阅读说明：本技术 保护膜及其使用方法 (Protective film and method of using the same ) 是由 乔恩·P·尼特费尔德 亚当·J·穆勒 摩西·M·戴维 理查德·J·波科尔尼 保罗·B·阿姆斯 于 2019-01-08 设计创作，主要内容包括：本发明公开了一种车辆传感器系统,所述车辆传感器系统包括外表面和在所述外表面上的聚合物膜。所述聚合物膜具有与所述外表面相反的第一表面,并且所述第一表面是疏水性的或亲水性的。(A vehicle sensor system includes an outer surface and a polymer film on the outer surface. The polymer film has a first surface opposite the outer surface, and the first surface is hydrophobic or hydrophilic.)

1. A vehicle sensor system comprising

An outer surface, and

a polymer film on the outer surface, wherein the polymer film has a first surface opposite the outer surface, and the first surface is hydrophobic.

2. The sensor system of claim 1, comprising a multilayer film comprising the polymeric film.

3. The sensor system of claim 2, wherein the multilayer film comprises an adhesive layer.

4. The sensor system of claim 1, wherein the sensor system comprises a camera.

5. The sensor system of claim 1, wherein the outer surface is a windshield surface.

6. The sensor system of claim 1, wherein the outer surface is a lens surface.

7. The sensor system of claim 1, wherein the hydrophobic surface has an advancing water contact angle greater than 130 °.

8. The sensor system of claim 1, wherein the hydrophobic surface has a contact angle hysteresis of less than 15 °.

9. The sensor system of claim 1, wherein the polymer film has a haze of less than 7% and a transmission of greater than 90%.

10. The sensor system of claim 1, wherein the polymer film is polyurethane.

11. A vehicle sensor system comprising

An outer surface, and

a polymer film on the outer surface, wherein the polymer film has a first surface opposite the outer surface, and the first surface is hydrophilic.

12. The sensor system of claim 11, comprising a multilayer film comprising the polymeric film.

13. The sensor system of claim 12, wherein the multilayer film comprises an adhesive layer.

14. The sensor system of claim 11, wherein the sensor system comprises a camera.

15. The sensor system of claim 11, wherein the outer surface is a windshield surface.

16. The sensor system of claim 11, wherein the outer surface is a lens surface.

17. The sensor system of claim 11, wherein the hydrophilic surface has an advancing water contact angle of less than 10 °.

18. The sensor system of claim 11, wherein the polymer film has a haze of less than 7% and a transmission of greater than 90%.

19. The sensor system of claim 11, wherein the polymer film is polyurethane.

20. A film, comprising:

a polymer layer having a hydrophobic nanostructured surface,

wherein the surface comprises a layer comprising silicon dioxide and a layer comprising fluorinated molecules, and

wherein the nanostructured surface has an advancing hexadecane contact angle greater than 80 °.

21. The film of claim 20, wherein the nanostructured surface has an advancing hexadecane contact angle greater than 100 °.

22. A sensor system comprising a sensor, an outer surface, and the film of claim 20 on the outer surface.

23. A film, comprising:

a polymer layer having a hydrophobic nanostructured surface,

wherein the surface comprises a hydrophobically modified silica-containing layer.

Technical Field

The present application relates to polymeric films for protecting surfaces, and in particular to such films for protecting surfaces (e.g., sensor surfaces) of vehicles (e.g., automobiles, aircraft, watercraft, etc.). For example, a protective film comprising polyurethane, which has a hydrophobic surface or a hydrophilic surface, is backed by a pressure sensitive adhesive. The invention also relates to a vehicle or a body part thereof protected by the film, and a process for producing the film.

Background

Vehicle sensor systems are becoming an important component of any modern automotive design, serving many different purposes. These sensor systems help automobile manufacturers to market safer, more fuel efficient, and more comfortable driving vehicle models. Over time, the sensors will also enable a greater degree of vehicle automation.

