High-transparency and super-hydrophobic automobile glass film

Abstract

The utility model discloses an automobile glass film, and particularly relates to a high-transparency and super-hydrophobic automobile glass film, the layered structure of which comprises a release film layer, a pressure-sensitive adhesive layer, a PET (Polyethylene Terephthalate) base material layer and a POSS-SH-DFMA7 light-cured transparent super-hydrophobic coating which are sequentially compounded, and the release film layer, the pressure-sensitive adhesive layer, the PET base material layer and the POSS-SH-DFMA7 light-cured transparent super-hydrophobic coating are sequentially compounded. According to the utility model, the technical problem that the automobile glass film has high visible light transmittance and good surface super-hydrophobic performance, mechanical stability, weather resistance and chemical stability is solved. The surface layer of the automobile glass film provided by the utility model is excellent in super-hydrophobic effect, the static water contact angle can reach 156.92 degrees, the rolling angle is as small as 3.24 degrees, and various application performances of the surface layer better meet the use requirements, so that the service life of the automobile glass film is prolonged. For example, the coating has reliable adhesive force after being subjected to a long-time water drop impact test, excellent coating weather resistance after long-term action in a multi-element environment and stable coating chemical resistance after corrosion of chemical reagents with different pH values. Meanwhile, the average light transmittance of the whole film is as high as 90.63%.

Description

TECHNICAL FIELD

[0001] The utility model relates to a kind of automobile glass films, in particular to a kind of high transparency and super hydrophobic automobile glass film. BACKGROUND

[0002] When automobile glass film is pasted on the outside of glass, it is easy to affect driving safety due to rainwater adhering to the surface of automobile glass film, and automobile glass film should also have hydrophobic property.

[0003] At present, the low-surface-energy materials commonly used to construct super-hydrophobic surface of automobile glass film mainly include long-chain perfluorosilane, fluorine-containing acrylate and fluorosilicon copolymer, which combine with the addition of nanoparticles to form a rough surface with low surface energy. Due to the poor adhesion of nanoparticles and polymer bonding and modified nanoparticles to the surface of the substrate, it is difficult to make it have good super-hydrophobic property, mechanical stability, weather resistance and chemical stability and other application properties without affecting the light transmittance.

[0004] Xu Yizhou, He Jinxin and others proposed a method for preparing a large-area transparent and durable super-hydrophobic coating on a smooth mirror substrate, i.e., a one-step method for preparing a transparent super-hydrophobic coating based on fluorine-containing modified cage-like silsesquioxane (Surface Technology, Vol. 51, No. 10, October 2022). By introducing fluorine-containing low-surface-energy modified cage-like silsesquioxane (POSS) into a polyurethane acrylate hydrophobic photocurable resin system, a super-hydrophobic photocurable coating was prepared on a polycarbonate (PC) surface by spraying and phase separation. The effects of the doping amount of low-surface-energy modified POSS and the addition amount of ethanol on the construction of super-hydrophobic coating were investigated. When the doping amount of POSS-SH-DFMA7 is 40% of the resin content and the addition amount of ethanol is 25% of the solvent THF, the coating exhibits excellent super-hydrophobic properties, with a static water contact angle and sliding angle of 156.92° and 3.24°, respectively; good optical transparency, with a light transmittance of 85.63%; reliable mechanical stability, maintaining super-hydrophobic properties after 6 hours of water droplet impact; stable weather resistance and chemical resistance, maintaining the original wetting properties of the coating after exposure to outdoor environments and different pH chemical reagents. The conclusion is that the introduction of a certain amount of fluorine-containing monomer modified POSS into the photocurable resin system combined with the action of ethanol can prepare a transparent, stable super-hydrophobic coating with good physical and chemical properties in one step.

[0005] Therefore, the applicant proposes the utility model. SUMMARY

[0006] The utility model aims at solving the above-mentioned deficiencies of the prior art and provides a kind of high transparency and super hydrophobic automobile glass film.

[0007] In order to achieve the above object, the utility model discloses a kind of high transparency and super hydrophobic car glass film, its layered structure includes sequentially complex release film layer, pressure sensitive adhesive layer, PET substrate layer and POSS-SH-DFMA7 photocuring transparent super hydrophobic coating.

[0008] Wherein, POSS-SH-DFMA7 photocuring transparent super hydrophobic coating is constructed nanometer material using cage-like oligomeric silsesquioxane (POSS) as roughness, because its natural scale advantage (2nm~5nm) and unique intramolecular structure, 8 vertex Si atoms can be connected to various reactive or non-reactive groups by chemical reaction. Therefore, fluorine-containing monomer can be introduced into POSS by thiol-ene click chemistry reaction, and the product not only has low surface energy characteristics, but also can participate in the construction of multi-level rough structure. In addition, because POSS has good solubility, dimensional stability and thermal stability and other advantages, the application performance of the coating will be significantly improved with the addition of POSS.

