CN217418592U - Automobile paint protective film - Google Patents
Automobile paint protective film Download PDFInfo
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- CN217418592U CN217418592U CN202221562313.2U CN202221562313U CN217418592U CN 217418592 U CN217418592 U CN 217418592U CN 202221562313 U CN202221562313 U CN 202221562313U CN 217418592 U CN217418592 U CN 217418592U
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Abstract
The utility model discloses a finish protection film, especially a car finish protection film, including TPU substrate layer and pressure sensitive adhesive layer, pressure sensitive adhesive layer coats on a side of TPU substrate layer is on the surface, its characterized in that: and a super-hydrophobic alumina thin film layer is compounded on the other side surface of the TPU substrate layer. The surface layer of the utility model has the characteristics of super-hydrophobicity, high corrosion resistance, strong scratch resistance, strong impact resistance and the like.
Description
Technical Field
The utility model relates to a finish protection film, especially an automobile finish protection film.
Background
The automobile paint surface protective film is also called as invisible automobile clothes, is a layer of transparent protective film attached to the surface of an automobile body, can effectively prevent scratching and hitting of sand grains, also isolates the contact of automobile paint and air, and can prevent acid rain, insects, bird droppings and the like from corroding the automobile body paint surface. The main purpose is that the original factory paint of the automobile can be bright as new after being torn off.
The existing automobile paint surface protective film is generally of a three-layer structure and sequentially comprises a repair coating, a TPU substrate layer and a pressure-sensitive adhesive layer. The repair coating is mostly made of polyurethane materials, and can be self-repaired under the heating condition after micro scratches are generated. However, the repair coating is soft, which results in relatively poor hydrophobicity, strong scratch resistance, corrosion resistance and strong impact resistance of the protective film for automobile paint.
Therefore, the utility model is provided.
Disclosure of Invention
The utility model aims to solve the defects of the prior art and provide an automobile paint surface protective film which adopts a sol-gel technology to form a super-hydrophobic alumina surface layer.
In order to realize the purpose, the utility model discloses a car lacquer painting protection film, including TPU substrate layer and pressure sensitive adhesive layer, pressure sensitive adhesive layer coats on a side of TPU substrate layer is surperficial, and it has super hydrophobic alumina thin film layer to compound on the opposite side surface of TPU substrate layer. Preferably, the surface of the super-hydrophobic alumina thin film layer, which is far away from the TPU base material layer, has a micron-scale petal-shaped coarse structure.
The super-hydrophobic alumina thin film layer on the surface layer of the protective film for the automobile paint surface of the utility model has the characteristics of high corrosion resistance, strong scratch resistance, strong impact resistance and the like; meanwhile, the contact angle between the surface of the water-repellent fabric and water can reach 154.2 degrees at most, namely the water-repellent fabric has super-hydrophobicity.
The pressure-sensitive adhesive layer is preferably a structure containing glass fiber filaments; the monofilament diameter of the glass fiber filament is less than or equal to 3 mu m, and the length of the glass fiber filament is 10 mm-20 mm; 2-5 parts by weight of glass fiber filament relative to 100 parts by weight of pressure-sensitive adhesive.
The pressure-sensitive adhesive layer contains glass fiber filament tissues, the pressure-sensitive adhesive can generate better mutual drag acting force due to the glass fiber filament tissues, the integrity of the pressure-sensitive adhesive layer can be better, and when the automobile paint surface protective film is peeled off after being adhered to automobile glass, the condition that adhesive residues are remained on the surface of the glass is not easy to occur.
The thickness of the super-hydrophobic alumina thin film layer is preferably 6-27 μm, and the whole thickness of the automobile paint surface protective film can be reduced to the greatest extent on the premise of ensuring the performances.
The TPU base material layer is preferably an aliphatic TPU layer, the surface hardness is preferably 80A-93A, the visible light transmittance is preferably more than 90%, the elongation at break is preferably more than 300%, the haze is preferably less than 2%, and the thickness is preferably 100-300 μm.
The pressure-sensitive adhesive layer is preferably a transparent acrylic pressure-sensitive adhesive layer or a polyurethane pressure-sensitive adhesive layer, the visible light transmittance is preferably more than 90%, and the thickness is preferably 10-50 μm.
The surface of the pressure-sensitive adhesive layer is preferably a composite release film layer; the release film layer is preferably a PET release film layer, more preferably a white PET release film layer, the haze is preferably more than 70%, the release force is preferably within 20g/inch, and the thickness is 23-100 μm.
