Externally-pasted car roof glass film with super-hydrophobic and wear-resisting properties

Abstract

The utility model discloses an externally-pasted car roof glass film with super-hydrophobic and wear-resisting properties. The externally-pasted car roof glass film comprises a super-hydrophobic composite coating based on a porous bonding layer, a metal coating layer, a PET (Polyethylene Terephthalate) base material layer, a pressure-sensitive adhesive layer and a release film layer which are compounded in sequence, the super-hydrophobic composite coating based on the porous bonding layer comprises a PU / FEVE mixed resin porous bonding bottom layer and a super-hydrophobic SiO2 nanoparticle surface coating, and a gully-shaped or pore-shaped rough structure is constructed on the surface of the PU / FEVE mixed resin porous bonding bottom layer. The technical problem of improving the long-time frosted effect and the super-hydrophobic performance of the externally-pasted car roof glass film is solved. The PU / FEVE mixed resin porous bonding bottom layer is adopted to improve the light-transmitting and non-perspective effect, the bonding strength between the super-hydrophobic coating and a substrate is improved, a pore structure is further formed in the surface of the PU / FEVE mixed resin porous bonding bottom layer, sprayed super-hydrophobic nano-particles can be embedded into resin pores, hardened resin protrusions can protect the embedded particles, and therefore the super-hydrophobic coating has the advantages of being capable of achieving the super-hydrophobic effect. And the overall wear resistance of the composite coating is improved.

Description

Technical Field

[0001] The utility model relates to an externally attached roof glass film, in particular to an externally attached roof glass film with super hydrophobic and wear-resistant properties. Background Art

[0002] The full glass roof and panoramic sunroof make the interior space appear more spacious due to their high light transmittance, but for the functional purposes of protecting privacy and preventing glare, translucent but not transparent (frosted) roof glass is currently more popular among market consumers (especially young people).

[0003] To alter the transparency of the original transparent roof glass and enhance safety by preventing flying stones from hitting the glass during driving, frosted roof glass films have emerged. These films are made by spraying a super-hydrophobic SiO2 nanoparticle coating onto the surface of a base film, utilizing the principle of light scattering to achieve a translucent, non-transparent effect. They also possess super-hydrophobic properties and strong stain resistance, making them easily removable from stains such as dust, bird droppings, oil, and water spots.

[0004] However, the super-hydrophobic SiO2 nanoparticle coating of existing exterior roof glass films has poor wear resistance. Factors such as air wear and human wear (wiping) during driving can easily lead to "the exterior roof glass film developing a frosted effect and a sharp drop in hydrophobicity after long-term use."

[0005] Wang Xikui, Su Yifan, and others proposed the preparation of a superhydrophobic composite coating based on a porous adhesive layer and its wear resistance research (SURFACE TECHNOLOGY, Vol. 52, No. 11, November 2023). The abstract clearly states: Purpose: To improve the wear resistance of superhydrophobic coatings. Methods: A bottom-surface composite method is used to enhance the adhesion and wear resistance of the superhydrophobic coating. A foaming agent is used to form a uniform pore structure on the surface of the resin primer, allowing some superhydrophobic nanoparticles sprayed on the primer surface to embed into the pores. The raised structure of the hardened resin effectively protects the superhydrophobic nanoparticles, thereby improving the overall wear resistance of the coating. Rubber wear tests were carried out on a friction and wear testing machine to comprehensively evaluate the wear resistance of the coating. The original morphology and wear morphology of the coating surface were analyzed using scanning electron microscopy and coaxial optical microscopy. The surface wettability of the coating before and after wear was tested using a contact angle meter. Results: When the mass fraction of isohexadecane was 50%, the preheating temperature was 130°C, and the preheating time was 100 s, a deep and evenly distributed pore structure was formed on the primer surface, resulting in a superhydrophobic composite coating prepared based on this primer exhibiting relatively improved wear resistance. Under a load of 30 N, the optimized coating maintained good hydrophobicity after 700 rubber abrasion cycles. Conclusion: Improving the bottom composite coating with a foaming agent effectively enhances the bond strength between the superhydrophobic nanocoating and the substrate. The pore structure on the primer surface facilitates the embedding of superhydrophobic particles, fully utilizing the raised structure of the hardened resin to protect the embedded superhydrophobic particles, effectively improving the overall wear resistance of the bottom composite superhydrophobic coating.

