TW593189B - Method for temporarily protecting glass articles - Google Patents

Abstract

Method for temporarily protecting a surface of a glass article by coating the surface are provides. The methods include providing a removable a film on the surface, wherein the film has a thickness of from about one molecule of film to about ten molecules of film. Methods of reducing chip adhesions when making a cut or ground glass article also are provided. The methods include (a) forming a stable hydrophobic film on the surface of the article, wherein the film has a thickness of from about one molecule of film to about ten molecules of film; (b) cutting or grinding the glass articles, and (c) removing the film.

Description

593189 A7 ___B7 V. Description of the Invention (I) Central Standard of the Ministry of Economic Affairs 扃 Printed by the Consumer Cooperatives Field of Invention: The present invention relates to a method for temporarily protecting glass objects, especially the surface of edge-protected glass objects such as liquid crystal display ^ § ( LCD) glass. This method is used to protect glass objects from external contamination and to prevent the adhesion of glass fragments during the cutting or grinding of glass objects. BACKGROUND OF THE INVENTION: Many glasses including LCD glass require the use of very clean glass surfaces that are substantially free of dust and organic contaminants. When exposed to the external environment, the glass is quickly contaminated with organics, and the contaminants are visible within minutes. Current cleanup processes often involve several steps and require different chemicals. There is a need to operate a method that protects the glass surface during manufacturing, shipping, and storage from external contaminants to minimize or eliminate chemicals to produce a clean glass surface. Current use to cut and grind glass surfaces and edges often produces small glass fragments (e.g., fragments larger than 1 micron and less than 100 microns). Some particles irreversibly adhere to the dry glass surface, rendering the glass useless for most wound applications. This is a particularly serious problem in the case of LCD glass surfaces. LCD glass can be manufactured by a fusion drawing process, which produces a flat, smooth glass surface that can be cut or ground to the required size. Some glass and glass fragments produced by the cutting process come from the glass surface. When the flat surfaces of these fragments are in contact with the surface of the glass plate, there is a considerable contact area between the fragments and the glass surface, which can cause strong adhesion. 2. If the water on the two surfaces is knotted, it will be permanently mixed. In this case,

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1T 593189 Α7 Β7 V. Description of the invention (7) Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs The glass fragments adhere to the surface and become irreversible. This can render glass useless in LCD applications. One known method of protecting glass sheets, particularly LCD glass sheets, is to apply a polymer film to both major surfaces of the glass to protect the glass during scribing, splitting, and chamfering. In the general method, one major surface adheres the polymer film with an adhesive, and the other major surface adheres the film with an electrostatic charge. The first film is removed after finishing (cutting or grinding) the glass edge, and the second film is removed before the final modification process. Although the protective surface of the adhesive-backed film is protected from scratches by the processing device, it can cause other problems. For example, polymers can trap glass fragments generated during the modification process, causing the formation of glass fragments and scratching the glass surface, especially near the edges of the surface. Another problem with thin films is that they can leave adhesive on the glass surface. There is a need for a method to protect the glass surface from debris adhesion, which does not leave any residual coating film on the glass surface, and a method of temporarily protecting the glass surface, so that glass objects with a clean coating-free surface can be immediately To reach as a further application. Organic coatings have been used for many years to protect glass surfaces. See, for example, Smay G. L. Glass Technology 1985, 26, 46-59. Usually an oleic or oleic acid solution is applied to create a lubricious coating that allows the glass bottles to slide between each other without cracking or cracking during the manufacturing process. Oleic acid and oleic acid are long fatty chains that are not easily soluble in water. Therefore, if the lubricating layer is applied by spraying, it requires an alcohol / water solution. In the manufacture of glass, especially LCD glass, alcohol can cause serious paper size in the alcohol / water solution. Use Chinese National Standard (CNS) 8-4 specifications (210 × 297 mm) (Please read the precautions on the back before filling (This page)

1T line 593189 A7 B7 4 V. Description of the invention (3) Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs, because when sprayed on the surface of high temperature glass, alcohol will immediately evaporate and flames and air and methyl gas will be generated The mixture may explode. Oleic and oleic acid coatings are not suitable for protecting LCD glass because of their strong chain-to-chain interaction. Therefore, it is difficult to remove the coating film or even clean it with a detergent. The key to any coating film used to temporarily protect LCD glass is removability. Liquid crystal display manufacturers use LCD glass as it was originally used in complex processes, which typically involve forming semiconductor devices such as thin film semiconductors on a glass substrate. In order not to adversely affect this process, any coating film that protects the LCD glass must be implemented immediately before the LCD manufacturing process. Some materials such as silane and siloxane can meet the criteria for removal in quality, that is, they can be completely removed from the glass surface under appropriate conditions, and some materials cannot be used in LCDs according to their same standards Accepted. This is because liquid crystal display manufacturers consider it unacceptable that these materials may break even the smallest amount of materials during the LCD manufacturing process. Although most of them are removed, these materials do not meet the removal standard in actual application (that is, the degree of removal of the protective coating film that must be achieved is a function of the composition of the coating film group). In addition, metal inspection materials must be avoided in the materials used to make glass for liquid crystal displays. This is because metal inspection, even very small amounts of metal inspection will be harmful to thin film semiconductors. Likewise—some metals are heavy metals that are unwanted because they change the electrical characteristics of the glass surface. Similar to the oleic and oleic acid coatings, anions, and cations described in the previous article, the paper size is suitable for financial and family standards (CNS) A4; -------- 7 --- Γ — (please first Read the note on the back and fill in this page) Line 593189 A7 _____B7 V. Description of the invention (f) The sub-surfactant printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs has been applied to the glass surface. However, most anionic surfactants dissolve in water, so they will not form a good and stable coating on the glass surface in the presence of water. As the data presented below, these surfactants are found to be unsuitable for use in protecting LCD glass. Many researchers have studied the cationic surfactants in the adsorption solution on Shi Xishi and understood the distribution of gelled Shi Xishi. See Gollub τ · ρ, Koopal LK, Bijsterbosch Β.Η, Langmuir 1986, 12 3188-3194; Goloub, Τ, Ρ., Koopal L.K., Langmuir 1997, 13, 673-681; Zajac , J., Torapette, JL, Partyka, S., Langmuir 1996, 12, 1357-1367; Rosen, MJ Surfacatants and Interfacial Phenomena, J. Wiley & Sons, New York, 1989, Chapter 2; and Harell, J. Η., Scamehorn, JF nAdsorption from Mixed Surfactant Systems ", in Mixed Surfactant Systems, Surfactant Series Vol. 46, Ogino, K, and Abe, M, Ed .; Marcel Dekker, Inc. New York, 1992, pp. 263- 281. At neutral pH, the surface of the silicate is usually negatively charged, which can immediately adsorb cationic species. Techniques for coating anionic surfactants to glass at temperatures below the boiling point of water have been disclosed in U.S. Patent No. 45,443,95 to Evans. As described in detail below, the present invention finds that various forms of cationic surfactants (as well as non-ionic surfactants and trimethylammonium internal salts) can be quickly structured on hot glass (eg, glass temperature is higher than 175.) :) And the formation of a coating film, which is quite hydrophobic (that is, the fixing contact angle is 40 degrees) I ----- 7 --- ^ — ^ 9 — (Please read the precautions on the back before filling in this page)

