with a thickness of 20 nm;

[0097] (3) Coat the coloring liquid on the surface of the electroplated layer to form a coloring layer with a thickness of 1 μm;

[0098] The coloring liquid comprises the following components in parts by weight: 60 parts of acrylic resin, 20 parts of solvent, 0.4 part of leveling agent, 0.2 part of antioxidant, 1.5 parts of isophorone diisocyanate, and 4 parts of color paste.

[0099] (4) Place it in the reaction chamber of a low-temperature plasma processor, introduce nitrogen at a flow rate of 50 sccm, and process it at a power of 200 W for 3 min;

[0100] Place the second PET film on the surface of the coloring layer, then place it in the reaction chamber of a low-temperature plasma processor, introduce nitrogen at a flow rate of 50 sccm, and process it at a power of 200 W for 3 min;

[0101] (5) Coat an anti-scratch coating on the surface of the second PET film to form an anti-scratch layer with a thickness of 5 μm.

[0102] The anti-scratch coating comprises the following components in parts by weight: 55 parts of hydroxy acrylic resin, 6 parts of cashew shell oil bio-based polyol-1, 12 parts of modified acicular wollastonite powder, 2 parts of polyvinyl alcohol (PVA-1000), 4 parts of isophorone diisocyanate, 0.2 part of defoaming agent, 0.2 part of catalyst, 0.5 part of titanium dioxide, and 25 parts of solvent.

[0103] The preparation method of the modified acicular wollastonite powder is as follows:

[0104] (1) Add 10 parts by weight of acicular wollastonite powder with a particle size of 600 mesh, 1 part by weight of stearic acid, 0.5 part by weight of oleic acid, and 10 parts by weight of absolute ethanol to 28.5 parts by weight of water, stir evenly at 80 °C at a rotation speed of 100 rpm, then add 0.5 part by weight of sorbitan monostearate, and stir evenly at a rotation speed of 100 rpm to obtain a precursor solution;

[0105] (2) Add 10 parts by weight of amino silicone oil, 6 parts by weight of N-oleoyl-N-methyl taurine sodium salt, and 6 parts by weight of dopamine hydrochloride to 38 parts by weight of water, stir evenly at a rotation speed of 100 rpm, then add 1 part by weight of tris(hydroxymethyl)aminomethane hydrochloride buffer solution, and stir evenly to obtain a modified solution;

[0106] (3) Drop 4 parts by weight of the modified solution into 10 parts by weight of the precursor solution, stir evenly at 80 °C at a rotation speed of 100 rpm, filter, and dry at 90 °C to obtain the modified acicular wollastonite powder.

[0107] Example 4

[0108] In this embodiment, compared with Embodiment 1, the same amount of cashew shell oil-based polyol-2 is used to replace cashew shell oil-based polyol-1.

[0109] A method for preparing a PET mirror film includes the following steps:

[0110] (1) Provide two PET films with a thickness of 20 μm (divided into the first PET film and the second PET film);

[0111] (2) Place the first PET film in the reaction chamber of a low-temperature plasma processor, introduce nitrogen at a flow rate of 50 sccm, and process it at a power of 200 W for 3 min;

[0112] Electroplate aluminum on the first PET film to form an electroplated aluminum layer with a thickness of 20 nm;

[0113] (3) Coat the surface of the electroplated layer with a coloring solution to form a coloring layer with a thickness of 1 μm;

[0114] The coloring solution includes the following components in parts by weight: 60 parts of acrylic resin, 20 parts of solvent, 0.4 part of leveling agent, 0.2 part of antioxidant, 1.5 parts of isophorone diisocyanate, and 4 parts of color paste.

[0115] (4) Place it in the reaction chamber of a low-temperature plasma processor, introduce nitrogen at a flow rate of 50 sccm, and process it at a power of 200 W for 3 min;

[0116] Place the second PET film on the surface of the coloring layer, then place it in the reaction chamber of a low-temperature plasma processor, introduce nitrogen at a flow rate of 50 sccm, and process it at a power of 200 W for 3 min;

[0117] (5) Coat the surface of the second PET film with an anti-scratch coating to form an anti-scratch layer with a thickness of 5 μm.

[0118] The anti-scratch coating includes the following components in parts by weight: 50 parts of hydroxyl acrylic resin, 10 parts of cashew shell oil-based polyol-2, 10 parts of modified acicular wollastonite powder, 4 parts of polyvinyl alcohol (PVA-1000), 3 parts of isophorone diisocyanate, 0.5 part of defoaming agent, 0.2 part of catalyst, 1 part of titanium dioxide, and 20 parts of solvent.

