Patent Grant
11851576
The present invention in general relates to a hydrophobic coating composition for wiper blades imparting a hydrophobic film to a contacted window glass through wiper usage, and in particular to a hydrophobic coating composition that resists absorption into the wiper blade insert surface.
Rain, sleet, and snow have always presented a vision problem for the operator of a vehicle. While mechanical movement of a wiper blade insert across a windshield is partly effective as a mechanical squeegee to displace water and snow from a windshield, the operation of a conventional wiper blade, regardless of whether made of organic elastomers or silicone rubbers, is only partially effective in clearing water and snow from a windshield. A wiper blade insert moving across a windshield leaves a thin film of water that partly impairs vision and promotes adhesion of additional liquid water or snow to the windshield. Additionally, as a wiper blade insert undergoes degradation through exposure to the environment, the uniformity of wiper blade insert contact with the windshield is degraded. These problems are compounded by debris that commonly adhere to the windshield and create regions in which the wiper blade insert is gapped from the windshield surface leading to vision obscuring streaks and water droplets.
To address limitations of windshield cleaning through mechanical squeegee action, hydrophobic glass treatment solutions have been applied to vehicle windshields to improve driver vision under high humidity conditions of rain, sleet, or snow. Representative of such glass treatments are those detailed in U.S. Pat. Nos. 3,579,540, 5,688,864, 6,432,181. While such glass treatments are effective in rendering the windshield hydrophobic so as to cause water to bead and not form windshield water film, these products have met with limited acceptance owing to the labor-intensive application, and somewhat toxic chemicals needed to be handled to create a hydrophobic windshield surface. Additionally, the application of such hydrophobic glass treatments while a windshield is being subjected to rain or other precipitation is impractical.
In recognition of the limitations of conventional hydrophobic glass treatments, coating compositions have been developed for a wiper blade insert that include a silicone wax, a silicone oil in a solid lubricant where the wax dissolves in the silicone oil, such that during operation of the wiper blade components of the coating layer are imparted onto a contacting windshield through the friction of the wiper blade insert against the windshield. Such a composition is detailed in U.S. Pat. No. 8,258,219. While such a coated wiper blade insert is effective in delivering a hydrophobic coating to a windshield upon wiper blade insert installation, the ability of the coating to be transferred to the windshield is rapidly degraded to the point where the ability to transfer coating components to a windshield is reduced in the time between wiper production and the actual installation of the blade on a vehicle. Additionally, the coatings imparted to a windshield tend to be irregular and impart a mottled hydrophobicity to the windshield surface.
U.S. Pat. No. 9,540,552 to the assignee of this application and incorporated herein by reference in its entirety teaches a coating composition for imparting a hydrophobic film on a target surface that includes an oil of a silicone oil or a fluoropolymer oil or a combination thereof, a resin, and a dry lubricant. A solvent is present to form a solution of the oil and resin. A coating is imparted to an applicator that in turn can transfer the coating as a hydrophobic film to glass. The coating composition is stable and able to impart hydrophobic film even after storage for several weeks at elevated temperature. The coating composition does so through the exclusion of synthetic waxes especially including silicone waxes. A kit is also provided that includes a wiper blade insert having the above coating composition applied along with instructions for the securement of the wiper blade insert to a vehicle to impart the hydrophobic film to a vehicle windshield contacted by the wiper blade.
It has been observed that typical hydrophobic glass treatments only last for a few months on the automotive windshield surface, primarily due to the abrasion by the wiper blade insert if the blade squeegee is made of non-silicone rubber. However, appropriately formulated polysiloxane fluid-based water repellent (WR) coating or treatment for automotive windshield surfaces resist the wiper blade insert abrasion if the wiper blade insert is composed of silicone rubber. As illustrated by the prior art chart shown in
Unfortunately, if a conventional, polysiloxane fluid-based WR coating is pre-applied directly onto the silicone rubber squeegee surface such as the teaching of U.S. Pat. No. 9,540,552, the water repelling component in the WR coating overtime is absorbed rather quickly into the silicone rubber, losing its ability to transfer the water repelling material of the coating composition to the wiped windshield surface to make it hydrophobic.
