TWI477541B - Automotive glass film and car - Google Patents

Description

Automotive glass film and car

The invention relates to a glass film, in particular to a glass film applied to an automobile and an automobile.

In the prior art, a glass film was attached to the surface of the glass to create a sense of beauty, to improve riot resistance, and to resist ultraviolet rays. Specifically, glass films are often applied to windows and doors of buildings, as well as window glass of automobiles. For cars, the glass film can improve the safety level of the car in the event of an accident, so that the possibility of car glass breakage is minimized, so as to minimize the damage to the driver and passengers caused by accidents.

However, in the prior art, the automotive glass film is required to have a high-strength safety base layer, an ultraviolet absorbing layer, and a polymer protective layer in order to achieve anti-riot and anti-UV effects. The high-strength safety substrate is usually a high-strength polymer film, and the ultraviolet absorbing layer is usually an ultraviolet absorber. However, the strength of the high-strength polymer film in the prior art is still not high enough, and the ultraviolet absorbing layer needs to form the ultraviolet absorbing agent on the surface of the polymer film through a complicated process, thereby making the process complicated.

In view of this, it is necessary to provide an automotive glass film with strong anti-storm performance and simple preparation process.

An automotive glass film comprising: a polymer film substrate; at least one layer of nano carbon The tube film is composited on the polymer film substrate; a polymer protective layer is disposed on the surface of the polymer film substrate. The carbon nanotube membrane is composed of a plurality of carbon nanotubes, and the plurality of carbon nanotubes are arranged in a preferred orientation in one direction by van der Waals force.

An automotive glass film comprising: a polymer film substrate; at least one composite carbon nanotube film composited in the polymer film substrate, the composite carbon nanotube film is composed of a plurality of carbon nanotubes, The plurality of carbon nanotubes are arranged in a preferred orientation by a van der Waals force, and each of the carbon nanotubes is coated with a metal layer; and a polymer protective layer is disposed on the surface of the polymer film substrate.

Compared with the prior art, the automotive glass film comprises at least one layer of carbon nanotube film disposed on the polymer film substrate, and the carbon nanotube film is composed of a plurality of carbon nanotubes. Since the carbon nanotubes have a very high hardness (comparable to diamond) and the carbon nanotubes have an extremely large aspect ratio (greater than 1000:1), the plurality of carbon nanotubes are connected end to end by Van der Waals force. The orientation of the preferred orientation is such that the polymer film substrate composited with the carbon nanotube film has high hardness and good flexibility. The automotive glass film using the carbon nanotube film has high strength and toughness, and since the carbon nanotube film also has good light transmittance, when the automobile glass film is attached to the automobile window Under the premise of maintaining sufficient transparency, the anti-riot performance of the car window can be improved, thereby improving the safety performance of the car. In addition, the carbon nanotube film has a good absorption effect on ultraviolet light. Therefore, the automobile glass film using the polymer film substrate composited with the carbon nanotube film described above does not require an additional ultraviolet absorption layer, and can simultaneously have Strong strength and good UV absorption.

10,20,30‧‧‧Auto glass film

15‧‧‧ polymer protective layer

16‧‧‧Nano carbon nanotube film

18‧‧‧ polymer film substrate

40‧‧‧Car

36‧‧‧Composite carbon nanotube film

1 is a schematic structural view of an automotive glass film provided by a first embodiment of the present invention.

Figure 2 is a cross-sectional view taken along line II-II of Figure 1.

3 is a scanning electron micrograph of a carbon nanotube film including carbon nanotubes arranged in a preferred orientation in the same direction according to an embodiment of the present invention.

4 is a scanning electron micrograph of a plurality of layers of carbon nanotube films including overlapping crossovers in an automotive glass film according to an embodiment of the present invention.

FIG. 5 is a schematic structural view of an automotive glass film including a plurality of layers of carbon nanotube film according to a second embodiment of the present invention.

FIG. 6 is a schematic structural view of an automotive glass film including at least one layer of a composite carbon nanotube film according to a third embodiment of the present invention.

Fig. 7 is a graph showing the relationship between the light transmittance of the composite carbon nanotube film of Fig. 6 and the wavelength of light.