[0006] Therefore, the applicant proposed the present utility model. Summary of the Invention

[0007] The purpose of the utility model is to provide a roof glass film with super hydrophobic and wear-resistant properties to solve the above-mentioned deficiencies in the prior art.

[0008] In order to achieve the above-mentioned purpose, the utility model designs a roof glass film with super-hydrophobic and wear-resistant properties for external use, whose layered structure includes: a super-hydrophobic composite coating based on a porous adhesive layer, a metal plating layer, a PET substrate layer, a pressure-sensitive adhesive layer and a release film layer compounded in sequence; the super-hydrophobic composite coating based on the porous adhesive layer includes a PU / FEVE mixed resin porous adhesive base layer and a super-hydrophobic SiO2 nanoparticle top coating, and the surface of the PU / FEVE mixed resin porous adhesive base layer constructs a groove-shaped or pore-shaped rough structure.

[0009] The porous adhesive layer-based super-hydrophobic composite coating utilizes a PU / FEVE hybrid resin porous adhesive base layer. This unique surface texture not only scatters light, further enhancing the translucent, opaque effect, but also effectively improves the adhesion strength between the coating and the substrate. The porous structure also facilitates the embedding of super-hydrophobic SiO2 nanoparticles within the resin. Once the resin dries and hardens, the high-hardness raised structures formed on its surface protect the super-hydrophobic SiO2 nanoparticles, effectively improving the wear resistance of the super-hydrophobic SiO2 nanoparticle topcoat.

[0010] The above-mentioned external roof glass film with super-hydrophobic and wear-resistant properties has a thickness of the super-hydrophobic composite coating based on the porous adhesive layer in its layered structure preferably selected to be 25μm-30μm, wherein the surface of the PU / FEVE mixed resin porous adhesive bottom layer is obviously grooved or pore-shaped, the width of its protruding structure is about 100μm, the width of the pit is about 50μm, and the depth of the pit can reach about 20μm, the SiO2 nanoparticles of the super-hydrophobic SiO2 nanoparticle top coating completely fill the pits, and there is a clear dividing line between the resin bottom layer and the super-hydrophobic coating, and the thickness of the super-hydrophobic coating above the dividing line is 100nm-200nm.

[0011] The super-hydrophobic and wear-resistant exterior roof glass film preferably utilizes a magnetron sputtering process to uniformly sputter nanoscale metal ions (e.g., metallic nanosilver ions) onto a PET substrate layer to create a highly heat-insulating, reflective metal coating layer. This layer achieves heat insulation primarily through light reflection, further enhancing the heat-insulating and UV-resistant properties of the exterior roof glass film provided by the present invention. The thickness of the metal coating layer is preferably 100-200 nm.

[0012] In the above-mentioned super-hydrophobic and wear-resistant exterior roof glass film, the thickness of the PET substrate layer in its layered structure is preferably 50 μm-150 μm, and further preferably 75 μm-125 μm.

[0013] The aforementioned super-hydrophobic and wear-resistant exterior roof glass film has a layered structure in which the pressure-sensitive adhesive layer is preferably made of acrylic pressure-sensitive adhesive or polyurethane pressure-sensitive adhesive, with a visible light transmittance of preferably 90% or higher. Furthermore, it is preferably made of a transparent nano-insulating pressure-sensitive adhesive prepared by a blending process using nanomaterials such as nano-antimony-doped tin dioxide (ATO) and tungsten oxide (WTO) as the insulating medium and a solvent-based acrylic pressure-sensitive adhesive as the film-forming material. The thickness of the pressure-sensitive adhesive layer is preferably 10 μm to 50 μm, and more preferably 25 μm to 35 μm.