[0119] The preparation method of the modified acicular wollastonite powder is as follows:

[0120] (1) Add 10 parts by weight of acicular wollastonite powder with a particle size of 600 mesh, 1 part by weight of stearic acid, 0.5 part by weight of oleic acid, and 10 parts by weight of absolute ethanol to 28.5 parts by weight of water, stir evenly at 80 °C at a rotation speed of 100 rpm, then add 0.5 part by weight of sorbitan monostearate, and stir evenly at a rotation speed of 100 rpm to obtain a precursor solution;

[0121] (2) Add 10 parts by weight of amino silicone oil, 6 parts by weight of N - oleoyl - N - methyl taurine sodium, and 6 parts by weight of dopamine hydrochloride to 38 parts by weight of water, stir evenly at a speed of 100 rpm, then add 1 part by weight of tris - hydroxymethyl aminomethane hydrochloride buffer solution, and stir evenly to obtain a modified liquid.

[0122] (3) Drop 4 parts by weight of the modified liquid into 10 parts by weight of the precursor liquid, stir evenly at 80 °C at a speed of 100 rpm, filter, and dry at 90 °C to obtain modified acicular wollastonite powder.

[0123] Example 5

[0124] In this example compared with Example 1, an equal amount of cashew shell oil bio - based polyol - 3 is used to replace cashew shell oil bio - based polyol - 1.

[0125] A preparation method of a PET mirror film includes the following steps:

[0126] (1) Provide two PET films with a thickness of 20 μm (divided into the first PET film and the second PET film);

[0127] (2) Place the first PET film in the reaction chamber of a low - temperature plasma processor, introduce nitrogen at a flow rate of 50 sccm, and process it at a power of 200 W for 3 min;

[0128] Electroplate aluminum on the first PET film to form an electroplated aluminum layer with a thickness of 20 nm;

[0129] (3) Coat the coloring liquid on the surface of the electroplated layer to form a coloring layer with a thickness of 1 μm;

[0130] The coloring liquid includes the following components in parts by weight: 60 parts of acrylic resin, 20 parts of solvent, 0.4 part of leveling agent, 0.2 part of antioxidant, 1.5 parts of isophorone diisocyanate, and 4 parts of color paste.

[0131] (4) Place it in the reaction chamber of a low - temperature plasma processor, introduce nitrogen at a flow rate of 50 sccm, and process it at a power of 200 W for 3 min;

[0132] Place the second PET film on the surface of the coloring layer, then place it in the reaction chamber of a low - temperature plasma processor, introduce nitrogen at a flow rate of 50 sccm, and process it at a power of 200 W for 3 min;

[0133] (5) Coat an anti - scratch coating on the surface of the second PET film to form an anti - scratch layer with a thickness of 5 μm.

[0134] The scratch-resistant coating comprises the following components in parts by weight: 50 parts of hydroxyl acrylic resin, 10 parts of cashew shell oil bio-based polyol-3, 10 parts of modified acicular wollastonite powder, 4 parts of polyvinyl alcohol (PVA-1000), 3 parts of isophorone diisocyanate, 0.5 part of defoamer, 0.2 part of catalyst, 1 part of titanium dioxide, and 20 parts of solvent.

[0135] The preparation method of the modified acicular wollastonite powder is as follows:

[0136] (1) Add 10 parts by weight of acicular wollastonite powder with a particle size of 600 mesh, 1 part by weight of stearic acid, 0.5 part by weight of oleic acid, and 10 parts by weight of absolute ethanol to 28.5 parts by weight of water. Stir evenly at 80 °C at a rotation speed of 100 rpm, then add 0.5 part by weight of sorbitan monostearate, and stir evenly at a rotation speed of 100 rpm to obtain a precursor solution;

[0137] (2) Add 10 parts by weight of amino silicone oil, 6 parts by weight of N-oleoyl-N-methyl taurine sodium salt, and 6 parts by weight of dopamine hydrochloride to 38 parts by weight of water. Stir evenly at a rotation speed of 100 rpm, then add 1 part by weight of tris(hydroxymethyl)aminomethane hydrochloride buffer solution, and stir evenly to obtain a modified solution;

[0138] (3) Drop 4 parts by weight of the modified solution into 10 parts by weight of the precursor solution, stir evenly at 80 °C at a rotation speed of 100 rpm, filter, and dry at 90 °C to obtain the modified acicular wollastonite powder.

[0139] Example 6

[0140] Compared with Example 1, in this example, an equal amount of cashew shell oil bio-based polyol-4 is used to replace cashew shell oil bio-based polyol-1.