FIG. 8 is a schematic structural view of an automobile glass film applied to an automobile according to an embodiment of the present invention.

The automotive glass film of the present invention will be described in detail below with reference to the accompanying drawings.

Referring to FIG. 1 and FIG. 2 , an embodiment of the present invention provides an automotive glass film 10 comprising a polymer film substrate 18 , at least one layer of carbon nanotube film 16 and a polymer protective layer 15 . The at least one layer of the carbon nanotube film 16 is embedded in the polymer film substrate 18 in the thickness direction and is compounded with the polymer film substrate 18. The polymer protective layer 15 covers the surface of the carbon nanotube film 16 exposed to the outside of the polymer film substrate 18. When the carbon nanotube film 16 is entirely immersed in the polymer film substrate 18, the polymer protective layer 15 covers the polymer film substrate. The surface of the bottom 18. When the at least one carbon nanotube film 16 is disposed near the surface of the polymer film substrate 18, the polymer protective layer 15 is disposed on the surface of the polymer film substrate 18 adjacent to the carbon nanotube film 16. In use, the automotive glass film 10 can be directly adhered to the glass surface, and the polymer protective layer 15 is exposed to the air, thereby protecting the composite carbon nanotube film 16 in the automotive glass film 10. The polymer film substrate 18 is separated from the outside.

The polymer film substrate 18 is not limited in shape and has flexibility. The polymer film substrate 18 can be bent and bent into any shape according to the shape and area of the glass surface to be attached when needed, and has a thickness of 0.1 mm. To 1 mm. The material of the polymer film substrate 18 is a transparent polymer material, which can be polystyrene, polyethylene, polycarbonate, polymethyl methacrylate (PMMA), polycarbonate (PC), and terephthalic acid. Polyester (PET), phenylcyclobutene (BCB) or polycycloolefin. In this embodiment, the polymer film substrate 18 is polyethylene terephthalate (PET) having a thickness of 0.5 mm.

Referring to FIG. 3, the carbon nanotube film 16 is a self-supporting structure composed of a plurality of carbon nanotubes. The plurality of carbon nanotubes are arranged in a preferred orientation along the same direction. The preferred orientation means that the overall direction of extension of most of the carbon nanotubes in the carbon nanotube membrane 16 is substantially in the same direction. Moreover, the overall direction of extension of the majority of the carbon nanotubes is substantially parallel to the surface of the carbon nanotube film 16. Further, most of the carbon nanotubes in the carbon nanotube film 16 are connected end to end by Van der Waals force. Specifically, each of the majority of the carbon nanotubes extending substantially in the same direction in the carbon nanotube film 16 and the carbon nanotubes adjacent in the extending direction are connected end to end by Van der Waals force . Of course, there are a small number of randomly arranged carbon nanotubes in the carbon nanotube film 16, and these carbon nanotubes do not constitute an obvious alignment of the majority of the carbon nanotubes in the carbon nanotube film 16. influences. The self-supporting carbon nanotube film 16 does not require a large-area carrier support, but can maintain its own membranous state by simply providing a supporting force on both sides, that is, placing the carbon nanotube film 16 (or When fixed to the two support bodies provided at a distance apart, the carbon nanotube film 16 located between the two supports can be suspended to maintain the self-film state. The self-supporting is mainly achieved by the presence of a continuous carbon nanotube in the carbon nanotube film 16 which is continuously arranged by van der Waals force. Since the carbon nanotube film 16 is a self-supporting structure, the carbon nanotubes in the carbon nanotube film 16 are connected to each other to form a unitary body, and the carbon nanotube film 16 is formed into a unitary body. The polymer film substrate 18 is formed with a self-supporting integral structure with the polymer film substrate 18, thereby further improving the strength of the polymer film substrate 18.

In addition, there is a gap between the adjacent carbon nanotubes of the carbon nanotube film 16, so that the carbon nanotube film 16 has light transmissivity, and the transmittance of the carbon nanotube film 16 is 60% to 95. Between %, it is understood that as the thickness of the carbon nanotube film 16 increases, its light transmittance also decreases. Due to the gap between the carbon nanotubes in the carbon nanotube film 16, the material of the polymer film substrate 18 will penetrate into the gap, so that the carbon nanotube film 16 is closely packed with the polymer film substrate 18. The composite is composited to increase the strength of the polymer film substrate 18, thereby improving the anti-riot performance of the automotive glass film 10.