[0014] The above-mentioned external roof glass film with super hydrophobic and wear-resistant properties, the release film layer in its layered structure is preferably a PET release film layer, and further preferably a transparent PET release film layer, its thickness is preferably 23μm-100μm, and further preferably 36μm-76μm, the haze is preferably less than 1%, and the release force is preferably within 20g / inch.

[0015] The aforementioned super-hydrophobic and wear-resistant exterior roof glass film also includes a protective film layer in its layered structure, which is laminated to the surface of the super-hydrophobic composite coating based on the porous adhesive layer. This protective film layer can maximize the protection of the super-hydrophobic composite coating based on the porous adhesive layer, thereby preventing the super-hydrophobic composite coating based on the porous adhesive layer from being scratched and worn during packaging, transportation, and application.

[0016] The protective film layer is preferably a PET protective film, and its thickness is preferably 12 μm-75 μm.

[0017] Compared with the prior art, the present invention provides a super-hydrophobic and wear-resistant exterior roof glass film, which has the following technical effects:

[0018] The super-hydrophobic composite coating based on the porous adhesive layer adopts a bottom composite structure, and scatters light through the unique surface texture of the bottom layer, thereby further improving the light-transmitting but not see-through effect, and effectively improving the bonding strength between the super-hydrophobic coating and the substrate. The PU / FEVE mixed resin porous adhesive bottom layer surface forms a pore structure, and the sprayed super-hydrophobic nanoparticles can be embedded in the resin pores. The hardened resin protrusions can protect the embedded particles, thereby improving the overall wear resistance of the composite coating.

[0019] The surface of the roof glass film has strong super-hydrophobicity and stain resistance. Dust, bird droppings, oil stains, water spots and other stains can be easily removed, and the super-hydrophobicity of the surface of the roof glass film can be maintained for a long time.

[0020] The surface of the roof glass film is not easy to adhere to by rainwater, so it also has anti-icing / de-icing and anti-corrosion properties. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 This is a schematic diagram of the layered structure of an external roof glass film with super hydrophobic and wear-resistant properties.

[0022] In the figure: protective film layer 1, super-hydrophobic composite coating based on porous adhesive layer 2, metal coating layer 3, PET substrate layer 4, pressure-sensitive adhesive layer 5, release film layer 6. DETAILED DESCRIPTION

[0023] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field are within the scope of protection of the present invention. Example 1:

[0024] like Figure 1 As shown, as an embodiment of the present invention, a super-hydrophobic and wear-resistant external roof glass film provided in this embodiment has a layered structure comprising: a protective film layer 1, a super-hydrophobic composite coating 2 based on a porous adhesive layer, a metal plating layer 3, a PET substrate layer 4, a pressure-sensitive adhesive layer 5 and a release film layer 6, which are compounded in sequence; the super-hydrophobic composite coating based on the porous adhesive layer comprises a PU / FEVE mixed resin porous adhesive base layer and a super-hydrophobic SiO2 nanoparticle top coating, and the surface of the PU / FEVE mixed resin porous adhesive base layer is constructed with a groove-shaped or pore-shaped rough structure.

[0025] The protective film layer in this embodiment is a PET protective film (Yihua Dongli, G01) with a thickness of 12 μm.

[0026] The thickness of the super-hydrophobic composite coating based on the porous adhesive layer described in this embodiment is preferably selected to be 25 μm, wherein the surface of the PU / FEVE mixed resin porous adhesive bottom layer is obviously grooved or pore-shaped, the width of its protrusion structure is about 100 μm, the width of the pit is about 50 μm, and the depth of the pit can reach about 20 μm. The SiO2 nanoparticles of the super-hydrophobic SiO2 nanoparticle top coating completely fill the pits, and there is a clear dividing line between the resin bottom layer and the super-hydrophobic coating. The thickness of the super-hydrophobic coating above the dividing line is 100nm-200nm.