[0009] Therefore, the utility model provides a kind of high transparency and super hydrophobic car glass film, it adopts modified nano POSS and photocuring resin (film-forming speed is fast, and substrate adhesion is strong) mixing, using one-step spraying method combined with phase separation method, and the operation is simple on the surface of PET substrate Preparation of POSS-SH-DFMA7 photocuring transparent super hydrophobic coating of large-scale implementation. The coating has good mechanical and weathering and chemical stability while not affecting the optical transparency of substrate itself.

[0010] As preferred, the thickness of the POSS-SH-DFMA7 photocuring transparent super hydrophobic coating in the layered structure of the above-mentioned high transparency and super hydrophobic car glass film is preferably 5μm~12μm.

[0011] As preferred, the thickness of the PET substrate layer in the layered structure of the above-mentioned high transparency and super hydrophobic car glass film is preferably 50μm-150μm, and further preferably 75μm-125μm.

[0012] As preferred, the material of the pressure sensitive adhesive layer in the layered structure of the above-mentioned high transparency and super hydrophobic car glass film is preferably transparent acrylic pressure sensitive adhesive, the visible light transmittance is preferably more than 90%, and the thickness is preferably 20μm~50μm.

[0013] As preferred, the high transparent and super-hydrophobic automobile glass film has the following technical effects:

[0014] Compared with the prior art, the high transparent and super-hydrophobic automobile glass film has the following technical effects:

[0015] The super-hydrophobic effect of the surface layer is excellent, the static water contact angle can reach 156.92°, and the rolling angle is as small as 3.24°, and the application performance of the surface layer is more suitable for the use requirement, such as reliable coating adhesion after long-time water drop impact test, excellent coating weather resistance after long-term effect of multiple environments, and stable coating chemical resistance after erosion of different pH chemical reagents. At the same time, the average light transmittance of the whole film is as high as 90.63%.

[0016] In addition, the surface layer has self-cleaning performance due to the super-hydrophobic performance, and has strong stain resistance, and dirt, bird droppings, oil stains and water stains can be easily removed. BRIEF DESCRIPTION OF DRAWINGS

[0017] Figure 1 is a schematic diagram of the layered structure of the high transparent and super-hydrophobic automobile glass film of the utility model.

[0018] In the figure: the transparent PET release film layer 1, the transparent acrylic pressure-sensitive adhesive layer 2, the PET substrate layer 3, and the POSS-SH-DFMA 7 photocured transparent super-hydrophobic coating layer 4. DETAILED DESCRIPTION

[0019] The technical solutions in the embodiments of the utility model will be clearly and completely described below with reference to the drawings in the embodiments of the utility model. Obviously, the described embodiments are only part of the embodiments of the utility model, not all the embodiments. Based on the embodiments in the utility model, all other embodiments obtained by those skilled in the art belong to the scope of protection of the utility model. Embodiment 1:

[0020] As Figure 1As shown, as an embodiment of the utility model discloses a kind of high transparency and super hydrophobic car glass film provided in the embodiment, it includes following sequentially compounded layer structure: transparent PET release film layer 1 (Wanrun Optoelectronics, C05-T1) of thickness 23 μm, transparent acrylic pressure-sensitive adhesive layer 2 (Henkel, Loctite 8087) of thickness 20 μm, PET substrate layer 3 (Yihua Toray UV34) of thickness 50 μm And the POSS-SH-DFMA7 photocuring transparent super hydrophobic coating 4 of thickness 5 μm.

[0021] In addition, the preparation method of the high transparent and super hydrophobic car glass film is also provided in the embodiment, which has the steps comprising:

[0022] Step one, preparation of POSS-SH-DFMA7 photocuring transparent super hydrophobic coating solution

[0023] 1.1 Hydrophobic modification of octavinyl POSS

[0024] 1.1.1 Thiolation of octavinyl POSS

[0025] On the basis of the synthesis method of POSS-SH8 proposed by Wu Chengfeng et al. (Wu Chengfeng, Zhu Weibiao, He Jinxin, et al. Polyether modified polyhedral oligomeric silsesquioxane for constructing water-resistant and hydrophilic anti-fog coating [J]. Surface Technology, 2020, 49(8): 123-131.), octavinyl POSS was first thiolated to obtain POSS-SH8. Then, the fluoralkyl modification of POSS-SH8 was carried out by thiol-ene click reaction.

