Automobile paint surface protective film with ultraviolet-proof performance and hydrophobic performance

Abstract

The utility model discloses an automobile paint surface protective film, in particular to an automobile paint surface protective film with ultraviolet-proof performance and hydrophobic performance, which has a layered structure and comprises a release film layer, a pressure-sensitive adhesive layer, a TPU (thermoplastic polyurethane) base material layer and a TPU / TiO2 / PDMS (thermoplastic polyurethane / TiO2 / polydimethylsiloxane) composite fiber film layer. According to the utility model, the technical problem that the surface layer of the automobile paint surface protective film has ultraviolet-proof performance and hydrophobic performance is solved. The automobile paint surface protective film provided by the utility model has a simple layered structure which is the same as a typical automobile paint surface protective film in the prior art and is of a three-layer structure, and the surface layer has excellent self-cleaning capability and self-repairing capability after mechanical damage; and dust on the surface of the automobile paint protective film can be taken away under the rolling action of water drops, so that self-cleaning is realized.

Description

Technical Field

[0001] The utility model relates to an automobile paint surface protective film, in particular to an automobile paint surface protective film with ultraviolet protection and hydrophobic properties. Background Art

[0002] Automotive paint protection film, commonly known as paint film, is applied to the painted surface of a car to protect the paint, providing scratch resistance, stain resistance, environmental corrosion resistance, and decorative aesthetics. Commercially available paint films are typically coated with a self-healing coating. If the car body is scratched or slightly impacted, minor scratches will disappear automatically or with heat, as long as the film itself is not damaged. If a serious impact damages the film, the film can be partially replaced.

[0003] The layered structure of common automotive paint protection films includes: a pressure-sensitive adhesive layer, a TPU substrate layer and a self-repairing coating. The above-mentioned self-repairing coating is now mostly made of polyurethane.

[0004] In the existing technology, automotive paint protection films often have UV blocking properties by adding ultraviolet absorbers (UV absorbers) to the TPU substrate layer or pressure-sensitive adhesive layer. However, this method has the problem of reduced UV blocking performance or even failure after long-term use.

[0005] Zhou Qi, Xiong Ziyin, et al. proposed the preparation and performance research of TPU / TiO2 / PDMS composite fiber membrane (Journal of Hunan Institute of Engineering (Natural Science Edition), Vol. 33, No. 1, March 2023). Specifically: In order to prepare a TPU / TiO2 / PDMS composite fiber membrane with both UV protection and hydrophobic properties, TiO2 nanoparticles were successfully loaded into the TPU electrospun fiber membrane by combining electrospinning with ultrasonic loading of nanoparticles, and the TPU electrospun fiber membrane loaded with TiO2 nanoparticles was cured with PDMS. The SEM results showed that the surface of the TPU / TiO2 / PDMS composite fiber membrane was successfully loaded with TiO2 nanoparticles, and the distribution was relatively uniform. The anti-UV test results showed that the loading of TiO2 nanoparticles on the fiber membrane greatly improved the UPF value of the TPU electrospun fiber membrane. With the increase of the TiO2 nanoparticle loading, the UPF value of the TPU / TiO2 / PDMS composite fiber membrane gradually increased, and when the TiO2 nanoparticle loading was 1.5 wt%, the UPF value increased significantly by 75.8%. The contact angle test results showed that the contact angle between TiO2 nanoparticles and PDMS was significantly improved. Under the rough, low-surface-energy composite fiber membrane, the membrane's surface transitioned from hydrophilic to hydrophobic. With increasing TiO2 nanoparticle loading, the contact angle of the TPU / TiO2 / PDMS composite fiber membrane gradually increased, reaching 124° at a TiO2 nanoparticle loading of 1.5 wt%. The resulting TPU / TiO2 / PDMS composite fiber membrane exhibited excellent UV protection and hydrophobic properties.

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

[0007] The purpose of the utility model is to solve the above-mentioned deficiencies in the prior art and to provide a car paint protection film having a surface layer with both UV protection and hydrophobic properties.

[0008] In order to achieve the above objectives, the utility model designs a car paint protection film with UV protection and hydrophobic properties, whose layered structure includes: a release film layer, a pressure-sensitive adhesive layer, a TPU substrate layer and a TPU / TiO2 / PDMS composite fiber membrane layer.