[0141] A preparation method of a PET mirror film comprises the following steps:

[0142] (1) Provide two PET films with a thickness of 20 μm (divided into a first PET film and a second PET film);

[0143] (2) Place the first PET film in the reaction chamber of a low-temperature plasma processor, introduce nitrogen at a flow rate of 50 sccm, and treat it at a power of 200 W for 3 min;

[0144] Perform electroplating aluminum on the first PET film to form an electroplated aluminum layer with a thickness of 20 nm;

[0145] (3) Coat the surface of the electroplated layer with a coloring solution to form a coloring layer with a thickness of 1 μm;

[0146] The color liquid comprises the following components in parts by weight: 60 parts of acrylic resin, 20 parts of solvent, 0.4 part of leveling agent, 0.2 part of antioxidant, 1.5 parts of isophorone diisocyanate, and 4 parts of color paste.

[0147] (4) Place it in the reaction chamber of a low-temperature plasma processor, introduce nitrogen at a flow rate of 50 sccm, and process it at a power of 200 W for 3 minutes;

[0148] Place the second PET film on the surface of the coloring layer, then place it in the reaction chamber of a low-temperature plasma processor, introduce nitrogen at a flow rate of 50 sccm, and process it at a power of 200 W for 3 minutes;

[0149] (5) Coat an anti-scratch coating on the surface of the second PET film to form an anti-scratch layer with a thickness of 5 μm.

[0150] The anti-scratch coating comprises the following components in parts by weight: 50 parts of hydroxyl acrylic resin, 10 parts of cashew shell oil bio-based polyol-4, 10 parts of modified acicular wollastonite powder, 4 parts of polyvinyl alcohol (PVA-1000), 3 parts of isophorone diisocyanate, 0.5 part of defoaming agent, 0.2 part of catalyst, 1 part of titanium dioxide, and 20 parts of solvent.

[0151] The preparation method of the modified acicular wollastonite powder is as follows:

[0152] (1) Add 10 parts by weight of acicular wollastonite powder with a particle size of 600 mesh, 1 part by weight of stearic acid, 0.5 part by weight of oleic acid, and 10 parts by weight of absolute ethanol to 28.5 parts by weight of water, stir evenly at 80 °C at a rotation speed of 100 rpm, then add 0.5 part by weight of sorbitan monostearate, and stir evenly at a rotation speed of 100 rpm to obtain a precursor solution;

[0153] (2) Add 10 parts by weight of amino silicone oil, 6 parts by weight of N-oleoyl-N-methyl taurine sodium, and 6 parts by weight of dopamine hydrochloride to 38 parts by weight of water, stir evenly at a rotation speed of 100 rpm, then add 1 part by weight of tris(hydroxymethyl)aminomethane hydrochloride buffer solution, and stir evenly to obtain a modified solution;

[0154] (3) Drop 4 parts by weight of the modified solution into 10 parts by weight of the precursor solution, stir evenly at 80 °C at a rotation speed of 100 rpm, filter, and dry at 90 °C to obtain the modified acicular wollastonite powder.

[0155] Comparative Example 1

[0156] The difference between Comparative Example 1 and Example 1 is that an equal amount of acicular wollastonite powder is used to replace the modified acicular wollastonite powder, and the others are the same.

[0157] The scratch-resistant coating comprises the following components in parts by weight: 50 parts of hydroxyl acrylic resin, 10 parts of cashew shell oil bio-based polyol-1, 10 parts of 600-mesh acicular wollastonite powder, 4 parts of polyvinyl alcohol (PVA-1000), 3 parts of isophorone diisocyanate, 0.5 part of defoamer, 0.2 part of catalyst, 1 part of titanium dioxide, and 20 parts of solvent.

[0158] Comparative Example 2

[0159] The difference between Comparative Example 2 and Example 1 is that the preparation method of the modified acicular wollastonite powder in Comparative Example 2 is different from that in Example 1, and the others are the same.

[0160] The preparation method of the modified acicular wollastonite powder is as follows:

[0161] (1) Add 10 parts by weight of 600-mesh acicular wollastonite powder, 1 part by weight of stearic acid, 0.5 part by weight of oleic acid, and 10 parts by weight of absolute ethanol to 28.5 parts by weight of water, stir evenly at 80 °C at a speed of 100 rpm, then add 0.5 part by weight of sorbitan monostearate, stir evenly at a speed of 100 rpm, filter, and dry at 90 °C to obtain the modified acicular wollastonite powder.