[0026] 1.1.2 Fluoroalkylation of thiol POSS

[0027] A solution: 5.6 g of dodecafluoroheptyl methacrylate (DFMA) and 0.06 g of photoinitiator I907 were dissolved in 20 mL of anhydrous THF, and the solution was wrapped with tin foil for light protection. B solution: 2.77 g of POSS-SH8 was weighed and dissolved in 20 mL of anhydrous THF. The whole reaction system was carried out in an atmosphere filled with dry N2. A solution was dropped into a flat-bottomed quartz single-necked flask containing B solution through a constant-pressure funnel at a constant speed of 20 mL / h. After the dropping of A solution was completed, the reaction was continued under ultraviolet light for 6 h. The insoluble matter in the post-reaction solution was filtered out with a polytetrafluoroethylene syringe filter, and then part of the THF solvent was removed by rotary evaporation. After a certain amount of anhydrous ethanol was added to the remaining solution, a white solid material was obtained by high-speed centrifugation using a centrifuge. Then, the white solid material was repeatedly washed with anhydrous ethanol for 5-8 times. Finally, after the solvent was completely removed in a vacuum drying oven at 50 °C for 36 h, the target product POSS-SH-DFMA7 was obtained.

[0028] 1.2 Preparation of coating solution

[0029] First, 0.05 g of polyurethane hydrophobically modified acrylate was uniformly mixed with diluent HDDA (hydrophobic resin: HDDA = 4:1), and then 2% of the mixed resin by mass fraction of photoinitiator (I907) was added. After the above system was uniformly mixed, it was added to 5 mL of THF. Under the condition of a rotation speed of 800 r / min, magnetic stirring was carried out at room temperature for 2 h to form a uniform resin solution. Then, 40% of POSS-SH-DFMA7 by mass fraction (accounting for the amount of resin added) and 25% of ethanol by volume fraction (accounting for the amount of THF added) were added to the solution in sequence, and then ultrasonic dispersion was carried out in an ultrasonic shaking device for 1 h, followed by magnetic stirring at room temperature for 24 h.

[0030] Step two, coating and curing of pressure-sensitive adhesive solution

[0031] A transparent acrylic pressure-sensitive adhesive solution (Henkel, Loctite 8087) was coated on the surface of a transparent PET release film (Wanrun Optoelectronics, C05-T1) with a thickness of 23 μm, and dried at 110 °C for 2 min to form a pressure-sensitive adhesive layer with a dry adhesive thickness of 20 μm. Then, the pressure-sensitive adhesive layer was covered on the surface of a PET substrate (Yuehua Toray UV34) with a thickness of 50 μm.

[0032] Step three, spraying and curing of POSS-SH-DFMA7 photocured transparent superhydrophobic coating solution

[0033] Spraying was performed under the settings of a spray gun caliber of 1.0 mm, a flow rate of 0.25 mL / s, and a compressed gas pressure of 0.6 MPa, the PET substrate in step two was 25-27 cm away from the spray gun nozzle, and the moving speed was 3 cm / s, and S-shaped spraying was performed from top to bottom. The naturally air-dried coating was placed in a UV curing instrument, the UV light source was a 1,000 W high-pressure mercury lamp, the substrate was 28-30 cm away from the UV light source, and curing was performed for 5 min in an N2 atmosphere, to obtain a POSS-SH-DFMA7 photocured transparent super-hydrophobic coating layer with a thickness of 5 μm.

[0034] Step four, the semi-finished product in step three was placed in a 50°C curing room, and after 72 h, a high-transparency and super-hydrophobic automobile glass film finished product was obtained. Example 2:

[0035] As a second embodiment of the utility model, the high-transparency and super-hydrophobic automobile glass film provided in the embodiment has the same layered structure and preparation process as those of the aforementioned example 1.

[0036] However, the thickness of the POSS-SH-DFMA7 photocured transparent super-hydrophobic coating layer in the embodiment is 8 μm; the thickness of the PET substrate (Toray Lumirror) is 100 μm; the dry adhesive thickness of the acrylic pressure-sensitive adhesive solution (Henkel, Loctite 8087) obtained after curing is 35 μm; and the thickness of the transparent PET release film (Toray, Lumirror) is 38 μm. Example 3:

[0037] As a third embodiment of the utility model, the high-transparency and super-hydrophobic automobile glass film provided in the embodiment has the same layered structure and preparation process as those of the aforementioned example 1.

[0038] However, the thickness of the POSS-SH-DFMA7 photocured transparent super-hydrophobic coating layer in the embodiment is 12 μm; the thickness of the PET substrate (Toray Lumirror) is 150 μm; the dry adhesive thickness of the acrylic pressure-sensitive adhesive solution (Henkel, Loctite 8087) obtained after curing is 50 μm; and the thickness of the transparent PET release film (Toray, Lumirror) is 50 μm.

