TW201813938A - Removable glass surface treatments and methods for reducing particle adhesion - Google Patents

Abstract

Disclosed herein are methods for treating a glass substrate, comprising bringing a surface of the glass substrate into contact with at least one surface treatment agent for a time sufficient to form a coating comprising the at least one surface treatment agent on at least a portion of the surface. Also disclosed herein are glass substrates comprising at least one surface and a coating on at least a portion of the surface, wherein the coated portion of the surface has a contact angle ranging from about 20 degrees to about 95 degrees, and/or a contact angle greater than about 20 degrees after contact with water, and/or a contact angle less than about 10 degrees after wet or dry cleaning of the glass substrate.

Description

Removable glass surface treatment and method for reducing particle adhesion

Disclosed herein are methods of treating glass substrates to reduce the adhesion of particles to the surface of glass substrates, and more particularly to glass surface treatments that improve soil resistance and enhance ease of removal.

In recent years, due to superior display quality, reduced weight and thickness, low power consumption, and increased device affordability, consumer demand for high performance display devices such as liquid crystal and plasma displays has increased significantly. Such high performance display devices can be used to display various information such as images, graphics and text. High performance display devices typically employ one or more glass substrates. As the resolution and image performance requirements increase, the surface quality requirements of glass substrates become more stringent, such as surface cleanliness. Surface quality can be affected by any glass processing steps from forming the substrate to storage to the final package.

The glass surface may have a high surface energy to some extent due to the presence of surface hydroxyl groups (X-OH, X = cation) on the surface of the glass, such as stanol (SiOH). When the surface of the glass is exposed to moisture in the air, surface hydroxyl groups can be formed rapidly. Hydrogen bonding between the surface hydroxyl groups can initiate further absorption of moisture, which in turn causes a viscous hydration layer containing molecular water to appear on the surface of the glass. Such viscous layers have various deleterious effects, including, for example, "capillary" action, which causes the particles to adhere firmly to the surface of the glass and/or the surface hydroxyl groups condense to form covalent oxygen bonds, so that the particles adhere firmly to the surface, especially at elevated temperatures. under.

Glass substrates with high surface energy attract particles in the air during transportation, handling and/or manufacturing. In addition, during deposition, strong adhesion creates covalent bonds between the particles and the glass, which in turn leads to reduced yields during processing and cleaning processes. Various possible methods of preventing particle adhesion include, for example, thermal evaporation, spray methods, lamination, or use of coated transfer paper. In some cases, the glass may be coated with a Visqueen film and/or separator paper and packaged in a crates or other storage container, such as a DensePak box. The storage container may remain in the warehouse for several months in an uncontrolled environment, such as 2-3 months. However, the longer the glass substrate is stored, for example, for several months, the particles may have been covalently bonded to the surface of the glass, making it more difficult to remove surface particles.

In the unprotected glass example, an unregulated warehouse environment provides the opportunity for organic contaminants to continuously land on the glass surface, resulting in adhesion, reduced cleanliness, and/or possible contamination. When the separator paper is placed between the glass substrates, vibration during transport causes the cellulose particles to fall off the paper and subsequently adhere to the glass surface. On the other hand, the use of Visqueen membranes to protect glass substrates reduces the possibility of environmental and/or cellulose contamination, but prolonged exposure to membrane materials, especially in hot and/or humid environments, may result in organic slip agents (eg mustard) The acid amide is transferred from the membrane to the glass surface. This organic residue is difficult to remove using conventional washing processes and/or causes staining of the glass substrate.

Therefore, current methods of preventing particle adhesion are not reliable and/or variability, and it is difficult and/or not feasible to integrate into a glass processing process. Other disadvantages include increased manufacturing costs and/or complexity, such as due to expensive materials and/or additional processing steps, such as lamination. When the end user attempts to clean and utilize the glass product, certain surface treatments may also be difficult to remove and/or may be removed too easily during the processing prior to storage.

Accordingly, it would be advantageous to provide a method of reducing particle-attached glass substrates to remedy one or more of the above disadvantages, such as methods that are more economical, feasible, and/or easier to integrate into current glass forming and processing processes. In some embodiments, the methods disclosed herein can be used to fabricate glass substrates having low surface energy, large contact angles, and improved handling and/or storage properties, such as reducing particle adhesion during a given storage time.

In various embodiments, the present invention is directed to a method of treating a glass substrate, the method comprising contacting a surface of the glass substrate with at least one surface treatment agent, for a time sufficient to form a coating on at least a portion of the surface, wherein the coated portion of the surface is deionized The contact angle of water is from about 20 degrees to about 95 degrees, wherein the contact angle of the coated portion after contact with water is greater than about 20 degrees, wherein the contact angle of the coated portion is less than about 10 degrees after contact with the detergent solution. . Also disclosed herein is a glass substrate comprising at least one surface and a coating on at least a portion of the surface, wherein the coated portion of the surface has a contact angle with deionized water of from about 20 degrees to about 95 degrees, wherein after contact with water, the coating The contact angle of the cover portion is greater than about 20 degrees, wherein the contact angle of the coated portion after contact with the detergent solution is less than about 10 degrees.

According to various embodiments, at least one surface treatment agent may be selected from the group consisting of surfactants, polymers, and fatty chain functional organic compounds, such as hydrophobic polymers, hydrophilic/hydrophobic copolymers, nonionic surfactants, including (C ₈ -C ₃₀ ) a cationic surfactant of an alkyl chain, a fatty alcohol comprising a (C ₆ -C ₃₀ ) alkyl chain, and combinations thereof. At least one surface treatment agent may be present in the solution, and the solution contains, for example, from about 0.1% by weight to about 10% by weight of the surface treating agent. In some embodiments, the thickness of the coating can be less than about 1 micrometer (μm), such as less than about 100 nanometers (nm) or even less than about 10 nm.

In certain embodiments, the contact angle of the coated portion of the surface with deionized water is greater than about 20 degrees after a period of contact with water having a temperature of from about 25 ° C to about 80 ° C for about 5 minutes or less. The contact angle of the coated portion of the surface with deionized water is less than about 20 degrees after exposure to a detergent solution having a temperature of from about 25 ° C to about 80 ° C for a period of about 2 minutes or less. In a further embodiment, the contact angle of the glass substrate to the deionized water is less than about 10 degrees after washing with the detergent.