[0009] The aforementioned UV-resistant and hydrophobic automotive paint protection film has a layered structure in which the surface TPU / TiO2 / PDMS composite fiber membrane layer has UV-resistant and hydrophobic properties. The principle is as follows:

[0010] Anti-ultraviolet performance: On the one hand, this is because TiO2 nanoparticles have good anti-ultraviolet function. On the other hand, as the concentration of TiO2 nanoparticles increases, more TiO2 is loaded on the surface of the fiber membrane, and the surface roughness of the fiber membrane also increases. The reflection and refraction of ultraviolet rays are also enhanced, thereby greatly improving the anti-ultraviolet performance of the TPU / TiO2 / PDMS composite fiber membrane.

[0011] Hydrophobicity: There are two ways to increase the water contact angle and hydrophobicity of a material's surface: (1) chemically modifying the material's surface chemical composition to reduce its surface free energy; and (2) changing the material's surface three-dimensional microstructure to increase its surface roughness. The surface layer of this automotive paint protection film is constructed by ultrasonically loading TiO2 nanoparticles onto a TPU electrospun fiber membrane and then curing it with PDMS to create a TPU / TiO2 / PDMS composite fiber membrane with both low surface free energy and surface roughness.

[0012] In the above-mentioned automobile paint protection film having UV protection and hydrophobic properties, the thickness of the TPU / TiO2 / PDMS composite fiber membrane layer in its layered structure is preferably 45μm-60μm.

[0013] The above-mentioned automotive paint protection film with UV protection and hydrophobic properties, in which the TPU substrate layer in the layered structure is preferably an aliphatic TPU substrate layer, the surface hardness is preferably 80A-93A, the visible light transmittance is preferably above 90%, the elongation at break is preferably above 300%, the haze is preferably below 2%, and the thickness is preferably 100μm-300μm.

[0014] The above-mentioned automobile paint protection film with UV protection and hydrophobic properties, the pressure-sensitive adhesive layer in its layered structure is preferably an acrylic pressure-sensitive adhesive layer or a polyurethane pressure-sensitive adhesive layer, the visible light transmittance is preferably above 90%, and the thickness is preferably 10μm-50μm.

[0015] In the above-mentioned automotive paint protection film having UV protection and hydrophobic properties, the release film layer in its layered structure is preferably a PET release film layer, more preferably a white PET release film layer, the haze is preferably above 70%, the release force is preferably within 20 g / inch, and the thickness is preferably 23 μm-100 μm.

[0016] The above-mentioned automobile paint protection film with UV protection and hydrophobic properties preferably includes a protective film layer in its layered structure, which is composited onto the surface of the TPU / TiO2 / PDMS composite fiber membrane layer.

[0017] The protective film layer can protect the TPU / TiO2 / PDMS composite fiber membrane layer to the greatest extent, so as to avoid the situation where "the TPU / TiO2 / PDMS composite fiber membrane layer is scratched and worn during packaging, transportation and construction."

[0018] In the above-mentioned automobile paint protection film with UV protection and hydrophobic properties, the protective film layer in its layered structure is further preferably selected to be a PET protective film, and its thickness is preferably selected to be 12μm-75μm.

[0019] Compared with the prior art, the automobile paint protection film with UV protection and hydrophobicity obtained by the present invention has the following technical effects:

[0020] The utility model provides an automobile paint protection film, the surface layer of which has both ultraviolet protection and hydrophobic properties.

[0021] The automobile paint protection film provided by the utility model has a simple layered structure, which is the same as the typical automobile paint protection film in the prior art, and has a three-layer structure.

[0022] The utility model provides an automobile paint protection film, the surface of which has excellent self-cleaning ability. The rolling effect of water droplets can be used to remove sand and dust on the surface of the automobile paint protection film, thereby achieving self-cleaning.

[0023] The utility model provides an automobile paint protection film, the surface of which has the ability to self-repair after mechanical damage. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 Schematic diagram of the layered structure of a car paint protection film with UV protection and hydrophobic properties.

[0025] In the figure: release film layer 1, pressure-sensitive adhesive layer 2, TPU substrate layer 3, TPU / TiO2 / PDMS composite fiber membrane layer 4, protective film layer 5. DETAILED DESCRIPTION

[0026] 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:

[0027] like Figure 1As shown, as an embodiment of the present invention, a car paint protection film with UV protection and hydrophobic properties is provided in this embodiment, and its layered structure includes: a release film layer 1, a pressure-sensitive adhesive layer 2, a TPU substrate layer 3, a TPU / TiO2 / PDMS composite fiber film layer 4 and a protective film layer 5.