Multilayer films comprising one or more layers of polymeric material (e.g. polyurethane material) are known. Some of these films are described in, for example, U.S. patent 6,607,831; 5,405,675, respectively; 5,468,532 and 6,383,644, and International (PCT) patent application PCT/EP93/01294 (i.e., publication WO 93/245131). Some of these films have been used in surface protection applications. For example, actual film products that have been used to protect the painted surface of selected automotive body parts include multilayer films, such as those manufactured by 3M Company of saint paul, minnesota (3M Company, stl, Minnesota) PUL 0612, PUL1212 and PUL1212 DC 3M^TMHigh performance protective film. Each of these 3M company film products includes a thermoplastic polyester polyurethane layer backed by a Pressure Sensitive Adhesive (PSA) on one major surface and covered by a water-based polyester polyurethane layer on the opposite major surface. Protective and/or decorative coatings can be applied to the exposed surfaces of these films and can provide various desired product attributes including, but not limited to, chemical resistance, water resistance, solvent resistance, toughness, abrasion resistance, and durability.

Disclosure of Invention

The present application relates to multilayer protective film technology that can be used to protect, for example, vehicle sensor systems.

In a first embodiment, the present disclosure provides a vehicle sensor system comprising an exterior surface and a polymer film on the exterior surface, wherein the polymer film has a first surface opposite the exterior surface, and the first surface is hydrophobic. The polymer film may be a monolayer, or a portion of a multilayer film. The polymer film may comprise polyurethane.

The multilayer film may include an adhesive layer that may bond the polymer film to the outer surface. The adhesive layer may comprise a pressure sensitive adhesive.

The sensor system may comprise a camera, a laser or lidar, a sonar sensor or a radar sensor.

The exterior surface may be a windshield surface, a protective housing surface, or a lens surface.

The hydrophobic surface may have an advancing water contact angle of greater than 130 °, 140 °, 150 °, or 160 °.

The hydrophobic surface may have a contact angle hysteresis of less than 15 °, 10 °, or 5 °.

The polymer film may have a haze of less than 7% and a transmission of greater than 90%. Where the polymer film is part of a multilayer film, the multilayer film may have a haze of less than 7% and a transmission of greater than 90%.

In a second embodiment, the present disclosure provides a vehicle sensor system comprising an exterior surface and a polymer film on the exterior surface, wherein the polymer film has a first surface opposite the exterior surface, and the first surface is hydrophilic. The polymer film may be a monolayer, or a portion of a multilayer film. The polymer film may comprise polyurethane.

The multilayer film may include an adhesive layer that may bond the polymer film to the outer surface. The adhesive layer may comprise a pressure sensitive adhesive.

The sensor system may comprise a camera, a laser or lidar, a sonar sensor or a radar sensor.

The exterior surface may be a windshield surface, a protective housing surface, or a lens surface.

The hydrophobic surface may have an advancing water contact angle of less than 10 °,8 °, or 5 °.

The polymer film may have a haze of less than 7% and a transmission of greater than 90%. Where the polymer film is part of a multilayer film, the multilayer film may have a haze of less than 7% and a transmission of greater than 90%.

In a third embodiment, the present disclosure provides a method of protecting an exterior surface of a vehicle sensor, the method comprising applying a polymeric film to the exterior surface, wherein the polymeric film has a first surface, and the first surface is hydrophobic. The polymer film may comprise a polyurethane film.

In a fourth embodiment, the present disclosure provides a method of protecting an exterior surface of a vehicle sensor, the method comprising applying a polymeric film to the exterior surface, wherein the polymeric film has a first surface, and the first surface is hydrophilic. The polymer film may comprise a polyurethane film.

In a fifth embodiment, the present disclosure provides a film comprising a polymeric layer having a hydrophobic nanostructured surface, wherein the surface comprises a layer comprising silicon dioxide and a layer comprising fluorinated molecules, and wherein the nanostructured surface has an advancing hexadecane contact angle of greater than 80 ° or 100 °.

In a sixth embodiment, the present disclosure provides a sensor system comprising a sensor, an outer surface, and the film according to the fifth embodiment on the outer surface.

In a seventh embodiment, the present disclosure provides a membrane comprising a polymer layer having a hydrophobic nanostructured surface, wherein the surface comprises a hydrophobically modified silica-containing layer.

Detailed Description

Although the present invention has been described herein with reference to particular embodiments, it will be apparent to those skilled in the art that various modifications, rearrangements, and substitutions can be made without departing from the spirit of the invention.

As used herein, the terms "preferred" and "preferably" refer to embodiments described herein that may provide certain benefits under certain circumstances. However, other embodiments may also be preferred, under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, and is not intended to exclude other embodiments from the scope of the invention.

As used herein and in the appended claims, the singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to "a" or "the" component may include one or more components or equivalents thereof known to those skilled in the art. Additionally, the term "and/or" means one or all of the listed elements or a combination of any two or more of the listed elements.