The additional features and advantages of the present invention will be described in detail in the light of the <RTIgt; Easy to understand.

It is to be understood that the foregoing general descriptions The accompanying drawings provide further understanding and are therefore incorporated in and constitute a part of the specification. The drawings depict various non-limiting embodiments and, together with

The drawn or cleaned glass surface has a very high surface energy (up to 90 millijoules per square meter (mJ/m ² ) in some examples). High surface energy increases the susceptibility of the surface to adsorption of particles in the air. Without being bound by theory, the high surface energy of the salty letter is due, at least in part, to the presence of surface hydroxyl groups (X-OH) on the surface of the glass, such as SiOH, AlOH and/or BOH, which will form hydrogen bonds with the available particles. In addition, if particles such as glass or oxide particles are still attached to the surface, the initial hydrogen bond adhesion and/or van der Waals force will be enhanced by agglomeration, resulting in stronger covalent bonds. Particles covalently bonded to the surface of the glass substrate are even more difficult to remove, resulting in reduced processing yields.

Glass granules of various sizes and shapes may be produced by, for example, a draw bottom (BOD) traveling chip machine (TAM) plus horizontal or vertical scribe and break, or edge processing, transport, handling, and/or storage of glass. Such particles are referred to as attached glass (ADG) in various industries. Particle adhesion and/or adsorption of the glass surface will increase over time and will vary depending on atmospheric conditions, such as temperature, humidity, cleanliness of the storage environment, and the like. Glass that has been stored for more than 3 months is particularly susceptible to high energy (eg, covalent) bonded particle adhesion and may be difficult to process to acceptable levels that meet stringent quality control guidelines. ADG particle density on the glass surface a first diagram illustrating store over time. As shown, as the storage time increases, the susceptibility of the substrate to particle attachment is significantly improved. method

Disclosed herein are methods of treating glass surfaces to reduce or eliminate the adhesion of particles to the glass surface. The term "particles" and variants as used herein are intended to mean any shape or size contaminant attached to and/or adsorbed on the surface of the glass. For example, the particles may include organic and inorganic contaminants such as glass particles (eg, ADG), cellulosic fibers, dust, M-OX particles (M = metal; X = cation), and the like. Particles during such periods as manufacturing, transporting and/or storing glass articles, such as cutting, machining, edge grinding, shipping (eg, using suction cups, conveyor belts and/or rolls) or storage (eg, boxes, paper, etc.) May be produced on the surface of the glass object.

The method disclosed herein comprises, for example, contacting a surface of a glass substrate with at least one surface treatment agent for a time sufficient to form a coating on at least a portion of the surface, wherein the contact angle of the coated portion of the surface with deionized water is from about 20 degrees to about 95 degrees, after contact with water, the contact angle of the coated portion of the surface with deionized water is greater than about 20 degrees, and after contact with the detergent solution, the contact angle of the coated portion of the surface with deionized water is less than about 10 degrees. .

According to various embodiments, at least one surface treatment agent can act as a chemical and/or physical barrier layer to prevent organic and inorganic contaminants from falling on the glass surface and/or forming bonds with the glass surface during storage. In some embodiments, the treatment methods disclosed herein neutralize at least a portion of the surface hydroxyl groups (X-OH) that may be present on the surface of the glass, for example, such that they do not react with particles or other possible reactants. Neutralization can be carried out by chemical adsorption (e.g., covalent and ionic bonding) or physical adsorption (e.g., hydrogen bonding with van der Waals). According to various embodiments, the treatment methods disclosed herein can neutralize at least about 50% of surface hydroxyl groups, such as greater than about 60%, greater than about 70%, greater than about 80%, greater than about 90%, greater than about 95%, or greater than about 99%, for example from about 50% to about 100%, including all ranges and subranges therebetween.

Evaluation of coating efficacy can be based, for example, on (a) whether the coating is improperly removed (eg, using water at room temperature or slightly elevated temperature), and (b) whether the coating is effectively removed when deliberately washed (eg, at elevated temperatures) Whether an alkaline detergent is used, and (c) whether the coating reduces the amount of attached particles compared to the untreated control. It is possible that the surface treatment agents can be classified into four categories: water-soluble reagents, organic soluble reagents, surface reactants, and surface deactivators. Each category has its own advantages and disadvantages in terms of the above properties (a)-(c) and/or other treatment considerations.

For example, water soluble agents are more environmentally friendly, safe, and/or less toxic, but such agents are not resistant to improper removal, such as during aqueous edge grinding processes. Organic soluble reagents are more resistant to water removal, but the handling is complicated by flammability and/or toxicity problems. Likewise, the surface reactants can be more firmly bonded (e.g., chemisorbed) to the glass surface, providing a stable coating that can withstand improper removal and/or improve glass adhesion to the particles. Coatings using such surface reactants are difficult to remove, resulting in prolonged and/or complicated downstream processing of the glass substrate. On the other hand, the coating comprising the surface passivating agent is easily washed away with the detergent solution and is not sufficiently firmly bonded (e.g., physically adsorbed) to the glass surface to withstand improper removal of water during the intermediate processing step.

Without being bound by theory, it is believed that surface treatment agents that produce highly hydrophobic coatings can improve particle adhesion resistance, thereby reducing the amount of particles to be washed off the glass surface, and/or assisting in the removal of any such adhering particles. In some embodiments, low surface energy (especially low polarity surface energy components) represents a more hydrophobic surface. The polarity of the glass surface is affected by, for example, the concentration of hydroxyl groups on the surface of the glass.

By neutralizing at least a portion of the surface hydroxyl groups on the surface of the glass, at least one surface treatment agent can reduce the total surface energy of the glass substrate to less than about 65 mJ/m ² , such as less than about 60 mJ/m ² and less than about 55 mJ/ m ² , less than about 50 mJ/m ² , less than about 45 mJ/m ² , less than about 40 mJ/m ² , less than about 35 mJ/m ² , less than about 30 mJ/m ² or less than about 25 mJ/m ² For example, in the range of from about 25 mJ/m ² to about 65 mJ/m ² , including all ranges and sub-ranges therebetween. The polar surface energy can, for example, be less than about 25 mJ/m ² , such as less than about 20 mJ/m ² , less than about 15 mJ/m ² , less than about 10, less than about 9, less than about 8, less than about 7, less than about 6, Less than about 5, less than about 4, less than about 3, less than about 2, or less than about 1 mJ/m ² , such as from about 1 mJ/m ² to about 25 mJ/m ² , including all ranges and subranges therebetween. In certain embodiments, the coating portion may have a dispersion energy greater than about 10 mJ/m ² , such as greater than about 15 mJ/m ² , greater than about 20 mJ/m ² , greater than about 25 mJ/m ² , greater than about 30. mJ/m ² , greater than about 35 mJ/m ² or greater than about 40 mJ/m ² , such as from about 10 mJ/m ² to about 40 mJ/m ² , including all ranges and subranges therebetween.