[0027] The metal coating layer in this embodiment is made of metal nano silver ion material, the particle size of the metal silver element is 20nm-50nm, and the thickness is 100nm.

[0028] The PET substrate layer in this embodiment is a PET film (Yihua Toray UV34) with a thickness of 50 μm.

[0029] The pressure-sensitive adhesive layer in this embodiment uses a transparent nano-thermal insulation pressure-sensitive adhesive liquid (Aladdin Biochemical Technology Co., Ltd.), with a visible light transmittance of 92% and a thickness of 10 μm.

[0030] In this embodiment, the release film layer is a transparent PET release film (Nan Ya special film) with a thickness of 23 μm.

[0031] This embodiment also provides a method for preparing a roof glass film with super-hydrophobic and wear-resistant properties, and the specific steps are as follows:

[0032] Step 1: Preparation of PU / FEVE mixed resin porous bonding bottom coating liquid

[0033] 1.1 Preparation of substrate materials

[0034] The main materials include polyurethane (50% by mass, PU), fluorocarbon resin (50% by mass, FEVE), butyl acetate as a diluent (1:1 mass ratio to the total resin), and isohexadecane (10%–100% by mass, a blowing agent). All of these raw materials were purchased from Nanjing Wanqing Chemical Glass Instrument Co., Ltd. The primer resin used was a two-component resin, with the mass ratios of the two raw resins to their corresponding curing agents being: m(PU resin) : m(curing agent) = 1:2, and m(FEVE resin) : m(curing agent) = 3:1.

[0035] 1.2 Preparation of PU / FEVE mixed resin porous adhesive bottom coating liquid

[0036] PU resin and FEVE resin were mixed in a mass ratio of 1:1 and stirred evenly for 10 minutes using a magnetic stirrer to obtain a PU / FEVE mixed resin. Then, isohexadecane accounting for 50% of the total mass of the mixed resin was added to the PU / FEVE mixed resin, and stirring was continued for 15 to 20 minutes to obtain a resin coating liquid containing a foaming agent.

[0037] Step 2: Apply pressure-sensitive adhesive layer

[0038] A transparent nano-thermal-insulating pressure-sensitive adhesive (Aladdin Biochemical Technology Co., Ltd.) was coated on one side of a 50μm thick PET film (Yihua Toray UV34) and dried at 110°C for 2 minutes to form a 10μm thick transparent nano-thermal-insulating pressure-sensitive adhesive layer. A 23μm transparent PET release film (Nanya Special Film) was then placed over the surface of the transparent nano-thermal-insulating pressure-sensitive adhesive layer.

[0039] Step 3: Applying a super-hydrophobic composite coating based on a porous adhesive layer

[0040] Use a high pressure airbrush at 10-15 g / dm 2 The resin coating liquid prepared in step 1 was evenly sprayed on the other side of the PET film (Yihua Toray UV34) with a spraying amount of 100g; the PET film sprayed with the resin coating liquid was placed on a 130°C CNC heating table for preheating (foaming) for 100 s. A porous rough structure was formed on the surface of the semi-cured resin coating by the thermal volatilization of the foaming agent; a high-pressure airbrush was used to spray the film at a pressure of 20 g / dm 2The super-hydrophobic SiO2 nanoparticle coating was modified on the surface of the rough resin coating by spraying a certain amount; the PET film was dried in an 80 ℃ oven and cured for 3-5 h.

[0041] Step 4: Composite protective film layer

[0042] In step 3, the super-hydrophobic composite coating based on the porous adhesive layer was covered with a 12 μm PET protective film (Yihua Dongli, G01).