Thus, there exists a need for a wiper blade coating that has a long-lasting shelf life after application to the wiper blade insert as to allow the coated wiper blade insert to impart a hydrophobic film to the contacted areas of the windshield rapidly during wiper blade operation and even after a long storage duration of the wiper blade coated with the coating composition, and even at elevated temperature. There further exists a need for a water repellent coating that resists absorption into silicon rubber based wiper blade materials.
A coating composition is provided for imparting water repellency from a rubber element of automotive wiper blade to a windshield, the coating includes a quaternary ammonium chloride silane, a polar solvent such as isopropanol, or non-polar solvent such as a mineral spirits in which the silane is dispersible, and a graphite powder.
An improved coating composition is provided for imparting a hydrophobic film, the coating composition including a quaternary ammonium chloride silane, a polar solvent such as isopropanol, or non-polar solvent such as a mineral spirits in which the silane is dispersible, and a graphite powder wherein the improvement lies in: the silane, which carries an electric charge on the molecule and is repelled by the rubber element of the wiper blade, preventing the coating composition from being absorbed into the rubber element.
A kit is provided for producing a hydrophobic film on a surface, the kit includes an applicator having an applicator surface and a nonvolatile layer formed from the a composition as described above, the nonvolatile layer adhered to the applicator surface or applied thereto from a container; and instructions for contacting the applicator surface with the windshield surface to produce a hydrophobic film having a water contact angle of greater than or equal to 60°.
A process of activating a windshield includes contacting the windshield with a wiper blade coated with a composition as described above, and wiping under wet, dry, or a combination of wet and dry conditions within 2000 wipe cycles to a water repellency of more than 60 degrees of water contact angle to activate the windshield.
The present invention is further detailed with respect to the following drawings. These figures are not intended to limit the scope of the present invention but rather illustrate certain attributes thereof.
The present invention has utility as a vehicle windshield wiper having a coating that resists absorption into silicone based wiper blade insert materials while also imparting a hydrophobic film to the contacted glass surface. Embodiments of the inventive water repellent (WR) coating composition are non-absorbable into, or otherwise not penetrative into the wiper blade insert onto which the inventive WR coating is applied, therefore, preserving its capability of transferring the WR ingredients of the coating from the wiper blade insert to the windshield surface on which the wiper blade insert is operated, even after the coated wiper blade insert has been aged for an extended period of time in storage. The performance of aged wiper blades is an important parameter to measure as a wiper blade insert following manufacturing can take from several weeks to many months before reaching the end user and contact with target windshield glass. The present invention achieves this result by formulating the water repelling component in the WR coating composition to be non-absorbable into, or otherwise not penetrative into the wiper blade insert coated therewith.
In embodiments of the inventive water repellant coating, the active ingredients of the coating composition are non-absorbable to the coated wiper blade insert substrate, and display a minimal affinity between the WR component and the rubber surface that is coated. As a result, the water repelling component in the WR coating is not absorbed into the wiper blade insert prior to installation, thereby preventing the loss of the ability of the composition to transfer the water repelling material of the coating to the wiped glass windshield surface to render the glass hydrophobic.
While the coating composition of the present invention is largely detailed hereafter with respect to a wiper blade insert formed of silicone, it is appreciated that the inventive coating also provides excellent performance on various non-silicone rubber materials commonly used in the wiper blade industry. These other materials including but not limited to, natural rubber, synthetic rubber such as CR rubber (chloroprene rubber), EPDM (ethylene propylene diene terpolymer) rubber, mixtures of natural and synthetic rubbers, silicone rubber, and mixtures of silicone rubber and non-silicone rubber.