The surface tension (or surface energy) of the material can be determined by methods well known to those skilled in the art, including the hanging drop method, the du Nuoy rk g method or the Wilhelmy plate method ("Physical Chemistry of Surfaces". , Arthur W. Adamson, John Wiley and Sons, 1982, pp. 28"). Furthermore, the surface energy of the surface of the material can be divided into polar and non-polar (dispersed) components by detecting the surface using a liquid of known polarity (e.g., water and diiodomethane) and measuring the contact angle with each of the probe liquids. Therefore, the water and diiodomethane control angles of each substrate can be measured by using any of the above surface tension methods or in combination with the following formula to determine the surface properties of the untreated (control) glass substrate and the surface of the treated glass substrate. Properties: σ _T = σ _D + σ _P , where σ _T is the total surface energy, σ _D is the dispersed surface energy, and σ _P is the polar surface energy.

The hydrophobicity of the surface can also be indicated by a large contact angle between the surface and the deionized water. Large contact angles tend to indicate that the surface is not easily wetted by water and is therefore more water resistant. Without being bound by theory, the water resistance of the letter prevents the glass or other particles from forming strong bonds with the glass surface and/or helps to subsequently remove particulates or organic contaminants using conventional washing methods. According to various embodiments, the contact angle of the coated portion of the glass with deionized water may be from about 20 degrees to about 95 degrees, such as from about 30 degrees to about 90 degrees, from about 40 degrees to about 85 degrees, after contact with the surface treatment agent. From about 50 degrees to about 80 degrees or from about 60 degrees to about 70 degrees, including all ranges and subranges therebetween.

Hydrophobicity or water resistance can also be confirmed by treating the substrate with a large contact angle even after washing with deionized water for 5 minutes or less. In some embodiments, the coating comprising at least one surface treatment agent can be suitably tolerated to only water removal, which advantageously coats the substrate for various processing steps prior to end use, such as edge processing or edge cleaning. Thus, in such embodiments, the contact angle of the coated surface (with deionized water) may be greater than about 20 degrees, such as greater than about, after contact with water (eg, at about 25 ° C to about 80 ° C for about 5 minutes). 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90 or 95 degrees, for example from about 20 degrees to about 95 degrees, including all ranges and subranges therebetween. In some embodiments, the time of contact with water can range from about 15 seconds to about 5 minutes, such as from about 30 seconds to about 4 minutes, from about 60 seconds to about 3 minutes, or from about 90 seconds to about 2 minutes, including all ranges therebetween. Subrange. Likewise, the water temperature can range from about 25 ° C to about 80 ° C, such as from about 30 ° C to about 70 ° C, from about 35 ° C to about 60 ° C, or from about 40 ° C to about 50 ° C, including all ranges and subranges therebetween.

The glass substrate can be in contact with at least one surface treatment agent for a time sufficient to coat at least a portion of the glass surface with the reagent. In certain embodiments, the entire glass surface can be coated with at least one surface treatment agent. In other embodiments, the predetermined glass surface portion, such as the edge or perimeter of the glass substrate, the central region, or any other region or pattern may be applied as desired, without limitation.

The term "contact" and variants as used herein are intended to mean the interaction of a glass surface with at least one surface treatment agent. The result of the physical contact of the glass surface with at least one surface treating agent will form a bond between at least one surface treating agent and the surface of the glass, for example with at least one surface hydroxyl group. The bond can be a covalent bond, an ionic bond, a hydrogen bond, and/or a van der Waals interaction.

At least one surface treatment agent can be contacted to the glass surface by any suitable method known in the art, such as spray coating, dip coating, meniscus coating, overflow coating, brush coating, roll coating, and the like. In certain embodiments, at least one surface treatment agent can be applied by spraying, such as at a spray station, as the glass substrate moves along the production line of the manufacturing process. Spraying can be airless or air assisted, or in additional embodiments, an aerosol can be used to create a surface treatment mist. In some embodiments, the surface treatment agent can be deposited to the glass surface as liquid or vapor. According to a further embodiment, the glass substrate can be transported using a continuous horizontal or vertical transport system, which can be located anywhere along the transport system.

At the time of coating, the temperature of the glass substrate during the manufacturing process may vary depending on the position at which the coating is applied. For example, the coating can be applied during or after the draw bottom (BOD) process, including a traveling anvil machine (TAM) to score and break the glass into sheets and vertical bead scribe and fracture separation (VBS) treatment. In some embodiments, the coating step can be incorporated into the BOD treatment, such as after the VBS. The surface temperature of the glass in the BOD region can be as high as about 300 ° C; however, after VBS, the surface temperature of the glass can be lowered, for example, less than or equal to about 100 ° C. Although conventional thick (eg, > 1 μm) coatings are often applied to hot glass surfaces prior to VBS processing, the coatings disclosed herein can be applied to the cooled glass surface after VBS. For example, the glass surface temperature can range from about 10 ° C to about 100 ° C, such as from about 20 ° C to about 90 ° C, from about 30 ° C to about 80 ° C, from about 40 ° C to about 70 ° C, or from about 50 ° C to about 60 ° C, including All ranges and sub-ranges.

The residence time (e.g., the time at which a surface treatment agent contacts the glass surface) may vary depending on the properties of the predetermined coating. By way of non-limiting example, the residence time can be from less than one second to several minutes, such as from about 1 second to about 10 minutes, from about 5 seconds to about 9 minutes, from about 10 seconds to about 8 minutes, from about 15 seconds to about 7 minutes. From about 20 seconds to about 6 minutes, from about 30 seconds to about 5 minutes, from about 1 minute to about 4 minutes, or from about 2 minutes to about 3 minutes, including all ranges and subranges therebetween. In various embodiments, a single coating of at least one surface treatment agent can be applied to the glass surface, or in other embodiments, multiple coatings can be performed, such as 2 or more, 3 or more, 4 or More times, or 5 or more coats, and the like. For example, the glass substrate may be immersed in the solution containing at least one surface treatment agent one or more times, or the surface treatment agent may be sprayed onto the glass substrate by a single sweep or multiple sweeps.