Specifically, most of the carbon nanotube membranes 16 that extend substantially in the same direction are not absolutely linear and may be appropriately bent; or are not completely aligned in the extending direction, and may be appropriately deviated from the extending direction. . Therefore, it is not possible to exclude partial contact between the carbon nanotubes juxtaposed in the majority of the carbon nanotubes of the carbon nanotube film 16 extending substantially in the same direction.

The carbon nanotubes in the carbon nanotube film 16 are single-walled carbon nanotubes and double-walled carbon nanotubes. One or more of the multi-walled carbon nanotubes. The single-walled carbon nanotube has a diameter of 0.5 nm to 10 nm, the double-walled carbon nanotube has a diameter of 1 nm to 15 nm, and the multi-walled carbon nanotube has a diameter of 1.5 nm to 50 nm. Nano. The length of the carbon nanotubes is greater than 50 microns. The length of the carbon nanotubes is greater than 50 microns, and preferably, the length of the carbon nanotubes is from 200 to 900 microns.

It can be understood that the strength of the automotive glass film 10 is enhanced as the number of layers of the carbon nanotube film 16 disposed on the polymer film substrate 18 is increased. When the automotive glass film 10 includes a plurality of layers of carbon nanotube film 16, the plurality of layers of carbon nanotube film 16 may be overlapped and disposed, and the carbon nanotubes in the adjacent two layers of carbon nanotube film structure are The alignment direction forms an angle α, wherein α is greater than or equal to zero degrees and less than or equal to 90 degrees (0≦α≦90°). Referring to FIG. 4, in the embodiment of the present invention, the automobile glass film 10 adopts four layers of overlapping cross-carbon nanotube film 16. The orientation of the preferential orientation of the carbon nanotubes in each of the two adjacent carbon nanotube membranes 16 forms an angle of 90 degrees, and the carbon nanotubes in the four layers of overlapping carbon nanotube membranes 16 are present between the carbon nanotubes. A lot of gaps. Therefore, when the four layers of the overlapping carbon nanotube film 16 are disposed in the polymer film substrate 18, the material of the polymer film substrate 18 will penetrate into the gap between the carbon nanotubes, thereby The carbon nanotube film 16 can be uniformly compounded with the polymer film substrate 18. Further, the automotive glass film 10 has a high strength.

The carbon nanotube film 16 has a thickness of from 0.5 nm to 100 μm. In the present embodiment, the carbon nanotube film 16 has a thickness of 100 μm. The carbon nanotube film 16 is placed in the polymer film substrate 18 in the thickness direction by the viscosity of the carbon nanotube film 16 itself, since the carbon nanotubes in the carbon nanotube film 16 have a large length. Ratio (greater than 1000:1) and higher strength, and the overall extension direction of the majority of the carbon nanotubes is substantially parallel to the surface of the carbon nanotube film 16, so that the carbon nanotube film 16 and the polymer film Base 18 has high strength after compounding, and when the automobile glass film 10 having the composite structure of the carbon nanotube film 16 and the polymer film substrate 18 is applied to the windshield of an automobile, if the automobile windshield is subjected to an external force impact The windshield does not break into small pieces but keeps the overall structure cracked, so the safety of the occupant can be well protected. In addition, the carbon nanotubes in the carbon nanotube film 16 have a high absorption rate for ultraviolet light. Therefore, the automobile glass film 10 using the carbon nanotube film 16 also has a good ultraviolet light absorbing effect, and the automobile glass film 10 can also effectively block ultraviolet rays, thereby protecting the occupant's skin from being damaged by sunlight.

The material of the polymer protective layer 15 is a transparent polymer material, which may be one or a plurality of thermoplastic polymers or thermosetting polymers, such as cellulose, polyethylene terephthalate, acrylic resin, polyethylene. One or more of polypropylene, polystyrene, polyvinyl chloride, phenolic resin, epoxy resin, silicone rubber and polyester. In this embodiment, the material of the polymer protective layer 15 is an epoxy resin having a thickness of 200 μm. When in use, the automotive glass film 10 can be directly adhered to the glass surface, and the polymer protective layer 15 is exposed to the air, so that the polymer film substrate 18 in the automotive glass film 10 can be protected from the outside.