It is noted that the term "comprises" and its derivatives, when such terms appear in the appended specification, are not to be taken in a limiting sense. Further, "a," "an," "the," "at least one," and "one or more" are used interchangeably herein.

Relative terms such as left, right, top, bottom, side, vertical, and the like, if any, may be used herein from the perspective as viewed in the particular drawing. However, these terms are only used to simplify the description, and do not limit the scope of the present invention in any way. The figures are not necessarily to scale.

Reference throughout this specification to "one embodiment," "certain embodiments," "one or more embodiments," or "an embodiment" means that a particular feature, structure, material, or characteristic described in connection with the embodiment is included in at least one embodiment of the invention. Thus, the appearances of the phrases such as "in one or more embodiments," "in certain embodiments," "in one embodiment," or "in an embodiment" in various places throughout this specification are not necessarily referring to the same embodiment of the invention. Furthermore, the particular features, structures, materials, or characteristics may be combined in any suitable manner in one or more embodiments.

Vehicle sensor system

The use of sensor technology in vehicles has increased. For example, autonomous vehicles and semi-autonomous vehicles have the potential to be used in an increasing number of applications. Such autonomous vehicles include at least one vehicle sensor system, a system configured to receive information about, for example, surrounding terrain, upcoming obstacles, particular paths, and the like. In some cases, the vehicle sensor system is configured to automatically respond to this information in lieu of the operator by commanding a series of maneuvers, enabling the vehicle to negotiate terrain, avoid obstacles, or track a particular path with little or no human intervention. Examples of various types of sensors for detecting objects in the surrounding environment may include laser or lidar (light detection and ranging), sonar, radar, cameras, and other devices that have the ability to scan and record data from the vehicle's surroundings. Such a scan would have to be initiated or received by an externally facing element. The externally facing element may be part of the scanning sensor itself, or may be an additional part of the vehicle sensor system that shields or protects the more fragile parts. Examples of such externally facing elements include the surface of the windshield (if the sensor is placed behind the windshield), the headlights (if the sensor is placed behind the headlights), the protective housing, and the camera lens.

The outwardly facing element has a surface (outer surface) that is exposed to environmental elements such as temperature, water, other weather, dirt and debris. Any of these environmental elements may interfere with the externally facing component and may impair the scanout or data entry into the vehicle sensor system.

Polymer film

A polymer film having a first surface is disclosed. In some embodiments, additional treatments and/or coatings are applied to the first surface. For the purposes of this disclosure, such additional treatments and/or coatings form part of the first surface of the polymer film. In certain embodiments, the polymer film is placed on an outer surface of the outward-facing element, and the first surface is opposite the outer surface. The polymer of the polymer film is not particularly limited, and may be at least one of thermoplastic plastics (e.g., polyester, polycarbonate, polyurethane, polyalkane (e.g., polyethylene and polypropylene), polysulfone, polyamide, polyacrylate (e.g., polymethyl methacrylate) and polyether ether ketone) and thermosetting plastics (e.g., epoxy resin, phenol resin, and polyurethane). Blends of various thermoplastics and blends of various thermosets may be used.

The polymer film may be a polyurethane film. In some embodiments, polyurethane films are preferred because they can be bent and conformable. Such layers may comprise solvent-or water-based polyurethanes, melt-processed thermoplastic polyurethanes, crosslinked thermoset polyurethanes (e.g., polyurethanes containing siloxane groups), or ultraviolet-curable polyurethanes (e.g., acrylates). In some embodiments, the polyurethane is a polyester-based polyurethane, a polycarbonate-based polyurethane, or a combination or blend of the two. The water-based polyurethane may be made from a water-based polyurethane dispersion (i.e., PUD), and the solvent-based polyurethane may be made from a solvent-based polyurethane solution (i.e., PUS). Typically, water and solvent (i.e., liquid) are removed from the polyurethane coating solution to form a polyurethane coating or film. Optionally, the polyurethane may be cured during the liquid removal step and/or after the liquid removal, thereby enhancing the properties of the polyurethane coating or film.