The residence time can also depend on the predetermined coating thickness. In some non-limiting embodiments, the coating thickness can be less than about 1 μm, such as less than about 900 nm, 800 nm, 700 nm, 600 nm, 500 nm, 400 nm, 300 nm, 200 nm, 100 nm, 10 nm, or Hereinafter, for example, from about 1 nm to about 100 nm, from about 2 nm to about 90 nm, from about 3 nm to about 80 nm, from about 5 nm to about 70 nm, from about 10 nm to about 60 nm, from about 20 nm to about 50 nm Or about 30 nm to about 40 nm, including all ranges and subranges in between. Without being limited to theory, thin layers (such as self-assembled monolayers) are easier to remove with conventional washing techniques and have shorter wash times. Thin coatings also have the added advantage of reducing material waste, rapid deposition time, and/or reducing environmental impact.

According to various embodiments, the surface treatment agent may incorporate a solution comprising one or more solvents. In some embodiments, the surface treatment agent concentration in the solution can range from about 0.1% to about 10% by weight, such as from about 0.25% to about 9% by weight, from about 0.5% to about 8% by weight, about 1% by weight. Up to about 7 wt%, from about 1.5 wt% to about 6 wt%, from about 2 wt% to about 5 wt%, or from about 3% to about 4 wt%, including all ranges and subranges therebetween. By way of non-limiting example, suitable solvents may include water, deionized water, alcohols (eg, methanol, ethanol, n-propanol, isopropanol, butanol, etc.), volatile hydrocarbons (eg, C ₁ -C ₁₂ hydrocarbons, and mixtures thereof, For example, petroleum brain), water-miscible organic solvents (such as dimethylformamide, dimethylhydrazine, and N-methyl-2-pyrrolidone) and the above mixtures. Such solvents can evaporate from the surface after deposition, for example by heating or otherwise drying the surface, or naturally evaporating under ambient conditions. Alternatively, in the case of vapor-depositing at least one surface treatment agent, the solvent may be omitted, and the treatment agent itself may evaporate and contact the glass surface.

In a non-limiting embodiment, the methods disclosed herein can provide a glass surface treatment to improve particle adhesion resistance and/or enhance the removal of such particles from the glass surface. For example, after washing with a detergent, the glass surface attachment particles can have a removal efficiency of at least about 50%, such as greater than about 60%, greater than about 70%, greater than about 80%, greater than about 90%, greater than about 95%, or Greater than about 99%, such as from about 50% to about 99%, including all ranges and subranges therebetween. Exemplary washing techniques can include washing with a mild detergent solution, such as an alkaline detergent solution, for from about 15 seconds to about 2 minutes, such as from about 20 seconds to about 90 seconds, from about 30 seconds to about 75 seconds, or from about 45 seconds to A period of about 60 seconds, including all ranges and sub-ranges in between.

Exemplary commercially available detergents can include, but are not limited to, Semi Clean KG. For example, the concentration of the aqueous detergent solution can be less than about 10% by volume, such as from about 1% to about 10%, from about 2% to about 9%, from about 3% to about 8%, from about 4% to about 7 by volume. % or about 5% to about 6%. The non-limiting wash temperature can be, for example, from about 25 ° C to about 80 ° C, such as from about 30 ° C to about 70 ° C, from about 35 ° C to about 60 ° C, or from about 40 ° C to about 50 ° C, including all ranges and subranges therebetween.

The glass substrate can be treated by one or more optional steps, such as polishing, processing, and/or cleaning the surface or edges of the glass substrate prior to contacting the surface treatment agent. Likewise, the glass substrate can be further processed using these optional steps after contacting the surface treatment agent. Such additional steps can be performed by any suitable method known in the art. For example, an exemplary glass cleaning step can include a dry cleaning or wet cleaning method. In some embodiments, the washing step can be performed using an alkaline detergent (eg, Semi Clean KG), SC-1, UV (ultraviolet) ozone, and/or oxygen plasma, and the like. Alternatively, the glass substrate may be selectively further treated after contacting the surface of the glass with at least one surface treatment agent, for example, by applying a polyethylene film (Visqueen) to further protect the glass sheet. Of course, the coating between the glass surface and the Visqueen film, if any, prevents the transfer of organic compounds from the film to the glass surface.

In some embodiments, the coated glass substrate is processed through various processing steps, such as edge processing or edge cleaning processes. Thus, in such embodiments, it may be desirable for the surface treatment to withstand removal by water only, for example as evidenced by little or no contact angle of the surface with deionized water, as will be further detailed below. In addition, it may be desirable for the surface treatment to be easily removed using a detergent or by other cleaning steps described above, for example, as the contact angle with deionized water is reduced to less than about 10 degrees, such as less than about 8 degrees or less than about 5 degrees, For example, from about 1 to about 10 degrees. Of course, treating the glass substrate may or may not have one or all of these properties, but still fall within the scope of the present invention. glass substrate

The invention also relates to glass substrates made by the methods disclosed herein. For example, the glass substrate can comprise at least one surface, wherein at least a portion of the surface is coated with a layer comprising at least one surface treatment agent, wherein the coated portion of the surface has a contact angle with deionized water of from about 20 degrees to about 95 degrees. In an additional embodiment, after the glass substrate is contacted with water, the coated portion of the surface may have a contact angle with deionized water of greater than about 20 degrees. In a further embodiment, after the glass substrate is contacted with the detergent solution, the contact angle of the coated portion of the surface with deionized water can be less than about 10 degrees.