Compared with the prior art, the utility model provides a pair of car lacquer painting protection film, it has possessed following advantage:
1) the surface layer of the automobile paint surface protective film has super-hydrophobicity, so that dust and dirt (bird dung, tree oil and the like) accumulated on the surface of the automobile paint surface protective film can be easily washed by rainwater in rainy days, and the automobile paint surface can be kept clean for a long time; simultaneously, because of dust and dirty difficult for remaining for a long time on car finish protection film, and then effectively stopped "because of dust and dirty remain in the protection film surface for a long time, can permeate the TPU substrate in situ along with the extension of contact time, lead to the later stage can't clear away, and then influence the life's of protection film the condition for the life of car finish protection film is longer relatively.
2) The utility model discloses pasting and peeling performance of car lacquer painting protection film are good, can must paste (adhesion) in car paint surface very easily, or peel off from car paint surface, and the difficult condition that takes place adhesive residue and remain on car paint surface.
3) The utility model discloses the top layer of car finish protection film possesses characteristics such as high corrosivity resistance, resistant strong scratch nature and resistant strong impact, and daily stability in use is good, long service life, and the top layer of car finish protection film can not be because of some bad weather or environment for example coastal waters alkaline environment, acid rain impaired, also can not be impaired because of the stone particle striking that splashes up in the car driving process.
Drawings
Fig. 1 is a schematic view of a layered structure of an automobile finish protective film.
In the figure: the super-hydrophobic alumina film layer 1, the TPU substrate layer 2, the pressure-sensitive adhesive layer 3 and the release film layer 4.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments in the present invention, all other embodiments obtained by a person skilled in the art all belong to the protection scope of the present invention.
Example 1:
as shown in fig. 1, as an embodiment of the present invention, the present invention provides an automobile paint surface protective film, which comprises a super-hydrophobic alumina thin film layer 1, a TPU substrate layer 2, a pressure sensitive adhesive layer 3 and a release film layer 4, which are sequentially covered. The surface of the super-hydrophobic alumina thin film layer 1, which is far away from the TPU substrate layer 2, is provided with a micron petal-shaped rough structure.
The thickness of the superhydrophobic alumina thin film layer 1 in this embodiment is 6 μm.
In this embodiment, the TPU substrate layer 2 is made of aliphatic TPU, has a surface hardness of 80A to 93A, a visible light transmittance of 90% or more, an elongation at break of 300% or more, a haze of 2% or less, and a thickness of 100 μm.
In this embodiment, the pressure sensitive adhesive layer 3 is made of a transparent acrylic pressure sensitive adhesive, and has a visible light transmittance of 90% or more and a thickness of 10 μm. Meanwhile, the pressure-sensitive adhesive layer 3 contains glass fiber filaments, and the filament diameter of the glass fiber filaments is less than or equal to 3 microns, and the length of the glass fiber filaments is 10 mm-20 mm; 2 parts by weight of glass fiber filaments per 100 parts by weight of pressure sensitive adhesive.
In this embodiment, the release film layer 4 is made of white PET release film, has a haze of 70% or more, a release force of 20g/inch or less, and a thickness of 23 μm.
The embodiment also provides a preparation method of the automobile paint protective film, which comprises the following specific steps:
1. preparation of super-hydrophobic alumina film
1.1 starting materials
Aluminum tributoxide and polyethyleneimine (PEI, 30 wt%), Shanghai Aldrich, diluted to a 0.2wt% solution with distilled water before use. Stearic acid (STA), Dicyclohexylcarbodiimide (DCC) and ethyl acetoacetate (EAcAc) were purchased from Shanghai reagent, national institute of medicine. Isopropanol, acetone, n-hexane, etc., and commercial products, all of which are analytically pure. A glass slide (76.2 mm × 25.4 mm × 1.2 mm), the national institute of standards of japan.
1.2 detailed procedures
Alumina sol is prepared by taking aluminum tributyl alkoxide as a precursor and adopting a sol-gel method. Mixing and stirring aluminum tributyl alcoholate and isopropanol at room temperature for 1h, then adding a chelating agent ethyl acetoacetate and stirring for 3h, then slowly adding a mixed solution of isopropanol and distilled water, and hydrolyzing for 24h to obtain the clear and stable alumina sol. Wherein, the molar ratio of isopropanol, ethyl acetoacetate, water and aluminum tributyrate is 20: 1: 4: 1. The sol is evenly coated on a glass slide which is cleaned by acetone and distilled water by a dipping and pulling method, and is roasted for 10min in a muffle furnace at 400 ℃ after being dried, and then is treated for 20min in boiling water, so that the alumina gel film is obtained. And finally, soaking the glass slide coated with the alumina film in a Polyethyleneimine (PEI) solution for 20min, then washing the glass slide by using distilled water, then placing the glass slide in a hexane solution of stearic acid (STA) and Dicyclohexylcarbodiimide (DCC) for reacting for 24h, taking the glass slide out, then washing the glass slide by using n-hexane, acetone and distilled water respectively, and airing the glass slide at room temperature to obtain the super-hydrophobic alumina film.