[0043] Step 5: Ripening

[0044] The semi-finished product in step 4 is placed in a 50° C. curing chamber for 72 hours to obtain the exterior car roof glass film of the present invention. Example 2:

[0045] As a second embodiment of the present invention, this embodiment provides an external roof glass film with super hydrophobic and wear-resistant properties and a preparation method, and its layered structure and preparation method are roughly the same as those in Example 1.

[0046] However, the PET protective film (Yihua Dongli, G01) used as the protective film layer in this embodiment has a thickness of 45 μm. The thickness of the super-hydrophobic composite coating based on the porous adhesive layer in this embodiment is 27 μm. The PET film (Yihua Dongli UV34) used as the PET substrate layer in this embodiment has a thickness of 100 μm. The pressure-sensitive adhesive layer in this embodiment also uses a transparent nano-insulating pressure-sensitive adhesive liquid (Aladdin Biochemical Technology Co., Ltd.), and the dry adhesive thickness is 30 μm. The transparent PET release film (Nanya Special Film) used as the release film layer in this embodiment has a thickness of 62 μm. Example 3:

[0047] As the third embodiment of the present invention, this embodiment provides an external roof glass film with super hydrophobic and wear-resistant properties and a preparation method, and its layered structure and preparation method are roughly the same as those in Example 1.

[0048] However, the PET protective film (Yihua Dongli, G01) used as the protective film layer in this embodiment has a thickness of 75 μm. The thickness of the super-hydrophobic composite coating based on the porous adhesive layer in this embodiment is 30 μm. The PET film (Yihua Dongli UV34) used as the PET substrate layer in this embodiment has a thickness of 150 μm. The pressure-sensitive adhesive layer in this embodiment also uses a transparent nano-insulating pressure-sensitive adhesive liquid (Aladdin Biochemical Technology Co., Ltd.), and the dry adhesive thickness is 35 μm. The transparent PET release film (Nanya Special Film) used as the release film layer in this embodiment has a thickness of 100 μm.

[0049] Comparative Example:

[0050] A method for preparing an external roof glass film comprises the following steps:

[0051] Step 1: Apply pressure-sensitive adhesive layer

[0052] A transparent nano-thermal-insulating pressure-sensitive adhesive (Aladdin Biochemical Technology Co., Ltd.) was coated on one side of a 50μm thick PET film (Yihua Toray UV34) and dried at 110°C for 2 minutes to form a 10μm thick transparent nano-thermal-insulating pressure-sensitive adhesive layer. A 23μm transparent PET release film (Nanya Special Film) was then placed over the surface of the transparent nano-thermal-insulating pressure-sensitive adhesive layer.

[0053] Step 2: Apply super-hydrophobic SiO2 nanoparticle topcoat

[0054] Use a high-pressure airbrush to press 20 g / dm 2 The other side of the PET film (Yihua Toray UV34) was modified with a super-hydrophobic SiO2 nanoparticle coating with a spraying amount of ; the PET film was dried in an 80 ℃ oven and cured for 3-5 h. The thickness of the super-hydrophobic SiO2 nanoparticle coating was 100nm-200nm.

[0055] Step 3: Composite protective film layer

[0056] The superhydrophobic SiO2 nanoparticle topcoat in step 2 was covered with a 12 μm PET protective film (Yihua Dongli, G01).

[0057] Step 4: Ripening

[0058] The semi-finished product in step 4 is placed in a 50° C. curing chamber for 72 hours to obtain the exterior car roof glass film of the present invention.

[0059] The following table shows the test data of water droplet rolling angle at different wear times of the exterior roof glass films provided in Examples 1-3 and Comparative Examples.

[0060]

[0061] The test data above demonstrates that after 100 abrasions, the water droplet rolloff angle of the roof glass films provided in Examples 1-3 rapidly increased from less than 5° to approximately 18°, maintaining a slow rolloff angle change (from 100 to 700 abrasions, the rolloff angle slowly increased from less than 18° to approximately 20°). It wasn't until the rubber was abraded 900 times that the rolloff angle on the worn surface rose sharply to over 40°, gradually losing its hydrophobicity.