The glass substrate may comprise any glass known in the art including, but not limited to, aluminosilicates, alkali aluminosilicates, alkali-free alkaline aluminosilicates, borosilicates, alkali borosilicates, alkali-free alkaline earths. Boron silicate, aluminoboronate, alkali aluminoborosilicate, alkali-free alkaline aluminoborosilicate and other suitable glasses. In certain embodiments, the thickness of the glass substrate can be less than or equal to about 3 millimeters (mm), such as from about 0.1 mm to about 2.5 mm, from about 0.3 mm to about 2 mm, from about 0.7 mm to about 1.5 mm, or about 1 Mm to about 1.2 mm, including all ranges and sub-ranges in between. Examples of non-limiting commercially available glasses include, for example, EAGLE XG ^® , Iris ^TM , Lotus ^TM , Willow ^{® ,} and Gorilla ^® glasses available from Corning Corporation.

In various embodiments, the glass substrate can comprise a glass sheet having a first surface and a second opposing surface. In some embodiments, the surface can be planar or substantially planar, such as substantially flat and/or horizontal. The glass substrate can be substantially planar or two-dimensional, and in some embodiments, can be non-planar or three-dimensional, such as curved about at least one radius of curvature, such as a convex or concave substrate. In various embodiments, the first and second surfaces may be parallel or substantially parallel. The glass substrate can further comprise at least one edge, such as at least two edges, at least three edges, or at least four edges. By way of non-limiting example, a glass substrate can comprise a rectangular or square piece of glass having four edges, although other shapes and configurations are also contemplated and intended to fall within the scope of the present invention. According to various embodiments, the glass substrate can have a high surface energy prior to processing, such as up to about 75 mJ/m ² or greater, such as from about 80 mJ/m ² to about 100 mJ/m ² .

Referring to the above method, the glass substrate may be coated with a layer containing at least one surface treatment agent. The coating or layer may comprise any suitable surface treatment agent that improves surface particle adhesion resistance, withstands improper removal by water only, and/or can be effectively and/or quickly removed by conventional laundering techniques. Exemplary surface treatment agents can include, but are not limited to, surfactants, polymers, decanes, fatty chain functional organic compounds, and combinations of the foregoing.

The fatty chain functional organic compound may include a fatty alkyl chain and a functional group. The functional group can have polar properties and can therefore be attracted to the hydrophilic glass surface such that the compound itself is oriented along the fatty alkyl portion extending away from the glass surface as a hydrophobic barrier layer to which the particles are attached. Functional groups of the fatty chain can include, but are not limited to, amines, alcohols, epoxides, acids, and oxiranes. Thus, in some embodiments, the fatty chain functional organic compound can be selected from the group consisting of (C ₆ -C ₃₀ )alkylamines, alcohols, epoxides, acids, and decanes. Exemplary (C ₆ -C ₃₀ )alkyl acids can include, but are not limited to, carboxylic acids, organic sulfonic acids, and organic phosphonic acids, and the like. Examples of the non-limiting (C ₆ -C ₃₀ ) fatty alcohol may include, for example, octanol, decyl alcohol, dodecyl alcohol, cetyl alcohol, stearyl alcohol, and the like.

The term "oxygen alkane" as used herein is intended to mean a group of the formula Si(R ¹ ) _3-n (OR ² ) _n wherein R ¹ is alkyl or lower alkyl, R ² is lower alkyl, n Equal to 1, 2 or 3. The term "alkyl" as used herein is intended to mean a straight or branched chain saturated hydrocarbon containing from 1 to 30 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, Tert-butyl, pentyl, hexyl, heptyl, octyl, decyl, tetradecyl, hexadecanyl, octadecyl, icosyl, twenty-four, and the like. "Lower alkyl" is intended to mean an alkyl group having 1 to 5 carbon atoms ((C ₁ -C ₅ )alkyl), such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl Base, tert-butyl and pentyl.

According to various embodiments, the fatty chain functional organic compound may be selected from fatty alcohols such as stearyl alcohol. Although the fatty alcohol is weakly bonded to the glass surface only by the hydrogen bond of the alcoholic hydroxyl group to the hydroxyl group on the surface of the glass, such alcohol has a low solubility in water and is therefore resistant to washing out when only in contact with water. However, such fatty alcohols are relatively quick and easy to remove in the presence of detergent. Another advantage associated with fatty chain functional organic compounds, such as fatty alcohols, is the ability to deposit reagents in liquid or vapor form. For example, fatty alcohols can be directly evaporated onto the glass surface without any solvent. This evaporation method avoids the evaporation step of subsequent solvent removal and does not require disposal of any solvent after use.

Surfactants can also be used as passivating surface treating agents, such as agents that are not covalently bound to the glass surface. Suitable surfactants can include ionic interactions with the glass surface as this exhibits a more stable non-covalent interaction and thus is more resistant to improper water removal during the intermediate processing steps. Suitable for use as a surface treating agent Exemplary surfactants include, without limitation, the length (e.g., C ₈ -C ₃₀₎ alkyl chain cationic surfactant agents, for example of coconut alkyl dimethyl ammonium chloride, didecyl Dimethylammonium chloride, dodecyltrimethylammonium chloride and octadecyltrimethylammonium chloride. Other suitable surfactants include, for example, nonionic surfactants such as ethoxylated cocoamine, PEG (polyethylene glycol) / PPG (polypropylene glycol) copolymer nonionic surfactants, and the like.

Surface passivation agents have some practical limitations. For example, water soluble agents tend to be insufficiently bonded to the glass surface to withstand improper dissolution in water so that they are removed when exposed to water. While water-insoluble agents can improve resistance to removal in water, such agents are also difficult to deposit, such as the need for improperly combustible and/or toxic organic solvents. The polymer material can be used as a surface passivation treatment agent which does not have the above disadvantages. For example, the polymeric material can have multiple anchor points (e.g., multiple hydrogen bonding groups) which can enhance the dynamic barrier of the coating in water. At the same time, such polymers can be dissolved or dispersed in water to be deposited from water or a portion of an aqueous solution. Furthermore, the polymer itself is directed toward the glass surface along the predominantly hydrophilic hydrogen bond to provide sufficient glass surface attachment. Likewise, most hydrophobic groups can be oriented away from the surface while providing a low friction, low surface energy interface on the glass substrate.