[0028] The protective film layer in this embodiment is a PET protective film (Yihua Dongli, G01) with a thickness of 12 μm.

[0029] The thickness of the TPU / TiO2 / PDMS composite fiber membrane layer in this embodiment is 45 μm.

[0030] The TPU substrate layer in this embodiment uses an aliphatic TPU base film (Argotec 49510) with a surface hardness of 93A, a visible light transmittance of 92%, an elongation at break of 550%, a haze of 1.0%, and a thickness of 100 μm.

[0031] The pressure-sensitive adhesive layer in this embodiment is made of acrylic pressure-sensitive adhesive (Henkel, Loctite 8087), with a visible light transmittance of 92% and a thickness of 10 μm.

[0032] The release film layer in this embodiment is a white PET release film (Toray, XZ31SR) with a haze of 73%, a release force of 10 g / inch, and a thickness of 23 μm.

[0033] The method for preparing the above-mentioned automobile paint protection film having UV protection and hydrophobic properties specifically comprises the following steps:

[0034] Step 1: Preparation of TPU / TiO2 / PDMS composite fiber membrane

[0035] 1.1 Preparation of TPU electrospinning solution

[0036] In order to prepare a TPU electrospinning solution with a concentration of 10 wt%, 1 g of TPU particles was first placed in 9 g of DMF / THF (volume ratio of 1:1) mixed solvent and stirred at room temperature for 6 h using a constant temperature magnetic stirrer (Model 85-2, Changzhou Langyue Instrument Manufacturing Co., Ltd.) to completely dissolve the TPU. The solution was then allowed to stand for 3 h to obtain a bubble-free and transparent spinning solution.

[0037] 1.2 Preparation of TPU electrospun fiber membrane

[0038] TPU electrospun fiber membranes were prepared using an electrospinning device (FM-130, Beijing Fuyouma Technology Co., Ltd.). The spinning temperature and humidity were controlled at (25 ± 2)°C and (40 ± 5)%, respectively. The prepared spinning solution was first transferred to a 10 mL plastic syringe equipped with a 22 G flat stainless steel needle. The syringe was then pumped at a rate of 1.0 mL / h. -1 The spinning voltage between the needle tip and the collector was 20 kV, and the spinning distance was 13 cm. After 1 h of electrospinning, the electrospun membrane was removed and dried in a vacuum oven at 80 °C for 2 h to remove residual solvent.

[0039] 1.3 Preparation of TPU / TiO2 / PDMS composite fiber membrane

[0040] TiO2 nanoparticles were added to deionized water and magnetically stirred at room temperature for 1 hour. The mixture was then ultrasonically dispersed for 30 minutes using an ultrasonic disperser (KQ-200TDE, Kunshan Ultrasonic Instrument Co., Ltd.) to prepare a 1.5 wt% TiO2 nanoparticle suspension. It should be noted that when the TiO2 concentration exceeds 1.5 wt%, significant precipitation will occur in the suspension. The TPU electrospun fiber membrane prepared in Section 1.2 was placed in a 1.5 wt% TiO2 nanoparticle suspension. The TiO2 nanoparticles were ultrasonically loaded for 1 hour, and the sample was dried in an 80°C vacuum drying oven for 2 hours to obtain a TPU / TiO2 composite fiber membrane. The TPU / TiO2 composite fiber membrane obtained above was immersed in a 1 wt% PDMS / n-hexane solution (where the volume ratio of PDMS prepolymer and cross-linking agent was 10:1) for 30 seconds and then dried in an 80°C vacuum drying oven for 2 hours to obtain a TPU / TiO2 / PDMS composite fiber membrane.

[0041] Step 2: Apply pressure-sensitive adhesive layer

[0042] An acrylic pressure-sensitive adhesive (Henkel, Loctite 8087) coating solution was applied to a 23 μm white PET release film (Toray, XZ31SR) and dried at 110°C for 2 minutes to form a 10 μm thick pressure-sensitive adhesive layer. This layer was then applied to one side of a 100 μm aliphatic TPU substrate (Argotec 49510).