It is further appreciated that while the coating composition of the present invention is largely detailed with respect to windshields, it is appreciated that other suitable target surfaces of usage for the present invention illustratively include buffing pads, buffing clothes, chamois, manual squeegees, vehicle rear windows, aircraft exterior surfaces, and other exterior surfaces where water repellency is desired. The term “wiper blade” as used herein is intended to encompass these aforementioned applicators as well. The present invention has the attribute of long term storage stability of more than 6 months at the ambient condition coupled with the ability to even after storage, impart a hydrophobic film to a contacted surface.
Numerical ranges cited herein are intended to recite not only the end values of such ranges but the individual values encompassed within the range and varying in single units of the last significant figure. By way of example, a range of from 0.1 to 1.0 in arbitrary units according to the present invention also encompasses 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, and 0.9; each independently as lower and upper bounding values for the range.
An inventive coating composition includes a film-forming, quaternary ammonium silicone compound having the formulas:
[(RO)3-aSi—R2—N(R1)(R1)(R3)]X− (I), or
(HO)2—Si(R4)—O—(R4)Si—(OH)2 (II)
where R in each occurrence is independently C1-C4 alkyl, R4, or H; a is an integer value of 0, 1, or 2, inclusive; R1 and R2 in each occurrence are independently C1-C8 alkyl or alkenyl groups; R3 is a C1-C22 alkyl group; and X represents an anion, and includes F−, Cl−, Br−, I−, divalent and trivalent anions with the proviso that a salt is formed with the quaternary ammonium cation; and R4 in each occurrence is N(R1)(R1)(R3)] X−. It is appreciated that any alkyl or alkenyl moieties present in formula (I) can be linear or branched. It is further appreciated that any alkyl group having of at least C3 can further include a pendant group that serves to modify the solubility and filming forming properties. Pendant groups operative herein illustratively include —OH, —SO4−2, or —SO3−.
Exemplary quaternary ammonium silicones operative herein illustratively include: (CH3O)3Si(CH2)3N+(CH3)2C18H37Cl−, (CH3CH2O)3Si(CH2)3N+(CH3)2C18H37Cl−, (CH3O)3Si(CH2)3N+(CH3)2C18H37Br−, (CH3O)3Si(CH2)3N+(C10H21)2CH3Cl−, (CH3O)3Si(CH2)3N+(CH3)2C14H29Cl−, (CH3O)3Si(CH2)3N+(CH3)2C14H29Br−, (CH3O)3Si(CH2)3N+(CH3)2C16H23Cl−, and combinations thereof.
The film-forming, quaternary ammonium silicone salt is present in some inventive embodiments from 0.5 to 75 total weight percent, in other inventive embodiments, the salt is present from 5 to 60 total weight percent.
A solvent or a combination of solvents capable of forming a solution with the salt is also provided. The solvents operative herein illustratively include polar or non-polar or mixture of polar or non-polar solvents suitable for dissolution of the salt that illustratively include methylethylketone, C1-C8 alkyl lactates, C1-C8 alkyl acetates, C1-C8 alcohols, glycols, glymes, polyalkyl glycols, ethers as well as combinations thereof. It is appreciated that the term “alkyl” as used herein is intended to include linear, branched, and cyclic forms thereof. In certain inventive embodiments, the solvent is the alcohol, of which isopropanol is exemplary. The nature of the solvent as operative herein is largely limited only to the ability to dissolve the silicone oil and the resin components. As will be made clear from the following description, as the inventive composition is applied to an applicator in certain inventive embodiments.