[0062] In the comparative example, the water droplet roll-off angle of the exterior roof glass film rapidly increased from less than 18° to approximately 40° between 100 and 700 abrasions. Similarly, after the rubber was abraded 900 times, the water droplet roll-off angle on the worn surface further increased to over 40°, gradually losing its hydrophobicity.

[0063] The reason for the above-mentioned changes is that the super-hydrophobic coating of the super-hydrophobic composite coating top layer based on porous adhesive layer in embodiment 1-3 is first worn away in the initial stage of wear and tear, causing part bottom layer to be exposed, surface wettability is enhanced, and rolling angle increases;After initial stage of wear and tear, the super-hydrophobic nano particles embedded in the bottom pores are gradually exposed, and the protection of this part of nano particles by hardened resin projections is such that bottom composite coating is still able to maintain stable hydrophobic properties after experiencing the wear test of hundreds of times. During this period, the water droplet rolling angle increase on the wear surface is about 2 °, is in a stable wear phase. Along with the increase of wear and tear number of times, the porous layer of resin bottom and the super-hydrophobic nano particles embedded therein are gradually worn out, causing bottom pure resin to be fully exposed, surface wettability is sharply increased, and finally loses hydrophobic properties.

[0064] The test methods for each performance in the above table are as follows:

[0065] The water droplet rolling angles on the roof glass films provided in Examples 1-3 and the comparative examples were measured using a contact angle meter (OCA 15Pro). Furthermore, the surface wear resistance was tested using a friction and wear tester. Given the performance differences between nanocoatings and common test materials, a rubber-wrapped friction tip was used during the tests, and the surface wettability of the coatings after friction was determined.

[0066] The present invention is not limited to the above-mentioned optimal implementation mode. Anyone can derive other forms of products under the inspiration of the present invention. However, no matter what changes are made in the shape or structure, any technical solution that is the same or similar to that of the present application falls within the scope of protection of the present invention.

Claims

1. A super-hydrophobic and wear-resistant exterior glass film, characterized by include: A super-hydrophobic composite coating based on a porous adhesive layer, a metal coating layer, a PET substrate layer, a pressure-sensitive adhesive layer and a release film layer are sequentially compounded; the super-hydrophobic composite coating based on the porous adhesive layer includes a PU / FEVE mixed resin porous adhesive bottom layer and a super-hydrophobic SiO2 nanoparticle top coating, and the surface of the PU / FEVE mixed resin porous adhesive bottom layer is constructed with a groove-shaped or pore-shaped rough structure.

2. The super-hydrophobic and wear-resistant exterior roof glass film according to claim 1, characterized in that: The thickness of the super-hydrophobic composite coating based on the porous adhesive layer is 25 μm-30 μm.

3. The super-hydrophobic and wear-resistant exterior roof glass film according to claim 1, characterized in that: The thickness of the metal coating layer is 100nm-200nm.

4. The super-hydrophobic and wear-resistant exterior roof glass film according to claim 1, characterized in that: The thickness of the PET substrate layer is 50 μm-150 μm.

5. The super-hydrophobic and wear-resistant exterior roof glass film according to claim 1, characterized in that: The thickness of the pressure-sensitive adhesive layer is 10 μm-50 μm.

6. The super-hydrophobic and wear-resistant exterior roof glass film according to claim 1, characterized in that: The thickness of the release film layer is 23 μm-100 μm.

7. The super-hydrophobic and wear-resistant exterior roof glass film according to claim 1, characterized in that: The invention also comprises a protective film layer which is compounded onto the surface of the super-hydrophobic composite coating based on the porous adhesive layer.

8. The super-hydrophobic and wear-resistant exterior roof glass film according to claim 7, characterized in that: The thickness of the protective film layer is 12 μm-75 μm.

Images