In certain embodiments, the polymeric membrane has a hydrophilic first surface. Due to the chemical nature of the membrane, the surface may be hydrophilic. Alternatively or in addition, a treatment on the surface or a coating on the surface may be used to render the surface hydrophilic. See, e.g., PCT publication WO 2011/084661; WO 2011/163175; WO 2013/102099; WO 2014/036448; US 2015/0166935; WO 2015/143262; WO2016/044082 and WO 2015/164468. In particular embodiments, the compositions may be as described in U.S. patent 5,888,594; 9,340,683, respectively; 9,206,335, respectively; 9,556,338 and U.S. publication 2010/0035039; 2016/0289454 and 2017/0045284, which are incorporated herein by reference in their entirety, describe diamond-like glass (DLG) coated films and DLG and zwitterionic silane coated films.

Suitable zwitterionic silanes include zwitterionic sulfonate-functional silanes, zwitterionic carboxylate-functional silanes, zwitterionic phosphate ester-functional silanes, zwitterionic phosphonic acid-functional silanes, zwitterionic phosphonate-functional silanes, or combinations thereof. In certain embodiments, the zwitterionic silane compounds used in the present disclosure have the following formula (I):

(R¹O)_p-Si(Q¹)_q-W-N⁺(R²)(R³)-(CH₂)_m-Z^t-

(I)

wherein:

each R¹Independently hydrogen, a methyl group or an ethyl group;

each Q¹Independently selected from the group consisting of a hydroxyl group, an alkyl group containing 1 to 4 carbon atoms, and an alkoxy group containing 1 to 4 carbon atoms;

each R²And R³A linear, branched, or cyclic organic group (preferably having 20 carbon atoms or less) that is independently saturated or unsaturated, which may optionally be joined together with atoms of the group W to form a ring;

w is an organic linking group;

Z^t-is-SO₃ ^-、–CO₂ ^-、–OPO₃ ^2-、–PO₃ ^2-、–OP(＝O)(R)O^-Or a combination thereof, wherein t is 1 or 2, and R is an aliphatic, aromatic, branched, linear, cyclic, or heterocyclic group (preferably R has 20 or fewer carbon atoms, more preferably R is an aliphatic group having 20 or fewer carbon atoms, and even more preferably R is methyl, ethyl, propyl, or butyl);

p and m are integers from 1 to 10 (or 1 to 4, or 1 to 3);

q is 0 or 1; and is

p+q＝3。

In certain embodiments, the organic linking group W of formula (I) may be selected from saturated or unsaturated, linear, branched, or cyclic organic groups. The linking group W is preferably an alkylene group, which may include carbonyl groups, urethane groups, urea groups, heteroatoms (such as oxygen, nitrogen, and sulfur), and combinations thereof. Examples of suitable linking groups W include alkylene groups, cycloalkylene groups, alkyl-substituted cycloalkylene groups, hydroxyl-substituted alkylene groups, hydroxyl-substituted monooxaalkylene groups, divalent hydrocarbon groups with an oxa-backbone substitution, divalent hydrocarbon groups with a mono-thia-backbone substitution, divalent hydrocarbon groups with an oxa-thia-backbone substitution, divalent hydrocarbon groups with a dioxo-thia-backbone substitution, arylene groups, arylalkylene groups, alkylarylene groups, and substituted alkylarylene groups.

Suitable examples of zwitterionic compounds of formula (I) are described in U.S. Pat. No. 5,936,703(Miyazaki et al) and International publications WO 2007/146680 and WO 2009/119690, and include the following zwitterionic functional groups (-W-N)⁺(R³)(R⁴)-(CH₂)_m-SO₃ ^-)：

Suitable examples of zwitterionic silanes are described in U.S. patent 5,936,703(Miyazaki et al), including, for example:

(CH₃O)₃Si-CH₂CH₂CH₂-N⁺(CH₃)₂-CH₂CH₂CH₂-SO₃ ^-(ii) a And

(CH₃CH₂O)₂Si(CH₃)-CH₂CH₂CH₂-N⁺(CH₃)₂-CH₂CH₂CH₂-SO₃ ^-。

other examples of suitable zwitterionic silanes that can be prepared using standard techniques as exemplified in U.S. publication 2012/0273000 (sting et al) include the following:

examples of zwitterionic carboxylate-functional silane compounds include:

wherein each R is independently OH or alkoxy, and n is an integer from 1 to 10. Examples of zwitterionic phosphate-functional silane compounds include:

(N, N-dimethyl, N- (2-phosphoethyl-ethyl) -aminopropyl-trimethoxysilane (DMPAMS)).

Examples of zwitterionic phosphonate-functional silane compounds include:

for the purposes of this application, a hydrophilic surface is defined as a surface having an advancing water contact angle of less than 15 ° (e.g., less than 10 °). In some embodiments, the advancing water contact angle is less than 8 °, for example less than 5 °.