[0162] Comparative Example 3

[0163] The difference between Comparative Example 3 and Example 1 is that the preparation method of the modified acicular wollastonite powder in Comparative Example 3 is different from that in Example 1, and the others are the same.

[0164] The preparation method of the modified acicular wollastonite powder is as follows:

[0165] (1) Add 10 parts by weight of 600-mesh acicular wollastonite powder, 1 part by weight of stearic acid, 0.5 part by weight of oleic acid, and 10 parts by weight of absolute ethanol to 28.5 parts by weight of water, stir evenly at 80 °C at a speed of 100 rpm, then add 0.5 part by weight of sorbitan monostearate, stir evenly at a speed of 100 rpm to obtain a precursor solution;

[0166] (2) Add 10 parts by weight of γ-aminopropyltriethoxysilane to 90 parts by weight of water, stir evenly to obtain a modified solution;

[0167] (3) Drop 4 parts by weight of the modified solution into 10 parts by weight of the precursor solution, stir evenly at 80 °C at a speed of 100 rpm, filter, and dry at 90 °C to obtain the modified acicular wollastonite powder.

[0168] Comparative Example 4

[0169] The difference between Comparative Example 4 and Example 1 is that in Comparative Example 4, an equal amount of modified silica is used to replace the modified acicular wollastonite powder (the preparation method of the modified silica is the same as that in Example 1), and the others are the same.

[0170] The preparation method of the modified acicular wollastonite powder is as follows:

[0171] (1) Add 10 parts by weight of silica with a particle size of 600 mesh, 1 part by weight of stearic acid, 0.5 part by weight of oleic acid, and 10 parts by weight of absolute ethanol to 28.5 parts by weight of water, stir evenly at 80 °C at a rotation speed of 100 rpm, then add 0.5 part by weight of sorbitan monostearate, and stir evenly at a rotation speed of 100 rpm to obtain a precursor solution;

[0172] (2) Add 10 parts by weight of amino silicone oil, 6 parts by weight of N-oleoyl-N-methyltaurine sodium, and 6 parts by weight of dopamine hydrochloride to 38 parts by weight of water, stir evenly at a rotation speed of 100 rpm, then add 1 part by weight of tris(hydroxymethyl)aminomethane hydrochloride buffer solution, and stir evenly to obtain a modified solution;

[0173] (3) Drop 4 parts by weight of the modified solution into 10 parts by weight of the precursor solution, stir evenly at 80 °C at a rotation speed of 100 rpm, filter, and dry at 90 °C to obtain modified silica.

[0174] Test Example

[0175] 1. Aging performance: Tested according to the standard GB / T 16422.2-2022. The irradiation spectrum of sunlight is simulated by a xenon arc lamp and a daylight filter. The aging cycle conditions include 102 min of light irradiation (0.51 W / (m·nm), 340 nm), then 18 min of light irradiation (0.51 W / (m·nm), 340 nm) plus spraying, the blackboard temperature is 50 ± 3 °C, the test chamber temperature is 38 ± 3 °C, and the relative humidity is 50 ± 10%. The aging test time is 120 h.

[0176] Table 1

[0177]

[0178]

[0179] 2. Abrasion resistance: The measurement method refers to GB1768-79(89), grind for 50 revolutions, and detect the loss amount (the higher the loss amount, the worse the abrasion resistance).

[0180] 3. Scratch resistance: Use a steel needle with a diameter of 1.0 mm and a spherical tip radius of 0.5 mm to pierce the PET mirror film at a speed of 50 mm / min, and measure the scratch resistance by the minimum load value at which the needle can pierce the release film (the larger the minimum load value, the better the scratch resistance).

[0181] Table 2

[0182] Loss amount (mg) Minimum load value (N) Example 1 3.5 19.8 Example 2 4.2 19.0 Example 3 3.8 19.3 Example 4 3.6 19.6 Example 5 8.5 16.6 Example 6 7.4 17.2 Comparative Example 1 13.9 11.9 Comparative Example 2 11.8 12.6 Comparative Example 3 11.3 12.8 Comparative Example 4 10.4 13.1

[0183] As can be seen from Table 1 to Table 2, the PET mirror film described in the present invention has excellent wear resistance, scratch resistance and aging resistance, and has broad application prospects.

[0184] By comparing Examples 1, 4 to 6, it can be seen that by controlling the hydroxyl value of the cashew shell oil bio-based polyol to be 224-256 mgKOH / g and the viscosity at 25°C to be 1200-1710 mPa·s, the wear resistance, scratch resistance and aging resistance can be further improved.