An inventive coating composition also includes an optional particulate lubricant. A particulate lubricant according to the present invention is either applied separately to an applicator or as a colloidal dispersion in the solvent along with the salt. The particulate lubricant in certain embodiments of the present invention has greater than 90 particle number percent of the particulate having a particle size smaller than 100 microns as determined by size guide number-(SGN). In still other embodiments of the present invention, 100 particle number percent are smaller than 100 microns. In still other embodiments of the present invention, the particulate has a mean particle size smaller than 50 microns. In certain embodiments of the present invention, a coating composition in solvated form is 1 to 10 total weight percent particulate lubricant. A particulate lubricant operative in the present invention illustratively includes graphite, turbostratic carbon, boron nitride, boric acid, and combinations thereof. In some inventive embodiments the particulate lubricant is only graphite.
In some inventive embodiments, an optional nonpolar hydrocarbon solvent such as mineral spirits are present. Mineral spirits, if present facilitates spreading on a hydrophobic applicator surface, such as a wiper blade. An inventive coating composition has superior storage stability as a nonvolatile layer on an applicator such as a wiper blade insert through the inclusion of the quaternary ammonium silicone salt to preclude penetration into the applicator. An inventive coating composition is applied to an applicator such as a wiper blade, cloth, or buffing pad and allowed to dry to a nonvolatile layer on the applicator. A layer of the inventive formulation on an applicator is amenable to storage for weeks or months even at extreme temperatures within the range of −50 to 70° C. and yet is still able to impart a hydrophobic film to a contacted glass surface. The resultant film imparts to the surface a water contact angle of at least 60° through simply rubbing the applicator against the target surface.
An applicator such as a wiper blade, shown generally at 10 in
Without intending to be bound to a particular theory, it is believed that cationic quaternary ammonium silicone salt with an inherent charge is hydrophilic at least on the part of the molecule that is close to the electric charge and repelled consequently by a hydrophobic applicator, such as an elastomeric wiper blade. As a result, the inventive formulation coating is prevented from being absorbed into the applicator interior and therefore extending the shelf life of the WR coating.
The present invention also provides a kit for producing a hydrophobic film on a surface. The kit includes an applicator having a nonvolatile layer of the coating composition adhered to the applicator, or the coating composition in a separate bottle for user application to the applicator; along with instructions for contacting the coated applicator with the target surface to produce a hydrophobic film on the surface with a water droplet contact angle of greater than 60° with the contact angle being measured by ASTM C813. The kit in order to have a storage stability of greater than three months, and in certain embodiments more than one year, and still in certain embodiments equal to or more than two years at an average of 25° C.
A process for activating a windshield with a wiper blade insert as an applicator according to certain embodiments of the present invention is achieved by wiping the windshield under wet, dry, or a combination of wet and dry conditions to a water repellency of more than 60 degrees of water contact angle within 2000 wipe cycles. In still other embodiments, this degree of water repellency is achieved while maintaining a wipe quality that is within 90% or greater of that for an uncoated wipe blade otherwise identical to the wiper blade while the water repellency on the wiped windshield surface remains. Wipe quality is typically graded from a scale of 1 to 10, as defined, for example, by Akron Rubber Development Laboratory (ARDL), Inc.
Table 1 lists the major components of an embodiment of the inventive WR coating composition that resists absorption into rubber materials.
It is appreciated that an inventive coating on an applicator represents a dried version of the composition that has lost most if not all of the solvent and in some instances mineral spirits through volatilization so as to be composed of the salt, particulate, additives and in some instances residual solvent and/or mineral spirits.
The present invention is further detailed with respect to the following nonlimiting examples. These examples are not intended to limit the scope of the invention but rather highlight properties of specific inventive embodiments and the superior performance thereof relative to comparative examples.
The coating composition of 50 total weight percent of a quaternary ammonium chloride silane, 30 total weight percent isopropanol, 15 total weight percent mineral spirits, 5 total weight percent of graphite powder with 90% particle size smaller or equal to 100 microns, and the remainder being isopropanol is applied to silicone rubber squeegees which were stored at 60° C. or room temperature for various periods of time before being evaluated for ability to transfer the water repellant (WR) property as measured by the water contact angle of the wiped windshield surface, from the coated blade to the windshield using a vehicle windshield and its wiper system under wet conditions. As illustrated in the chart of
The plotted results of
The coated wiper squeegee that was aged at 60° C. for 36 days and then at room temperature for 85 days is predicted to have a shelf life equal to or greater than 661 days if stored under the ambient condition, and the coated wiper squeegee that was aged at 60° C. for 51 days and then at room temperature for 19 days is predicted to have a shelf life equal to or greater than 835 days if stored under the room temperature ambient conditions.