The ratio or equilibrium of the hydrophobic and hydrophilic groups of the polymer will govern the adhesion strength of the polymer to the glass surface and the corresponding improper water removal resistance. In one embodiment, a polymer having a suitable hydrophobic/hydrophilic balance may have a diblock structure AB, wherein A is a hydrophobic block and B is a hydrophilic block. The term "amphoteric polymer" is also commonly used to describe this polymer structure. The hydrophilic block B in the amphiphilic block copolymer can be prepared from different monomers or oligomers, for example selected from the group consisting of acrylic acid, maleic acid, hydroxyethyl methacrylate (HEMA), polyethylene glycol (meth)acrylic acid. Ester, ethoxypolyethylene glycol (meth) acrylate, methoxy (meth) acrylate, ethoxy (meth) acrylate, 2-dimethylamino-(ethyl) acrylate (DMAEMA) or a monomer of the above combination. Likewise, exemplary hydrophobic block A in the amphiphilic block copolymer can be made from known hydrophobic monomers including, but not limited to, monovinyl aromatic monomers such as styrene and a-alkyl styrene. Other alkylated styrene or alkyl (meth) acrylate or vinyl ester.

The hydrophobic and hydrophilic blocks are each selected to provide a balanced polymer that is hydrophilic enough to adhere to the glass surface, but not too hydrophilic, so that insufficient water removal resistance is insufficient and hydrophobic enough to act as a particle adhesion barrier But it is not too hydrophobic to be washed off by detergent. Non-limiting exemplary polymer types may, for example, include styrene and maleic acid (pSMA) hydrophilic/hydrophobic copolymers and salts, and the like.

According to various embodiments, the invention relates to a glass substrate comprising at least one surface and a coating on at least a portion of the surface, wherein the coating comprises at least one polymer, wherein the coated portion of the surface is in contact with deionized water It is from about 30 degrees to about 95 degrees, wherein the contact angle of the coated portion after contact with water is greater than about 30 degrees, wherein the contact angle of the coated portion is less than about 10 degrees after contact with the detergent.

The decane can also be used as a surface treatment treating agent, for example, a substituted alkyl decane or a bridged dioxane. The structure of the substituted alkyl decane is similar to the above alkyl oxane, except that the alkyl group is also substituted with one or more organic functional groups selected from the group consisting of amino, ammonium, hydroxyl, ether and carboxylic acid. In many cases, a substituted alkyl decane can be substituted with an organofunctional group at the end of the alkyl group or at any point along or within the alkyl chain. In many cases, the substituted alkyl group is substituted for the lower alkyl group. Some exemplary substituted lower alkyl decanes include, but are not limited to, gamma-aminopropyltriethoxydecane, gamma-aminopropyltrimethoxydecane, beta-aminoethyltriethoxydecane, and delta-aminobutyl Triethoxydecane.

In some embodiments, the substituted alkyl decane comprises one or more functional groups selected from the group consisting of a quaternary nitrogen, an ether, and a thioether. According to certain embodiments, the substituted alkyl decane comprises a pendant (C ₆ -C ₃₀ ) alkyl group extending from a functional group, such as a substituted alkyl decane having a quaternary nitrogen and having a pendant (C ₁₀ -C ₂₄ ) alkyl group. Non-limiting exemplary substituted alkyl decanes may, for example, include N,N-dimethyl-N-(3-(trimethoxyindolyl)propyl)octadecyl ammonium chloride ("YSAM C18"), which The chemical structure is expressed as follows. YSAM C14 and YSAM C1 are also expressed as follows. YSAM C18 has a pendant (C ₁₈ ) alkyl group derived from a quaternary nitrogen. Similarly, YSAM C14 has a pendant (C ₁₄ ) alkyl group derived from a quaternary nitrogen.

The bridged dioxane may be selected from the group consisting of the following formula (I): Wherein R ² is a lower alkyl group. X is NH or O. One type of bridged dioxane is referred to as diazane, wherein X is NH.

Exemplary proprietary silicon-based compound may include, but are not limited to, commercially available from the Sura Instruments GmbH Virtubond ^TM and Pyrosil®. According to various embodiments, the decane may be water soluble so that it can be deposited on the glass surface in an aqueous solution. In an additional embodiment, the decane itself is oriented along a hydrophobic monolayer that is outwardly (eg, extending away from the glass surface), and the hydrophobic monolayer can serve as a protective coating that is resistant to particle attachment. The decane is more optional to react with the glass surface and is resistant to removal by water alone and/or soluble in water. In a further embodiment, the decane can be removed by applying an alkaline detergent solution and/or using atmospheric plasma. For example, RF plasma can be produced from atmospheric gases that react with decane and decompose the decane coating into gaseous species or small molecules that are washed away from the glass surface. The decane coating can also be removed using a relatively more concentrated alkaline detergent and/or at a relatively higher temperature, such as a detergent concentration of up to 20% by volume, such as from about 10% to about 18% by volume or about 12% by volume. To about 15% by volume, the temperature is up to 100 ° C, such as from about 40 ° C to about 90 ° C, from about 50 ° C to about 80 ° C or from about 60 ° C to about 70 ° C, including all ranges and subranges therebetween.

According to various embodiments, the present invention relates to a glass substrate comprising at least one surface and a coating on the at least a portion of the surface, wherein the coating comprises at least one decane, wherein the coated portion of the surface has a contact angle with deionized water. From about 30 degrees to about 95 degrees, wherein the contact angle of the coated portion after contact with water is greater than about 30 degrees, wherein the contact angle of the coated portion is less than about 10 degrees after contact with the plasma or UV ozone.

As described in the above methods, the coated substrate can be cleaned prior to use to remove the surface treated layer. After cleaning, the contact angle (with deionized water) of the previously coated portion will be greatly reduced, for example as small as 0 degrees. For example, when applied, the contact angle (with deionized water) can be as high as about 95 degrees, and after cleaning, the contact angle (with deionized water) is less than about 10 degrees, such as less than about 9 degrees, less than about 8 degrees, less than about 7 degrees, less than about 6 degrees, less than about 5 degrees, less than about 4 degrees, less than about 3 degrees, less than about 2 degrees, or less than about 1 degree, such as from about 1 degree to about 10 degrees, including all ranges and subranges therebetween. In various embodiments, the cleaning may include wet washing (eg, washing with a detergent solution) or dry cleaning (eg, the plasma or ozone cleaning method).