[0039] The following table is the test data of the average light transmittance of the high-transparency and super-hydrophobic automobile glass film provided in examples 1-3, and the static water contact angle (WCA) and the rolling angle (SA) of the surface coating.

[0040] Static water contact angle (WCA) in ° Rolling angle (SA) in ° Average light transmittance in % Example 1 156.92 3.24 90.63 Example 2 156.92 3.24 90.63 Example 3 156.92 3.24 90.63

[0041] From the above test data can be known, the utility model provides a kind of high transparency and super-hydrophobic car glass film, the super-hydrophobic effect of its surface layer is excellent, static water contact angle can reach 156.92 ° (static water contact angle ≥150 ° is super-hydrophobic), and rolling angle is as small as 3.24 °.Meanwhile, the average light transmittance of film whole is as high as 90.63 %.

[0042] The test method of each performance in the above table is as follows:

[0043] 1, static water contact angle and rolling angle

[0044] Select a car glass film, tear off release film, paste on 3mm transparent glass, using SDC-200S contact angle tester to measure the static water contact angle and rolling angle of car glass film surface layer.Each sample is measured 5 times, and the average value of measurement is recorded.

[0045] 2, average light transmittance

[0046] Select a car glass film, tear off release film, paste on 3mm transparent glass, using ultraviolet-visible spectrophotometer (Agilent Cary 5000) to measure the average light transmittance of film, and the test range is 380-800 nm.

[0047] In addition, the mechanical stability of the surface coating of the high transparency and super-hydrophobic car glass film provided in the above examples and the weather resistance and chemical stability of the surface coating are determined.

[0048] Among them, the coating mechanical stability test: select a car glass film, tear off release film, paste on 3mm transparent glass, using self-made device, water droplets are released at a rate of 2 drops / s at a height of 30 cm, and the static water contact angle of the coating surface at different times is measured.The test results are:

[0049] The surface coating system of the car glass film in the above examples 1-3 maintains good super-hydrophobic properties even after 6 hours of continuous water droplet impact, with a very small decrease in static water contact angle (the static water contact angle remains at 154.93 ° after 6 hours of continuous water droplet impact), which indicates that it has excellent water droplet impact resistance and good mechanical stability.

[0050] Among them, the coating weather resistance test: select a car glass film, tear off release film, paste on 3mm transparent glass, and place it in an outdoor environment, record the change of static water contact angle once every 3 days.The test results are:

[0051] The static water contact angle of the surface coating of the automobile glass films of the above embodiments 1-3 all showed a certain downward trend in the 30-day test period, but the decrease was extremely small (the static water contact angle recorded after 30 days was 155.41°), indicating that the weather resistance of the coating was stable.

[0052] The chemical stability test: select an automobile glass film, tear off the release film, paste on a 3mm transparent glass, immerse in HCl and NaOH solution with pH value of 1-14 for 24h, and record the static water contact angle under each pH value. The test results are as follows:

[0053] The effective connection between the rough structure after phase separation and the photocuring resin in the surface coating system of the above automobile glass films 1-3 tends to the saturation value of the system, has a dense rough structure and higher surface relief, and has a large contact area with air, not easy to directly contact with the inside of the coating, and the degree of erosion is smaller. After being immersed in acid and alkali solution with pH value of 1-14 for 24h, the lowest static water contact angle can still be kept at 153.62°, and the hydrophobic performance has good retention ability.

[0054] The utility model is not limited to the above best implementation, and anyone can draw other various forms of products under the enlightenment of the utility model, but no matter make any change in its shape or structure, if it has the same or similar technical scheme with the application, it falls in the protection scope of the utility model.

Claims

1. A high transparent and super-hydrophobic car glass film, characterized in that The layered structure comprises, in sequence, a release film layer, a pressure-sensitive adhesive layer, a PET substrate layer and a POSS-SH-DFMA7 photocured transparent super-hydrophobic coating layer.

2. The high transparent and super-hydrophobic car glass film according to claim 1, characterized in that: The thickness of the POSS-SH-DFMA7 photocured transparent super-hydrophobic coating layer is 5-12 microns.

3. The high transparent and super-hydrophobic car glass film according to claim 1, characterized in that: The thickness of the PET substrate layer is 50-150 microns.

4. The high transparent and super-hydrophobic car glass film according to claim 1, characterized in that: The thickness of the pressure-sensitive adhesive layer is 20-50 microns.

5. The high transparent and super-hydrophobic car glass film according to claim 1, characterized in that: The thickness of the release film layer is 23-50 microns.

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