2. Preparation of pressure-sensitive adhesive coating liquid
2 parts of glass fiber filaments are added to 100 parts of acrylic pressure sensitive adhesive (Henkel, Loctite 8087), fully stirred for 30min and mixed uniformly for later use.
3. Coating pressure-sensitive adhesive layer 3
The pressure-sensitive adhesive coating liquid in the above step 2 was coated on a 23 μm white PET release film (Toray, XZ31 SR) and dried at 110 ℃ for 2min to form a pressure-sensitive adhesive layer 3 having a dry adhesive thickness of 10 μm. The pressure sensitive adhesive was then coated on one side of a 100 μm aliphatic TPU substrate (Argotec 49510).
4. Composite super-hydrophobic alumina film
In the third step, the other side surface of the aliphatic TPU substrate is compounded with the super-hydrophobic alumina film prepared in the first step, the compounding temperature is 120 ℃, the compounding time is 2min, and the thickness of the super-hydrophobic alumina film is 6 mu m.
5. Late stage maturation
Putting the semi-finished product in the fourth step into a curing chamber with the temperature of 50 ℃, and obtaining the protective film for the automobile paint surface through 72 hours.
In the embodiment, the surface super-hydrophobic alumina film of the automobile paint protective film takes aluminum alkoxide as a raw material, and generates Al (OH) through hydrolysis reaction in the presence of isopropanol, ethyl acetoacetate and water 3 Sol; after coating, the gel is obtained by polycondensation reaction at high temperature. After the film is immersed in a Polyethyleneimine (PEI) solution, a PEI monomolecular layer is adsorbed and self-assembled on the surface and the holes of the film through hydrogen bonds and van der Waals force; then immersing the alumina film in a normal hexane solution of Stearic Acid (STA), under the action of Dicyclohexylcarbodiimide (DCC), carrying out dehydration condensation reaction on the self-assembled PEI and the STA, further grafting a long carbon chain, and growing a layer of hydrophobic long carbon chain molecule on the surface of the alumina filmAnd forming petal-shaped rough structures. The petal-shaped coarse structure of the surface of the film and the unique hydrophobic long-chain monomolecular layer act together to endow the alumina film with super-hydrophobic property, and the contact angle of the surface of the alumina film and water can reach 154.2 degrees at most. Moreover, after the super-hydrophobic film is placed in the air for one year, the surface of the super-hydrophobic film still maintains the super-hydrophobic characteristic, and the super-hydrophobic characteristic of the film is very stable.
Example 2:
as a second embodiment of the present invention, there is provided an automobile paint protective film having a general structure in accordance with example 1.
The thickness of the superhydrophobic alumina thin film layer 1 in this example was 17 μm.
In this embodiment, the TPU substrate layer 2 is also made of aliphatic TPU, and has a surface hardness of 80A to 93A, a visible light transmittance of 90% or more, an elongation at break of 300% or more, a haze of 2% or less, and a thickness of 200 μm.
In this embodiment, the pressure sensitive adhesive layer 3 is also made of a transparent acrylic pressure sensitive adhesive, and has a visible light transmittance of 90% or more and a thickness of 30 μm. Meanwhile, the pressure-sensitive adhesive layer 3 contains glass fiber filaments, and the filament diameter of the glass fiber filaments is less than or equal to 3 microns, and the length of the glass fiber filaments is 10 mm-20 mm; the glass fiber filament was 3.5 parts by weight with respect to 100 parts by weight of the pressure sensitive adhesive.
In this embodiment, the release film layer 4 is also made of white PET release film, the haze is above 70%, the release force is within 20g/inch, and the thickness is 65 μm.
In addition, the method for preparing the protective film for automobile paint surface in this embodiment is substantially the same as that of the foregoing embodiment 1. The pressure-sensitive adhesive coating liquid of this example was prepared in such an amount that the glass fiber filaments were 3.5 parts by weight relative to 100 parts by weight of the pressure-sensitive adhesive.
Example 3:
as a third embodiment of the present invention, there is provided a protective film for a paint surface of an automobile, the general structure of which is the same as that of example 1.