As described herein, additional treatments and/or coatings applied to the polymeric film to render the surface otherwise hydrophilic are intended to be included in the polymeric film surface.

In certain embodiments, the polymeric film has a hydrophobic first surface. Due to the chemical nature of the film, the surface may be hydrophobic. Alternatively or in addition, the surface may be rendered hydrophobic through the use of treatments on the surface, coatings on the surface, or potentially through the incorporation (e.g., melting) of additives. For example, as described in U.S. patent 8,974,590; 8,741158, respectively; 7,396,866 and U.S. publication 2012/0107556, which are incorporated herein by reference in their entirety. Membranes can also be prepared as disclosed in U.S. patent 5,888,594, which is incorporated herein by reference in its entirety, which creates a hydrophilic surface that can be further modified to render it hydrophobic, for example with an additional coating such as a dispersion of hydrophobically modified particles.

In a specific embodiment, the surface is rendered hydrophobic as defined herein. The surface may be structured, for example, using the methods disclosed in U.S. publication 2017/0067150, which is incorporated herein by reference in its entirety. Such structured surfaces may then be additionally treated or coated as described above.

For the purposes of this application, a hydrophobic surface is defined as a surface having an advancing water contact angle greater than 125 ° and a hysteresis less than 40 °. In some embodiments, the advancing water contact angle is greater than 130 °, for example greater than 135 ° or 140 °. In specific embodiments, the advancing water contact angle is greater than 145 ° or 150 °, for example greater than 155 ° or 160 °. In some embodiments, the hysteresis is less than 20 °, such as less than 15 ° or less than 10 °, and in some embodiments less than 5 °.

As described herein, additional treatments and/or coatings applied to the polymer film to render the surface otherwise hydrophobic are intended to be included in the polymer film surface. For example, nanostructured surfaces can be fabricated using plasma treatment as described, for example, in U.S. publication 2016/0141149 a 1. As used herein, the term "nanostructure" or "nanostructured" refers to an article or surface having at least one nanoscale feature or structure having a dimension of about 10 to 500 nm. The nanostructured surfaces produced by the methods of the present disclosure may have nanostructured anisotropic surfaces. The nanostructured anisotropic surface can generally include nanoscale features having a ratio of about 2:1 or greater; preferably about 5:1 or greater. In some embodiments, the aspect ratio may even be 50:1 or greater, 100:1 or greater, or 200:1 or greater. The nanostructured anisotropic surface may have nanofeatures such as nano-pillars or nano-cylinders, or continuous nanowalls comprising nano-pillars or nano-cylinders. Typically, the nanofeatures have steep sidewalls that are substantially perpendicular to the substrate.

In some embodiments, a majority of the nanofeatures may be covered by a mask material. The concentration of the mask material on the surface may be from about 5 wt% to about 90 wt% or from about 10 wt% to about 75 wt%.

In some embodiments, the film is coated with DLG as described above.

In addition to this, fluorinated organosilane compounds may be utilized. Fluorinated organosilane compounds suitable for use in the present invention are described in detail in U.S. publication 2013/0229378Al and include those monodentate (monodentate) fluorinated organosilane compounds comprising: (a) a monovalent segment selected from the group consisting of polyfluoroalkyl, polyfluoroether, polyfluoropolyether, and combinations thereof (preferably, polyfluoropolyether) and (b) a monovalent end group comprising at least one silyl moiety (preferably, 1 to about 20; more preferably, 1 to about 5; most preferably, 1 or 2) comprising at least one group selected from the group consisting of hydrolyzable groups, hydroxyl, and combinations thereof.

Suitable fluorinated organosilane compounds also include those polypentafluorinated organosilane compounds comprising (a) a multivalent (preferably, divalent) segment selected from polyfluoroalkanes (preferably, polyfluoroalkylenes), polyfluoroethers, polyfluoropolyethers, and combinations thereof (preferably, polyfluoropolyethers) and (b) at least two monovalent end groups, each monovalent end group independently comprising at least one silyl moiety (preferably, 1 to about 20; more preferably, 1 to about 5; most preferably, 1 or 2) comprising at least one group selected from hydrolyzable groups, hydroxyl groups, and combinations thereof.