[0185] By comparing Example 1 with Comparative Examples 1 to 4, it can be seen that the modified acicular wollastonite powder prepared in the present invention can significantly improve the wear resistance, scratch resistance and aging resistance, and the modified acicular wollastonite powder prepared by different methods has different improvements in wear resistance, scratch resistance and aging resistance. Compared with other methods, the method of the present invention can more significantly improve the wear resistance, scratch resistance and aging resistance.

[0186] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and not to limit the protection scope of the present invention. Although the present invention has been described in detail with reference to the preferred embodiments, those of ordinary skill in the art should understand that the technical solutions of the present invention can be modified or equivalently replaced without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. A method for preparing a PET mirror film, characterized in that: The following steps are involved: (1) providing a first PET film and a second PET film; (2) performing plasma surface treatment on the first PET film, and electroplating the first PET film to form an electroplated layer; (3) applying the coloring liquid on the surface of the electroplating layer to form a coloring layer; (4) performing plasma surface treatment on the coloring layer, placing a second PET film on the surface of the coloring layer, and then performing plasma surface treatment on the second PET film; (5) Applying a scratch-resistant coating on the surface of the second PET film to form a scratch-resistant layer.

2. The method for preparing a PET mirror film according to claim 1, characterized in that: The power of the plasma surface treatment is 100-300W, and the time is 1-4 minutes.

3. The method for preparing a PET mirror film according to claim 1, characterized in that: The electroplating layer is aluminum, silver, copper, chromium or zinc; the thickness of the electroplating layer is 10-20nm.

4. The method for preparing a PET mirror film according to claim 1, characterized in that: The thickness of the coloring layer is 0.5-1.2 μm.

5. The method for preparing a PET mirror film according to claim 1, characterized in that: The coloring liquid comprises the following components in parts by weight: 50 to 70 parts of acrylic resin, 10 to 30 parts of a first solvent, 0.1 to 0.5 parts of a leveling agent, 0.1 to 0.3 parts of an antioxidant, 1 to 2 parts of isophorone diisocyanate, and 3 to 5 parts of a color paste.

6. The method for preparing a PET mirror film according to claim 1, characterized in that: The anti-scratch coating comprises the following components in parts by weight: 45 to 55 parts of hydroxy acrylic resin, 6 to 12 parts of cashew nut shell oil bio-based polyol, 9 to 12 parts of modified needle-shaped wollastonite powder, 2 to 5 parts of polyvinyl alcohol, 2 to 4 parts of isophorone diisocyanate, 0.2 to 0.6 parts of defoaming agent, 0.1 to 0.2 parts of catalyst, 0.5 to 1.2 parts of titanium dioxide, and 15 to 25 parts of a second solvent.

7. The method for preparing the PET mirror film according to claim 6, characterized in that: The cashew nut shell liquid bio-based polyol has a hydroxyl value of 224 to 256 mg KOH / g and a viscosity of 1200 to 1710 mPa·s at 25° C.

8. The method for preparing the PET mirror film according to claim 6, characterized in that: The hydroxy acrylic resin has a solid content of 44-46 wt %, a viscosity of 1000-4000 mPa·s at 25° C., a hydroxy content of 2-2.5 wt %, and a glass transition temperature of 40-50° C.

9. The method for preparing a PET mirror film according to claim 6, characterized in that: The preparation method of the modified needle-shaped wollastonite powder is: (1) adding 10 parts by weight of needle-shaped wollastonite powder, 0.8 to 1.2 parts by weight of stearic acid, 0.4 to 0.8 parts by weight of oleic acid, and 6 to 12 parts by weight of anhydrous ethanol to 25 to 40 parts by weight of water, stirring evenly at 70 to 85° C., and then adding 0.2 to 0.6 parts by weight of sorbitan monostearate, stirring evenly, to obtain a precursor solution; (2) adding 10 parts by weight of amino silicone oil, 6 to 8 parts by weight of sodium N-oleoyl-N-methyltaurate, and 4 to 6 parts by weight of dopamine hydrochloride to 30 to 50 parts by weight of water, stirring evenly, and then adding 0.8 to 1.5 parts by weight of tris(hydroxymethyl)aminomethane hydrochloride buffer solution, stirring evenly, to obtain a modified solution; (3) 2 to 5 parts by weight of the modified liquid are dropped into 10 parts by weight of the precursor liquid, stirred evenly at 70 to 85° C., filtered, and dried to obtain modified needle-shaped wollastonite powder.

10. The method for preparing a PET mirror film according to claim 9, characterized in that: The particle size of the needle-shaped wollastonite powder is 200-1000 meshes.

Images