The thickness of the superhydrophobic alumina thin film layer 1 in this example was 27 μm.
In this embodiment, the TPU substrate layer 2 is also made of aliphatic TPU, and has a surface hardness of 80A to 93A, a visible light transmittance of 90% or more, an elongation at break of 300% or more, a haze of 2% or less, and a thickness of 300 μm.
In this embodiment, the pressure sensitive adhesive layer 3 is also made of a transparent acrylic pressure sensitive adhesive, and has a visible light transmittance of 90% or more and a thickness of 50 μm. Meanwhile, the pressure-sensitive adhesive layer 3 contains glass fiber filaments, and the filament diameter of the glass fiber filaments is less than or equal to 3 microns, and the length of the glass fiber filaments is 10 mm-20 mm; 5 parts by weight of glass fiber filaments per 100 parts by weight of pressure sensitive adhesive.
In this embodiment, the release film layer 4 is also made of white PET release film, the haze is above 70%, the release force is within 20g/inch, and the thickness is 100 μm.
In addition, the method for preparing the protective film for automobile paint surface in this embodiment is substantially the same as that of the foregoing embodiment 1. The pressure-sensitive adhesive coating liquid of this example was prepared in 5 parts by weight of the glass fiber filaments with respect to 100 parts by weight of the pressure-sensitive adhesive.
Comparative example 1:
a preparation method of a paint protective film comprises the following steps:
(1) preparation of repair coating liquid
860 parts of polycaprolactone polyol resin (Daicel ChemTech, PLACCEL 210 CP), 20 parts of stannous isooctanoate (alatin chemical reagent net), 15 parts of ultraviolet absorbent TINUVIN 400 (BASF), 15 parts of light stabilizer TINUVIN 292 (BASF) and 10 parts of flatting agent BYK 320 (BYK) are sequentially added into 1000 parts of ethyl acetate, and finally 150 parts of toluene diisocyanate (BASF) are added, stirred for 30min and mixed uniformly.
(2) Coating pressure sensitive adhesive layer 3
The transparent acrylic pressure-sensitive adhesive solution (Henkel, Loctite 8087) was coated on a 75 μm white PET release film (Toray, XZ31 SR) under drying conditions of 110 ℃ for 2min to form a pressure-sensitive adhesive layer 3 having a dry adhesive thickness of 25 μm. The pressure sensitive adhesive was then coated onto a 150 μm aliphatic TPU surface (Argotec 49510).
(3) Coating repair coating liquid
In the second step, the other side of the aliphatic TPU substrate is coated with the repair coating liquid prepared in the first step, the curing condition is 120 ℃, the curing time is 2min, the thickness after drying is 8 microns, and finally the surface is covered with a PET protective film (Toray instruments, G01) with the thickness of 50 microns.
(4) Late stage curing
And (4) putting the semi-finished product in the third step into a curing chamber at 50 ℃, and carrying out 72 hours to obtain the conventional automobile paint surface protective film.
Comparative example 2:
a preparation method of a paint protective film comprises the following steps:
(1) preparation of repair coating liquid
1200 parts of polycarbonate polyol resin (Daicel ChemTech, PLACCEL 220 CPB), 26 parts of stannous isooctanoate (Allantin chemical network), 20 parts of ultraviolet absorber TINUVIN 400 (BASF), 20 parts of light stabilizer TINUVIN 292 (BASF) and 13 parts of flatting agent BYK 320 (BYK) are added to 1200 parts of ethyl acetate in sequence, and finally 100 parts of hexamethylene diisocyanate (BASF) are added, stirred for 30min and mixed uniformly.
(2) Coating pressure sensitive adhesive layer 3
A transparent acrylic pressure-sensitive adhesive solution (Ashland, 9510H) was coated on a 75 μm white PET release film (Toray, XZ31 SR) under drying conditions of 110 ℃ for 2min to form a pressure-sensitive adhesive layer 3 having a dry adhesive thickness of 25 μm. The pressure sensitive adhesive was then coated onto a 150 μm aliphatic TPU surface (Argotec 49510).
(3) Coating repair coating liquid
In the second step, the other side of the aliphatic TPU substrate is coated with the repair coating liquid prepared in the first step, the curing condition is 120 ℃, the curing time is 2min, the thickness after drying is 8 microns, and finally the surface is covered with a PET protective film (Toray instruments, G01) with the thickness of 50 microns.