[0043] Step 3: Composite TPU / TiO2 / PDMS composite fiber membrane layer

[0044] The TPU / TiO2 / PDMS composite fiber membrane prepared in step 1 was covered on the other surface of a 100 μm thick TPU substrate (49510, Argotec) by thermal bonding technology. After curing, the thickness of the TPU / TiO2 / PDMS composite fiber membrane layer was 45 μm.

[0045] Step 4: Composite protective film layer

[0046] In step 3, the TPU / TiO2 / PDMS composite fiber membrane layer was covered with a 12 μm PET protective film (Yihua Dongli, G01).

[0047] Step 5: Ripening

[0048] The semi-finished product in step 4 is placed in a 50° C. curing chamber for 72 hours to obtain the automotive paint protection film of the present invention. Example 2:

[0049] As a second embodiment of the present invention, the present embodiment provides an automobile paint protection film with UV protection and hydrophobic properties, and its layered structure and preparation method are substantially the same as those of Example 1.

[0050] However, the PET protective film (Yihua Toray, G01) used as the protective film layer in this example has a thickness of 45 μm. The TPU / TiO2 / PDMS composite fiber membrane layer in this example has a thickness of 52 μm. The aliphatic TPU base film (Argotec 49510) used as the TPU substrate layer in this example has a thickness of 200 μm. The pressure-sensitive adhesive layer in this example also uses acrylic pressure-sensitive adhesive (Henkel, Loctite 8087), with a dry adhesive thickness of 30 μm. The white PET release film (Toray, XZ31SR) used as the release film layer in this example has a thickness of 62 μm. Example 3:

[0051] As a third embodiment of the present invention, a car paint protection film with UV protection and hydrophobic properties is provided in this embodiment. Similarly, its layered structure and preparation method are roughly the same as those in Example 1.

[0052] However, the PET protective film (Yihua Toray, G01) used as the protective film layer in this example has a thickness of 75 μm. The TPU / TiO2 / PDMS composite fiber membrane layer in this example has a thickness of 60 μm. The aliphatic TPU base film (Argotec 49510) used as the TPU substrate layer in this example has a thickness of 300 μm. The pressure-sensitive adhesive layer in this example also uses acrylic pressure-sensitive adhesive (Henkel, Loctite 8087), with a dry adhesive thickness of 50 μm. The white PET release film (Toray, XZ31SR) used as the release film layer in this example has a thickness of 100 μm.

[0053] Comparative Example 1:

[0054] A method for preparing an automobile paint protection film comprises the following steps:

[0055] (1) Preparation of polyurethane coating liquid

[0056] 860 parts of polycaprolactone polyol resin (Daicel ChemTech, PLACCEL 210CP), 20 parts of stannous isooctanoate (Shanghai Aladdin Reagent Co., Ltd.) and 10 parts of leveling agent BYK 320 (BYK) were added to 1000 parts of ethyl acetate in sequence, and finally 150 parts of toluene diisocyanate (BASF) was added and stirred for 30 minutes to mix evenly.

[0057] (2) Coating pressure-sensitive adhesive layer

[0058] An acrylic pressure-sensitive adhesive (Henkel, Loctite 8087) was coated onto a 23 μm white PET release film (Toray, XZ31SR) and dried at 110°C for 2 minutes to form a 10 μm thick pressure-sensitive adhesive layer. This layer was then coated onto a 100 μm aliphatic TPU (Argotec 49510).

[0059] (3) Applying polyurethane coating

[0060] In the second step, the other side of the aliphatic TPU substrate was coated with the polyurethane coating liquid prepared in the first step, and the curing conditions were 120°C for 2 minutes. The thickness after drying was 6 μm. Finally, a 12 μm thick PET protective film (Yihua Toray, G01) was covered on the surface.

[0061] (4) Late maturation

[0062] The semi-finished product in the third step is placed in a 50°C curing chamber for 72 hours to obtain the existing conventional automobile paint protection film.

[0063] Comparative Example 2:

[0064] A method for preparing an automobile paint protection film comprises the following steps:

[0065] (1) Preparation of polyurethane coating liquid

[0066] 1200 parts of polycarbonate polyol resin (Daicel ChemTech, PLACCEL 220CPB), 26 parts of stannous isooctanoate (Shanghai Aladdin Reagent Co., Ltd.) and 13 parts of leveling agent BYK 320 (BYK) were added to 1200 parts of ethyl acetate in sequence, and finally 100 parts of hexamethylene diisocyanate (BASF) was added and stirred for 30 minutes to mix evenly.