A test is conducted under Society for Automotive Engineers (SAE) J903 to test the durability of the water repellant coating on a wiper squeegee with respect to storage length and ambient conditions. A first blade was coated with the inventive composition and is aged for 36 days at 60° C. and then at room temperature for 85 days. A second blade is aged for 51 days at 60° C. and then at room temperature for 19 days. As shown in
Commercially available CR-NR blended squeegees are coated with composition corresponding to Examples 1-3 of US2010/0234489 A1 and are aged at room temperature for about 3 months after production. The windshield WR tests show that these coatings are not able to activate the windshield to a water CA of more than 80 degrees. The water repellency of the wiped area is observed to not be uniform, indicative that the wiped area of the windshield is not fully activated.
Patents and publications mentioned in the specification are indicative of the levels of those skilled in the art to which the invention pertains. These patents and publications are incorporated herein by reference to the same extent as if each individual patent or publication is specifically and individually incorporated herein by reference.
The forgoing description is illustrative of particular embodiments of the invention but is not meant to be a limitation upon the practice thereof. The following claims, including all equivalents thereof are intended to define the scope of the invention.
This application claims priority benefit of U.S. Provisional Application Ser. No. 62/848,249 filed 15 May 2019, the contents of which are hereby incorporated by reference.
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/US2020/033036 | 5/15/2020 | WO |
| Publishing Document | Publishing Date | Country | Kind |
|---|---|---|---|
| WO2020/232323 | 11/19/2020 | WO | A |
| Number | Name | Date | Kind |
|---|---|---|---|
| 6461537 | Turcotte et al. | Oct 2002 | B1 |
| 6994890 | Ohlhausen et al. | Feb 2006 | B2 |
| 9637670 | Fang | May 2017 | B2 |
| 20050096250 | Ohlhausen et al. | May 2005 | A1 |
| 20090047475 | Jeon | Feb 2009 | A1 |
| 20130017242 | Richardson et al. | Jan 2013 | A1 |
| 20130045332 | Fang et al. | Feb 2013 | A1 |
| 20140116465 | Fang | May 2014 | A1 |
| 20190061401 | Ozawa | Feb 2019 | A1 |
| Number | Date | Country |
|---|---|---|
| 1874855 | Dec 2006 | CN |
| 103025520 | Apr 2013 | CN |
| 104769088 | Jul 2015 | CN |
| 105925388 | Sep 2016 | CN |
| 107057101 | Aug 2017 | CN |
| 107099400 | Aug 2017 | CN |
| 108024602 | May 2018 | CN |
| 1059213 | Dec 2000 | EP |
| 2003180592 | Jul 2003 | JP |
| 2014046734 | Mar 2014 | JP |
| 446654 | Jul 2001 | TW |
| WO-2007070714 | Jun 2007 | WO |
| WO-2008076839 | Jun 2008 | WO |
| Entry |
|---|
| First Office Action issued in CN 202080032840.X, dated Aug. 18, 2022. |
| Zhou, et al., “Troubleshooting Problem Solving of Textile Sizing”, China National Textile Press, Aug. 31, 2005, p. 17 (A type reference). |
| Int'l Search Report for PCT/US2020/033036, dated Aug. 19, 2020. |
| Number | Date | Country | |
|---|---|---|---|
| 20220195204 A1 | Jun 2022 | US |
| Number | Date | Country | |
|---|---|---|---|
| 62848249 | May 2019 | US |