The carbon nanotube film 16 and the polymer film substrate 18 can be realized by a method: first, providing at least one carbon nanotube film and a prepolymerized polymer solution; and second, the carbon nanotube base The film is placed at the bottom of a container, and the prepolymerized polymer solution is poured into the container containing at least one carbon nanotube film; in the third step, the prepolymerized polymer solution is polymerized and reacted with the carbon nanotube The base film is composited to form a structure in which a carbon nanotube film 16 is laminated to the polymer film substrate 18.

The carbon nanotube film 16 and the polymer film substrate 18 can be realized by a method: first, a polymer film is provided, and at least one carbon nanotube film 16 is disposed in the The surface of the polymer film. Next, a polymer film is provided, and the polymer film covers the at least one carbon nanotube film 16. Finally, the at least one carbon nanotube film 16 is compounded with the two polymer films by hot pressing to form a polymer film substrate compounded with at least one carbon nanotube film 16. 18.

Referring to FIG. 5, a second embodiment of the present invention provides an automotive glass film 20 comprising a polymer film substrate 18 and a plurality of carbon nanotube films composited in the polymer film substrate 18. The difference from the first embodiment is that the plurality of carbon nanotube films 16 are disposed in parallel with each other in the polymer film substrate 18.

The material of the polymer film substrate 18 penetrates into the micropores of the carbon nanotube film 16, so that the carbon nanotube film 16 and the two polymer film substrates 18 are well combined, due to the plurality of layers The carbon nanotube film 16 is disposed in parallel in the polymer film substrate 18 such that the plurality of layers of the carbon nanotube film 16 are more evenly distributed in the polymer film substrate 18, so that the polymer film substrate 18 and the plurality The layer of carbon nanotube film 16 is better bonded together, thereby greatly increasing the strength of the polymer film substrate 18. In addition, the plurality of layers of the carbon nanotube film 16 can also absorb ultraviolet light in a plurality of times, so that the automotive glass film 20 of the present invention has a better ultraviolet absorption effect.

In the automotive glass film 20 of the present embodiment, the composite of the polymer film substrate 18 and the plurality of layers of the carbon nanotube film 16 can be realized by the following method: in the first step, a carbon nanotube film 16 and a pre-preparation are provided. Polymerized polymer solution; in the second step, the carbon nanotube film 16 is placed on the bottom of a container, and the prepolymerized polymer solution is poured into the container containing the carbon nanotube film 16; The prepolymerized polymer solution is polymerized and combined with the carbon nanotube film 16 to form a first layer of carbon nanotube/polymer composite; and the fourth step, the first layer of carbon nanotubes formed above/ Polymer composite Another layer of the carbon nanotube film 16 is placed on the surface of the polymer layer of the material, and a certain amount of the prepolymerized polymer solution is poured to polymerize the prepolymerized polymer solution, and the another layer of the carbon nanotube film 16 is laminated. And the surface of the polymer layer of the first layer of carbon nanotube/polymer composite is composited to form a second layer of carbon nanotube/polymer composite; in the fifth step, the fourth step is repeated on the basis of the fourth step. A polymer film substrate 18 in which a plurality of layers of carbon nanotube film 16 are uniformly distributed is obtained.

Referring to FIG. 6, a third embodiment of the present invention provides an automotive glass film 30 having a structure similar to that of the automotive glass film 10, 20 of the first embodiment or the second embodiment. The difference is that the composite carbon nanotube film 36 having a surface coated with nano metal particles is compounded in the polymer film substrate 18. The composite carbon nanotube film 36 is formed by depositing a metal layer on the carbon nanotube film 16 in the first embodiment or the second embodiment, and the metal layer is wrapped in the carbon nanotube film 16. The surface of each carbon nanotube. The metal layer may be formed by physical vapor deposition (PVD), such as vacuum evaporation or ion sputtering or electroplating. The metal coated material is gold, silver, copper, nickel, palladium or titanium. The thickness is 1~20 nm. In this embodiment, the metal coating is gold and has a thickness of 10 nm.