The monodentate fluorinated organosilane compound and the multidentate fluorinated organosilane compound may be used in combination. When the monovalent and/or polyvalent segment of a compound is fluorinated rather than perfluorinated, it is preferred that no more than one atom of hydrogen be present per two carbon atoms in the segment.

The monovalent and/or polyvalent segments of the fluorinated organosilane compound are preferably perfluorinated. Preferably, the monovalent segment of the monodentate compound comprises a perfluoroalkyl group, a perfluoroether, a perfluoropolyether, or a combination thereof (more preferably, a perfluoroalkyl group, a perfluoropolyether, or a combination thereof; most preferably, a perfluoropolyether), and/or the polyvalent segment of the multidentate compound comprises a perfluoroalkane, a perfluoroether, a perfluoropolyether, or a combination thereof (more preferably, a perfluoroalkane, a perfluoropolyether, or a combination thereof; most preferably, a perfluoropolyether).

In some embodiments, compounds having the formula R' f [ Q- (C (R))₂-Si(Y)_3-x(R^1a)_x]_y]_zWherein R' f is perfluoroalkyl and Q ═ CH₂,R＝H,Y＝N(CH₃)₂，R^1aMethyl, x-2, y-1, and z-1.

In a most preferred embodiment, compounds having the formula R' f [ Q- (C (R))₂-Si(Y)_3-x(R^1a)_x]_y]_zWherein R' F is a silane of the formula F (CF)₃)CF₂O)_aCF(CF₃) Perfluoroethers of (a) whereinAverage value of 4 to 120, Q ═ CONHCH₂CH₂，R＝H，Y＝OCH₃，R^1a-methyl, -x-0, -y-1, and-z-1.

In some embodiments, compounds having the formula R' f [ Q- (C (R))₂-Si(Y)_3-x(R^1a)_x]_y]_zWherein R' f is a silane having the formula- (CF)₃)CF₂O)_aCF(CF₃) Perfluoro ethers of (a) wherein a has an average value of 4 to 120, Q ═ CH₂OCH₂CH₂，R＝H，Y＝OCH₃，R^1aMethyl, x-0, y-1, and z-1.

Advancing water contact angle

The advancing water contact angle was measured using a Ramse-Hart goniometer (Ramse-Hart Instrument Co., Succasunna, N.J.). The advance angle (θ) was measured as fluid was provided via a syringe to form a sessile drop (drop volume about 5 μ L) or as a sessile drop break-up_adv) And receding angle (theta)_rec). Measurements were taken at three different points on the surface of each film sample and the reported measurements were the average of the six values for each sample (left and right measurements for each droplet). The probe fluid used in this test was deionized water. The contact angle hysteresis (θ) was determined using the following equation_hys)：θ_hys＝θ_adv-θ_rec。

Haze degree

In some embodiments, the polymer films of the present disclosure may have high transmission and low haze with respect to one or more specific wavelengths of electromagnetic radiation, such as visible radiation (visible light), infrared radiation, ultraviolet radiation, acoustic waves, and radio waves. In some embodiments, the polymeric film may have a transmittance of greater than 80%, greater than 85%, greater than 90%, greater than 95%, or even greater than 97% for one or more wavelengths of radiation. In some embodiments, the polymer film may have a transmittance relative to visible light of greater than 80%, greater than 85%, greater than 90%, greater than 95%, or even greater than 97%. In some embodiments, it is beneficial to maintain the polymer film with a haze measurement of less than 10%, less than 7%, less than 5%, or even less than 3% relative to one or more specific wavelengths of electromagnetic radiation. In some embodiments, the polymer film may have a haze relative to visible light of less than 10%, less than 7%, less than 5%, or even less than 3%. This is particularly useful in embodiments where the polymeric membrane has a hydrophobic or hydrophilic surface, as defined herein.

The measurement may be determined by using BYK Haze-Gard Plus (BYK Gardner USA, Columbia, Maryland) in Columbia, Md. Measurements should be taken at three different points on each film sample and averaged.