Additionally, in some embodiments, the surface treatment layer can be suitably tolerated to only water removal, which advantageously coats the substrate through various processing steps prior to end use, such as edge processing or edge cleaning. Thus, in such embodiments, the contact angle of the coated surface (with deionized water) may be greater than about 20 degrees, such as greater than about 20 degrees after contact with water (eg, at about 25 ° C to about 80 ° C for up to about 5 minutes). Approximately 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90 or 95 degrees, such as from about 20 degrees to about 95 degrees, including all ranges and subranges therebetween. Of course, treating the glass substrate may or may not have one or all of the properties, but still fall within the scope of the present invention.

The glass substrate and method of the present invention can have at least one advantage over prior art substrates and methods. For example, the method has superior performance in terms of high throughput, low cost, and/or improved integration, scalability, reliability, and/or consistency compared to prior art methods. Furthermore, glass substrates treated in accordance with this method can have less particle adhesion, are easier to clean, and/or have improved performance over extended shelf times. In addition, the reduced amount of attached glass particles can also provide a less scratched glass substrate, for example because of the reduced frictional contact between the low friction surface and the glass particles and the glass surface. Of course, it is to be understood that the substrates and methods disclosed herein may not have one or more of the above characteristics, but still fall within the scope of the invention and the scope of the appended claims.

It is understood that the various embodiments disclosed may be related to specific features, elements or steps described in the specific embodiments. It is also understood that the specific features, elements, or steps are described in the specific embodiments, but may be interchanged or combined with alternative embodiments.

It should also be understood that the terms "the" or "an", as used herein, mean "at least one" and should not be limited to "the one". Thus, for example, reference to "a surface treating agent" includes examples with two or more surface treating agents, unless the context clearly dictates otherwise.

The range is here expressed as a "specific value" from "about" and/or to another specific value of "about". When the range is expressed herein, the examples will include from a particular value and/or to another particular value. Similarly, when values are expressed as approximations by the antecedent "about", the understanding of a particular value will constitute another aspect. It will be further understood that the endpoints of each range are meaningful relative to the other endpoint and are independent of the other endpoint.

Any method referred to herein is not intended to be construed as requiring a method step in a particular order, unless explicitly stated. It is not intended to infer any particular order when the method claim does not actually recite the steps, or if the scope of the application and the embodiments do not specifically indicate that the steps are limited to a particular order.

Although various features, elements or steps of a particular embodiment are described in the context of "including", it is to be understood that alternative embodiments including the description of "consisting of" or "consisting of" are also used. Covered. Thus, for example, an alternative structure or method embodiment comprising A+B+C implies an embodiment comprising an embodiment or method consisting of A+B+C and an embodiment in which the structure or method consists essentially of A+B+C.

It will be apparent to those skilled in the art that various changes and modifications can be made in the present invention without departing from the spirit and scope of the invention. Modifications, combinations, sub-combinations and variations of the embodiments may be obtained by those skilled in the art, and the invention is to be construed as being included in the scope of the appended claims. Everything and equals.

The following examples are for illustrative purposes only and are not intended to be limiting, and the scope of the invention is defined by the scope of the claims. Example contact angle

Corning EAGLE XG ^® glass substrates were subjected to various surface treatments to evaluate the effect of each treatment on the contact angle after application, after contact with water, and after contact with detergent. The glass samples were coated with different surface treatment agents, and the contact angle of the surface treated glass substrate with deionized water was measured. The substrate was then rinsed in deionized water at room temperature for 60 seconds and the contact angle was measured again. Finally, the substrate was washed with a 2% alkaline detergent at 50 ° C in an ultrasonic bath for 60 seconds and the contact angle was measured again. The results are shown in Table I below. Table I contact angle ¹ IPA: isopropanol ² NMP: N-methyl-2-pyrrolidone

As shown in Table I above, after coating, the glass sample coated with pSMA, SMA N30, PEAA or PHS polymer has a relatively large contact angle with deionized water, which means that the surface hydrophobicity or water resistance can be improved by the treatment. That is, after 60 seconds of washing with deionized water, the surface treated samples still had relatively large contact angles and confirmed the water resistance of these treated samples (PEAA not measured). However, in the examples of pSMA and SMA N30, after the glass substrate was treated with the detergent for 60 seconds, the contact angle of the substrate was significantly reduced, which indicated that the surface treatment was successfully removed, but the PEAA and PHS treated samples still had relatively large contact angles. This means that the surface treatment has not been removed easily or effectively. In some embodiments, a contact angle of less than about 20 degrees, less than about 10 degrees, or even less than about 5 degrees indicates a "clean" glass surface. Hydrophilic polymers (PVA, PEI, PAA, PEVA) and cellulose-derived polymers do not perform well because the contact angle after coating is not large enough, the contact angle after rinsing with water is not large enough or washed with detergent The contact angle afterwards is not small enough.

Similarly, glass samples treated with cationic (eg C ₈ -C ₃₀ ) alkyl chain cationic surfactants (Coco DMA, DDAC, DTAC, OTAC) have a relatively large contact angle with deionized water after coating. It can maintain a large contact angle after rinsing with water and a relatively small contact angle after washing with detergent. Conversely, short-chain cationic surfactants (HTAB) perform poorly, in particular due to insufficient contact angles after rinsing with water. On the other hand, nonionic surfactants (Eth C25, Pluronic F127) have a large contact angle with deionized water after application, maintain a relatively large contact angle after rinsing with water, and have been washed with detergent. Relatively small contact angle.

Finally, octadecyl alcohol, such as steam and solution, has a relatively large contact angle with deionized water after coating, maintains a relatively large contact angle after rinsing with water, and is relatively small after washing with detergent. Contact angle. Two surface reaction decane treatments (YSAM, Aquapel) were also evaluated. Although these surface treatments have high glass surface adhesion (as indicated by the contact angle before and after rinsing with water), their covalent bonding to the glass surface also makes these coatings difficult to remove by conventional wet cleaning methods (eg Indicated by the large contact angle after washing with detergent. However, such coatings may be removed by other methods, such as high temperature and/or high concentration alkaline detergent washing and/or plasma removal methods. Particle attachment

The surface treated glass sample and the untreated sample are edge-grinded and subsequently washed to assess the protective effect of the coating on the glass surface from glass particle attachment and/or by washing to aid in the removal of any adhering particles. The edge of the glass sample (4" x 4") was ground in such a way that the glass particles were thrown onto the surface of the glass. The wet sample was air dried in a vertical orientation through a HEPA air filter. A Toray particle counter using light scattering treatment is then used to count the number of particles deposited on the glass surface by the edge grinding process. The glass samples were then washed with a 2% alkaline detergent at 50 ° C for 90 seconds in an ultrasonic bath. The particles remaining on the surface of the glass after washing are then re-counted. Test results are plotted in FIGS. 2 to 3. Normal resolution counts particles larger than 1 micrometer (μm) in diameter, and high resolution counts small particles as small as 0.3 μm in diameter.