Referring to FIG. 7, a relationship between the transmittance of the composite carbon nanotube film 36 and the wavelength of light in the automotive glass film 30 of the third embodiment of the present invention. It can be seen from the curve that the metal-coated composite carbon nanotube film 36 has low transmittance in the ultraviolet band and the infrared and far-infrared bands at the same time, so the composite carbon nanotube film 36 has both ultraviolet light absorption and reflection. The effect of infrared light. Further, the composite carbon nanotube film 36 has a high transmittance in the visible light band. Therefore, the automotive glass film 30 using the composite carbon nanotube film can simultaneously absorb ultraviolet light and reflect infrared light, and can also transmit visible light. It can protect the infrared light emitted by the inside of the car and be reflected back into the car, so that the insider is not At the same time as the infrared detection device outside the car detects the effect. In addition, the automotive glass film 30 can also reflect infrared light in the natural environment outside the vehicle, and has the effect of a heat insulating film. Therefore, the automotive glass film 30 of the third embodiment of the present invention has both ultraviolet light prevention and heat insulation, and prevents the inside of the vehicle from being detected by the infrared detecting device outside the vehicle.

It can be understood that the composite method of the composite carbon nanotube film 36 and the polymer film substrate 18 in the automotive glass film 30 of the third embodiment is the same as that described in the first embodiment and the second embodiment.

Referring to FIG. 8 together, when the automobile glass film 10 of the embodiment of the present invention is used, the automobile glass film 10 can be first cut into the shape of the glass to be coated, and then the automotive glass film 10 is adhered through a bonding agent. On the window glass, the polymer film substrate 18 composited with the carbon nanotube film 16 is disposed between the automobile glass and the polymer protective layer 15, and exposes the polymer protective layer 15 to the air to avoid External force scratches damage the car glass film 10.

It can be understood that the automobile film provided by all the embodiments of the present invention can be applied to the automobile glass of FIG. 7, and FIG. 8 only takes the automotive glass film 10 of the first embodiment as an example.

It can be understood that the automotive glass film provided by the present invention is not limited to application on an automobile windshield, but can also be applied to architectural glass, as well as other glass to be protected.

Compared with the prior art, the automotive glass film comprises at least one carbon nanotube film disposed in a polymer film substrate, the carbon nanotube film being composed of a plurality of carbon nanotubes, the plurality of nano tubes The end-to-end connection of the carbon tubes is arranged in a preferred orientation in one direction, and the carbon nanotube membrane is described as the carbon nanotubes have an extremely large aspect ratio. After the polymer film substrate is composited, the strength of the polymer film substrate is greatly enhanced, thereby enhancing the strength of the automotive glass film. In addition, the carbon nanotube film has a good absorption effect on ultraviolet light. Therefore, the automobile glass film using the polymer film substrate composited with the carbon nanotube film has strong strength and has a relatively high strength. Good UV absorption to protect the occupant's skin from the sun. In addition, in the invention, the automobile glass composited with the composite carbon nanotube film containing the metal layer can also reflect the infrared light, can better protect the privacy of the inside of the vehicle, and can be used for the automobile film of the anti-smashing car window glass to prevent Infrared night vision glances through the car glass to the occupants inside the car.

Compared with the prior art, the automotive glass film comprises at least one carbon nanotube film disposed in a polymer film substrate, the carbon nanotube film being composed of a plurality of carbon nanotubes, the plurality of nano tubes The carbon nanotubes are arranged in an optimal orientation in one direction. Since the carbon nanotubes have an extremely large aspect ratio, the carbon nanotube film is composited with the polymer film substrate to greatly enhance the polymer film substrate. The strength, which in turn enhances the strength of the automotive glass film. In addition, the carbon nanotube film has a good absorption effect on ultraviolet light. Therefore, the automobile glass film using the polymer film substrate composited with the carbon nanotube film has strong strength and has a relatively high strength. Good UV absorption to protect the occupant's skin from the sun. In addition, in the invention, the automobile glass composited with the composite carbon nanotube film containing the metal layer can also absorb infrared light, can better protect the privacy of the inside of the vehicle, and can also be used for the automobile film of the bulletproof car window glass. Prevent infrared night vision devices from peeping into the car through the car glass.