Multilayer film

According to the present invention, a polymer film may be incorporated into a multilayer film. In one embodiment, a multilayer film includes a polymer film and an adhesive layer. The adhesive layer may be a pressure sensitive adhesive or a hot melt adhesive. In such an embodiment, the adhesive layer may bond the polymer film to the outer surface, as described herein. In some embodiments, the adhesive layers of the present disclosure can have high transmission and low haze with respect to one or more specific wavelengths of electromagnetic radiation, such as visible radiation (visible light), infrared radiation, ultraviolet radiation, acoustic waves, and radio waves. In some embodiments, the adhesive layer may have a transmittance of greater than 80%, greater than 85%, greater than 90%, greater than 95%, or even greater than 97% for one or more wavelengths of radiation. In some embodiments, the adhesive layer may have a transmittance with respect to visible light of greater than 80%, greater than 85%, greater than 90%, greater than 95%, or even greater than 97%. In some embodiments, it is beneficial to maintain the adhesive layer with a haze measurement of less than 10%, less than 7%, less than 5%, or even less than 3% relative to one or more specific wavelengths of electromagnetic radiation. In some embodiments, the haze of the adhesive layer relative to visible light may be less than 10%, less than 7%, less than 5%, or even less than 3%. The polymer film may be a multilayer structure with an additional polymer layer between the polymer film and the adhesive layer. Such structures can be found, for example, in U.S. publication 2017/0107398a1, which is incorporated by reference herein in its entirety.

Method for producing polymer film

The polymer films of the present application can be prepared using known techniques. Examples of making polymeric films include, for example, melt extrusion, melt blowing, or reacting/crosslinking monomer species. Methods of film manufacture are fully disclosed in, for example, U.S. patent 8,765,263 and U.S. publication 2017/0107398, which are incorporated herein by reference in their entirety.

Method for depositing fluorine-containing compounds

The fluorinated organosilane may be deposited using known coating methods such as dip coating. In some embodiments, the fluorinated composition is vapor deposited.

If vapor deposition is used, the conditions under which the fluorinated composition can be vaporized during chemical vapor deposition may vary depending on the structure and molecular weight of the fluorinated organosilane. For certain embodiments, vaporization may occur at a pressure of less than about 1.3Pa (about 0.01 Torr), at a pressure of less than about 0.013Pa (about 10-4 Torr), or even at a pressure of from about 0.0013Pa to about 0.00013Pa (about 10-s Torr to about 10-6 Torr). For certain of these embodiments, the vaporizing may occur at a temperature of at least about 80 ℃, at least about 100 ℃, at least about 200 ℃, or at least about 300 ℃. Vaporization may include applying energy by, for example, conduction heating, convection heating, and/or microwave radiation heating.

Polymer protective film and method of using the same

The polymeric films described herein may be added to a surface to be protected, such as an exterior surface of a vehicle sensor system. Polymer films with hydrophobic surfaces can be used as protective films for vehicle sensors, for example, because rain and salt water are condensed from the surface. In some embodiments, the hydrophobic protective film includes a hardcoat layer for imparting durability. For example, in some embodiments, the hydrophobic protective film comprises a polymeric substrate, optional nanostructures, a hardcoat layer, and a nanostructured hydrophobic surface (e.g., plasma treated or HFPO).

In some embodiments, the polymer film is coated with a hydrophobically modified silica-containing layer. Examples of hydrophobically modified silica-containing layers include Armor All wheel protectant part number 78482 available from Armorall/STP Products Company (The Armorall/STP Products Company, Oakland, California) of Oakland, California, and Armor All wheel protectant from winning corporation (Evonik)A solution of R812 (e.g., a 0.5% solution in an alcohol solvent or a silica-based solvent). In some embodiments, the polymer film is a polyurethane. In some embodiments, the polymeric film is a multilayer film, more particularly, a multilayer film comprising an adhesive on a side of the polymeric film opposite the side comprising the coating.

Polymer films with hydrophilic surfaces can also be used as protective films for vehicle sensors, for example, because they prevent fogging. In some embodiments, the hydrophilic protective film includes a hard coat layer for imparting durability. In some embodiments, the hydrophilic protective film is coated with DLG and a hydrophilic coating to provide washability and anti-fog properties. For example, in some embodiments, a hydrophilic protective film includes a polymeric substrate, optional nanostructures, a hardcoat layer, a DLG layer, and a hydrophilic coating (e.g., a zwitterionic silane).

The polymeric films described herein can be added to the surface to be protected using methods known in the art. For example, a premask may be used to assist in the application process. Specifically, a polymeric film is applied to a substrate (e.g., the exterior surface of a vehicle sensor system) using a layer of premask material that includes a polymeric cover sheet or polymeric cover layer and a removable pressure sensitive adhesive layer that is securely adhered to one surface of the cover sheet along with the layer of premask material, wherein the premask is removed after placement. In addition, the film may be die cut to match the desired surface to be protected.