2 through FIG. FIG. 3 shows all the surface treatment of glass as compared to the untreated glass was washed with fewer substantive particles. In various treatments, the copolymer treatment agent (pSMA, SMA N30) outperforms the hydrophobic polymer (PHS) and the aliphatic chain functional organic compound (octadecyl alcohol), which outperforms the surfactant (Eth C25). However, all surface treated surfaces are significantly better than untreated samples. Referring to FIG. 4, FIG. 4 show the removal efficiency of particles after washing, this copolymer was confirmed again treating agent (pSMA, SMA N30) than the hydrophobic polymer (PHS), and a functional aliphatic chain organic compound (stearyl alcohol) This is better than the surfactant (Eth C25). In all cases, the surface treated samples were significantly better than the untreated samples.

no

The various features, aspects, and advantages of the invention will be apparent from the

FIG 1 adhered to a glass-based particle density over time in FIG store;

FIG 2 FIG particle count based glass surface treated with the surface of a variety of untreated glass samples (normal resolution);

FIG 3 based on the number of particles of various FIG untreated glass surface treated with the surface of glass samples (high resolution); and

FIG 4 FIG based particle removal efficiency of various surface treatments and untreated glass samples.

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Claims (25)

A glass substrate comprising at least one surface and a coating on at least a portion of the surface, wherein: a coated portion of the surface has a contact angle with deionized water of from about 20 degrees to about 95 degrees; after contact with water The coated portion of the surface has a contact angle with the deionized water of greater than about 20 degrees; and after contacting a detergent solution, the coated portion of the surface has a contact angle with the deionized water of less than about 10 degree. The glass substrate of claim 1, wherein the coating has a thickness of less than about 1 μm. The glass substrate of claim 1, wherein the coating has a thickness of from about 1 nm to about 100 nm. The glass substrate according to claim 1, wherein the coating layer comprises at least one surface treatment agent selected from the group consisting of a surfactant, a polymer, an aliphatic chain functional organic compound, decane, and the combination thereof. The glass substrate of claim 1 wherein the coated portion of the surface has a surface energy of less than about 65 mJ/m ² . The glass substrate of claim 1, wherein the contact water comprises contacting the glass substrate with water at 25 ° C to about 80 ° C for a period of about 5 minutes or less. The glass substrate according to claim 6, wherein the glass substrate is exposed to room temperature water for about 60 seconds or less. The glass substrate of claim 1, wherein contacting the detergent solution comprises contacting the glass substrate with the detergent solution at a temperature of from about 25 ° C to about 80 ° C for a period of about 2 minutes or less. The glass substrate of claim 8, wherein the glass substrate is contacted with an alkaline detergent solution for about 60 seconds or less. A method of treating a glass substrate, the method comprising: contacting a surface of the glass substrate with at least one surface treatment agent for a residence time sufficient to form a coating on at least a portion of the surface, wherein: coating the surface The contact angle of the covering portion with the deionized water is from about 20 degrees to about 95 degrees; after contacting the water, the contact angle of the coated portion of the surface with the deionized water is greater than about 20 degrees; After the scale, the coated portion of the surface has a contact angle with deionized water of less than about 10 degrees. The method of claim 10, wherein the at least one surface treatment agent is selected from the group consisting of a surfactant, a polymer, an aliphatic chain functional organic compound, and combinations thereof. The method of claim 10, wherein the at least one surface treatment agent is selected from the group consisting of a hydrophobic polymer, a hydrophilic/hydrophobic copolymer, a nonionic surfactant, a cation comprising a (C ₈ -C ₃₀ ) alkyl chain A surfactant, a fatty alcohol comprising a (C ₆ -C ₃₀ ) alkyl chain, and combinations thereof. The method of claim 10, wherein the coating has a thickness of less than about 1 μm. The method of claim 10, wherein the coating has a thickness of from about 1 nm to about 100 nm. The method of claim 10, wherein contacting the surface of the glass substrate with the at least one surface treatment agent comprises dip coating, spin coating, spray coating, meniscus coating, overflow coating, roll coating, brush coating, Aerosol coating, vapor deposition, and combinations thereof. The method of claim 10, wherein the surface of the glass substrate has a temperature of about 100 ° C or below when the at least one surface treatment agent is contacted. The method of claim 10, further comprising grinding an edge of the glass substrate. The method of claim 17, wherein the coated portion of the glass substrate has a contact angle with deionized water of greater than about 20 degrees after grinding. The method of claim 10, further comprising washing the glass substrate with a detergent solution. The method of claim 19, wherein the glass substrate has a contact angle with the deionized water of less than about 10 degrees after washing. The method of claim 10, further comprising applying a polyethylene film to the surface of at least a portion of the glass substrate. A glass substrate comprising at least one surface and a coating on at least a portion of the surface, wherein: the coating comprises at least one polymer; a coated portion of the surface has a contact angle with deionized water of about 30 degrees Up to about 95 degrees; after contact with water, the coated portion of the surface has a contact angle with deionized water of greater than about 30 degrees; and after contact with a detergent solution, the coated portion of the surface is deionized A contact angle of water is less than about 10 degrees. The glass substrate of claim 22, wherein the at least one polymer is selected from the group consisting of block copolymers comprising styrene and maleic acid monomers and copolymer salts described above. A glass substrate comprising at least one surface and a coating on at least a portion of the surface, wherein: the coating comprises at least one decane; a coated portion of the surface has a contact angle with deionized water of about 20 degrees to About 95 degrees; after contact with water, the coated portion of the surface has a contact angle with deionized water of greater than about 20 degrees; and after contact with a plasma or UV ozone, the coated portion of the surface is deionized A contact angle of water is less than about 10 degrees. The glass substrate of claim 24, wherein the at least one decane is selected from the group consisting of substituted alkyl decanes comprising a quaternary nitrogen and a pendant (C ₁₀ -C ₂₄ ) alkyl group.