In summary, the present invention has indeed met the requirements of the invention patent, and has filed a patent application according to law. However, the above is only a preferred embodiment of the present invention, and cannot be limited by this. The scope of the patent application in this case. Equivalent modifications or variations made by those skilled in the art in light of the spirit of the invention are intended to be included within the scope of the following claims.

10‧‧‧Auto glass film

15‧‧‧ polymer protective layer

16‧‧‧Nano carbon nanotube film

18‧‧‧ polymer film substrate

Claims (14)

An automotive glass film comprising: a polymer film substrate, the material of which is polystyrene, polyethylene, polycarbonate, polymethyl methacrylate, polycarbonate, and ethylene terephthalate An ester, a benzocyclobutene or a polycycloolefin; at least one layer of a carbon nanotube film compounded in the polymer film substrate, the carbon nanotube film being composed of a plurality of carbon nanotubes, the plurality of The carbon nanotubes are aligned in one direction by the van der Waals force; and a polymer protective layer is disposed on the surface of the polymer film substrate, the polymer protective layer being one of a thermoplastic polymer or a thermosetting polymer Multiple species. The automotive glass film of claim 1, wherein the majority of the carbon nanotubes in the carbon nanotube film extend in the same direction and parallel to the surface of the carbon nanotube film. The automotive glass film according to claim 2, wherein the carbon nanotube film is a self-supporting structure, and the carbon nanotube film is composited to the polymer film substrate in a unitary form. The automotive glass film according to claim 2, wherein each of the plurality of carbon nanotubes extending in the same direction in the carbon nanotube film is adjacent to each other in the extending direction The carbon nanotubes are connected end to end by Van der Valli. The automotive glass film according to claim 3, wherein a gap exists between adjacent carbon nanotubes in the carbon nanotube film. The automotive glass film according to claim 4, wherein a material of the polymer film substrate penetrates into the gap. The automotive glass film according to claim 1, wherein the automotive glass film comprises a plurality of laminated carbon nanotube films laminated in the polymer film substrate. The automotive glass film according to claim 6, wherein the automotive glass film comprises a plurality of layers of carbon nanotube films arranged in parallel spaced apart in the polymer film substrate. The automotive glass film according to claim 1, wherein the polymer film substrate is made of polystyrene, polyethylene, polycarbonate, polymethyl methacrylate, polycarbonate, and ethylene terephthalate. Alcohol ester, phenylcyclobutene or polycycloolefin. The automotive glass film according to claim 1, wherein the carbon nanotube film has a thickness of from 0.5 nm to 100 μm. An automotive glass film comprising: a polymer film substrate, the material of which is polystyrene, polyethylene, polycarbonate, polymethyl methacrylate, polycarbonate, and ethylene terephthalate An ester, a benzocyclobutene or a polycycloolefin; at least one composite carbon nanotube film composited in the polymer film substrate, the composite carbon nanotube film being composed of a plurality of carbon nanotubes, a plurality of carbon nanotubes are arranged in an orientation by van der Waals force, and a surface of each of the carbon nanotubes is coated with a metal layer; and a polymer protective layer is disposed on the surface of the polymer film substrate, The polymer protective layer is one or a plurality of thermoplastic polymers or thermosetting polymers. An automobile using an automotive glass film according to any one of claims 1 to 11, the automobile comprising a vehicle body and a windshield, wherein the automotive glass film is disposed on a surface of an automobile glass by a bonding agent, wherein the composite has The polymer film substrate of the carbon nanotube film is disposed between the automobile glass and the polymer protective layer. The automotive glass film according to claim 1 or 11, wherein the polymer protective layer is cellulose, polyethylene terephthalate, acrylic resin, polyethylene, polypropylene, polystyrene, poly One or more of vinyl chloride, phenolic resin, epoxy resin, silicone rubber and polyester. The automotive glass film according to claim 11, wherein the metal coating material is gold, silver, copper, nickel, palladium or titanium, and has a thickness of 1 to 20 nm.