[0067] (2) Coating pressure-sensitive adhesive layer

[0068] An acrylic pressure-sensitive adhesive (Ashland, 9510H) was coated onto a 23 μm white PET release film (Toray, XZ31SR) and dried at 110°C for 2 minutes to form a 10 μm thick pressure-sensitive adhesive layer. This layer was then covered with a 100 μm aliphatic TPU (Argotec 49510).

[0069] (3) Applying polyurethane coating

[0070] In the second step, the other side of the aliphatic TPU substrate was coated with the polyurethane coating liquid prepared in the first step, and the curing conditions were 120°C for 2 minutes. The thickness after drying was 6 μm. Finally, a 12 μm thick PET protective film (Yihua Toray, G01) was covered on the surface.

[0071] (4) Late ripening

[0072] The semi-finished product in the third step is placed in a 50°C curing chamber for 72 hours to obtain the existing conventional automobile paint protection film.

[0073] The following table shows the test data for the UV transmittance and water contact angle (CA) of the automotive paint protection films provided in Examples 1-3 and Comparative Examples 1 and 2. The self-healing properties of the surface layers of the automotive paint protection films provided in the above Examples and Comparative Examples were also measured.

[0074] Examples UV transmittance (%) Water contact angle (CA / °) Self-repair performance Example 1 23.5 124 qualified Example 2 30.8 124 qualified Example 3 35.2 124 qualified Comparative Example 1 70.4 88.6 qualified Comparative Example 2 70.9 88.5 qualified

[0075] From the above test data, it can be seen that the UV transmittance of the automotive paint protection film provided by the present invention has been significantly reduced, by at least 50%; while the surface water contact angle (CA) has been significantly improved, by 40%.

[0076] At the same time, it can be seen from the above test data that the automobile paint protection film of the present invention also has self-repairing properties.

[0077] The test methods for each performance in the above table are as follows:

[0078] 1. Surface water contact angle (CA)

[0079] Select a piece of paint protection film, remove the protective film and release film, and apply it to a 3mm thick transparent glass. Use an SDC-200S contact angle tester to measure the water contact angle of the paint protection film. Perform five measurements for each sample and record the average value.

[0080] 2. Ultraviolet transmittance

[0081] A piece of paint protection film was selected, the protective film and release film were removed, and the film was attached to a 3mm transparent glass. The transmittance in the 280nm-380nm band was tested using a UV-visible spectrophotometer (Agilent Cary 5000), and the UV transmittance was then calculated.

[0082] 3. Self-repair performance

[0083] Select a paint protection film, tear off the release film, and wet-stick it on a black painted panel. Use 500g of #0000 steel wool to slide back and forth on the surface of the paint protection film three times, then place the painted panel in a 60℃ oven for 30 minutes to observe whether the scratches are repaired.

[0084] 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 car paint protection film with UV protection and hydrophobic properties, characterized by a layered structure comprising: Release film layer, pressure-sensitive adhesive layer, TPU substrate layer and TPU / TiO2 / PDMS composite fiber membrane layer.

2. The automotive paint protection film with UV protection and hydrophobic properties according to claim 1, characterized in that: The thickness of the TPU / TiO2 / PDMS composite fiber membrane layer is 45 μm-60 μm.

3. The automobile paint protection film with UV protection and hydrophobic properties according to claim 1, characterized in that: The TPU substrate layer is an aliphatic TPU substrate layer with a thickness of 100 μm-300 μm.

4. The automobile paint protection film with UV protection and hydrophobic properties according to claim 1, characterized in that: The pressure-sensitive adhesive layer is an acrylic pressure-sensitive adhesive layer or a polyurethane pressure-sensitive adhesive layer, and has a thickness of 10 μm-50 μm.

5. The automobile paint protection film with UV protection and hydrophobic properties according to claim 1, characterized in that: The release film layer is a PET release film layer with a thickness of 23 μm-100 μm.

6. The automobile paint protection film with UV protection and hydrophobic properties according to claim 1, characterized in that: It also includes a protective film layer, which is compounded onto the surface of the TPU / TiO2 / PDMS composite fiber membrane layer.

7. The automobile paint protection film with UV protection and hydrophobic properties according to claim 6, characterized in that: The protective film layer is a PET protective film with a thickness of 12 μm-75 μm.

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