(4) Late stage maturation
And (4) putting the semi-finished product in the third step into a curing chamber at 50 ℃, and carrying out 72 hours to obtain the conventional automobile paint surface protective film.
The following table shows the test data of surface water contact angle (hydrophobicity), high corrosion resistance, strong scratch resistance and strong impact resistance of the samples of examples 1-3 and comparative examples 1 and 2.
| Examples of the invention | Water contact angle | High corrosion resistance | Resistance to strong scratching | High impact resistance |
| Example 1 | 154.2° | Qualified | Qualified | Qualified |
| Example 2 | 154.2° | Qualified | Qualified | Qualified |
| Example 3 | 154.2° | Qualified | Qualified | Qualified |
| Comparative example 1 | 90° | Qualified | Fail to be qualified | Fail to be qualified |
| Comparative example 2 | 89° | Qualified | Fail to be qualified | Fail to be qualified |
From the above test data, it can be known that the surface water contact angle of the protective film for automobile paint surface of the present invention has a significant increase (> 150 °) and can have outstanding hydrophobicity (super hydrophobicity).
Meanwhile, the test data also show that the surface layer of the automobile paint protective film has high corrosion resistance, strong scratch resistance and strong impact resistance.
The test method for each property in the above table is as follows:
1. surface water contact angle
Selecting a paint surface protective film, tearing off the protective film and a release film, pasting the protective film and the release film on 3mm transparent glass, and testing the water contact angle of the paint surface protective film coating by using an SDC-200S contact angle tester. 5 measurements were made for each sample and the mean values calculated were recorded.
2. High corrosion resistance
According to the salt spray test method of the national standard GB/T1771-1991, the high corrosion resistance test is carried out on the automobile paint surface protective film.
3. Resistance to strong scratch
Selecting a paint surface protective film, tearing off the protective film and a release film, wet-sticking the protective film and the release film on a black paint panel, and sliding a #0000 steel wool loaded with 500g back and forth on the surface of the paint surface protective film once to observe whether scratches are generated on the surface.
4. High impact resistance
According to the test method of the impact resistance of the plastic film and the sheet in the national standard GB/T9639.1-2008, a dart impact tester BMC-H developed by Jinan Seisai electronics technologies Co., Ltd is used for testing the impact resistance of the automobile paint surface protective film.
The present invention is not limited to the above-mentioned preferred embodiments, and any other products in various forms can be obtained by the teaching of the present invention, but any changes in the shape or structure thereof, which have the same or similar technical solutions as the present invention, fall within the protection scope of the present invention.
Claims (7)
1. The utility model provides an automobile paint surface protection film, includes TPU substrate layer and pressure sensitive adhesive layer, and pressure sensitive adhesive layer coats on one side of TPU substrate layer is surperficial, its characterized in that: and a super-hydrophobic alumina thin film layer is compounded on the other side surface of the TPU substrate layer.
2. The protective film for automobile paint surfaces according to claim 1, characterized in that: the surface of the super-hydrophobic alumina thin film layer, which is far away from the TPU base material layer, is provided with a micron-scale petal-shaped coarse structure.
3. The protective film for automotive finishes of claim 1 or 2, comprising: the thickness of the super-hydrophobic alumina thin film layer is 6-27 μm.
4. The protective film for automotive finishes of claim 1 or 2, comprising: the TPU substrate layer is an aliphatic TPU substrate layer, and the thickness of the TPU substrate layer is 100-300 mu m.
5. The protective film for automobile paint surfaces according to claim 1 or 2, characterized in that: the pressure-sensitive adhesive layer is an acrylic pressure-sensitive adhesive layer or a polyurethane pressure-sensitive adhesive layer, and the thickness of the pressure-sensitive adhesive layer is 10-50 mu m.
6. The protective film for automobile paint surfaces as claimed in claim 1 or 2, further comprising a release film layer laminated to the surface of the pressure sensitive adhesive layer.
7. The protective film for automobile paint surfaces according to claim 6, characterized in that: the release film layer is a PET release film layer, and the thickness of the release film layer is 23-100 mu m.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202221562313.2U CN217418592U (en) | 2022-06-22 | 2022-06-22 | Automobile paint protective film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202221562313.2U CN217418592U (en) | 2022-06-22 | 2022-06-22 | Automobile paint protective film |
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| Publication Number | Publication Date |
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| CN217418592U true CN217418592U (en) | 2022-09-13 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN202221562313.2U Active CN217418592U (en) | 2022-06-22 | 2022-06-22 | Automobile paint protective film |
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- 2022-06-22 CN CN202221562313.2U patent/CN217418592U/en active Active
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