1. The paper size of the 1T line is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) 593189 A7 B7 V. Description of the invention (f) Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs to substantially reduce the adhesion of glass fragments to the glass (Eg reduce the adhesion of glass fragments larger than 1 micron in size by at least 80%). Previous studies including cationic surfactants and glass did not reveal this important result. Briefly, there is a need in the industry for a method of protecting glass objects, especially LCD glass sheets. The method is mainly characterized by: (1) This method must be able to be immediately added to the overall manufacturing glass processing process, especially to form the end of the processing process, so The newly formed glass is protected immediately after it is manufactured. In order to comply with this standard, the coating film must be able to withstand the environment in which the glass production line is manufactured and (b) the method of coating materials must be safely used in that environment; (2) The coating film must be reasonably hydrophobic to protect the adhesion of debris caused by cutting and / or grinding of the glass sheet, as well as adhesion of other contaminants such as particles, which will interact with these contaminants during storage and transportation before use Contact; (3) the coating film is sufficiently strong to provide continuous protection after exposure to considerable moisture during the cutting and / or grinding process; (4) the coating film must be substantially completely removed from the glass before final use in order to produce Liquid crystal display and display; and (5) The coating film must be composed of a material, which is relatively rare in the final use of glass. Quantity. Summary of the invention: The present invention provides methods for temporarily protecting the surface of glass objects from external dust and temporarily protecting glass objects from adhering debris. According to the first aspect of the present invention, the present invention provides a method by using the surface (please read the precautions on the back before filling this page)

* 1T This paper size is applicable to Chinese National Standard (CNS) A4 (210X29 * 7mm), Central Ministry of Economic Affairs, Staff Consumption Cooperation, Du Printing 593189 A7 -------- ----- B7 5 2. Description of the invention (fe) Coating can remove the hydrophobic film (called the hydrophobic coating film or surface) to temporarily protect the surface of the glass object. _Thickness is—Molecules to tenths, or thickness can be greater than tenths if necessary. The second aspect of the present invention is to provide a method for reducing fragmentation when cutting or grinding glass objects. The financial method includes a ⑴axis⑴ hydrophobic film on the surface of the object; (B) cutting or grinding glass objects; And (c) removing the film. Similarly, the thickness of the film is from one molecule to the tenth, or it may be greater than tenths of the thickness if necessary. The present invention provides a method for processing glass. The glass has at least one flat surface. The method includes: (a) forming a hydrophobic coating film on the surface of a glass object by applying a water-soluble solution; Contains at least one surfactant on the surface of the glass object, where (ly manufacturing process produces novel glass at south temperature; (2) the temperature of the newly formed glass in contact with the solution is higher than 丨 is preferably higher than 200 ° C ); (3) surfactants are selected from cationic surfactants, non-ionic surfactants, and trimethylammonium internal salts; and (4) the coating film reduces the adhesion of glass fragments to the surface; (b) cutting Glass; (c) grinding and / or polishing at least one edge of the cut glass; and (d) removing the film from the surface; wherein (i) water or contains water in at least one of steps (b) and (c) Part of the solution is coated on the surface of the coating film; and the paper size is suitable for the home, and the CNS Γα4 specification (210x297 mm 7 (Please read the precautions on the back before filling in this page)

5. Description of the invention (*)) (11) After the steps (b) and (C), the contact angle of the coating film fixing liquid droplet is less than 40 degrees. In a specific preferred embodiment, the coating film is applied to the demon glass by spraying: it can make other coating branches such as buttons, liquid descent, lamp core applicators, etc., but it is less preferred because The termination of the glass manufacturing process usually depends on concealment. The system is in the process of drawing down using an overflow. In other preferred embodiments, the coating film is removed using a water-soluble detergent solution, for example, for commercial cleaning, and preferably combined with a basic and / or ultrasonic cleaning. In addition, the surface of the coating film can be exposed to an oxidizing environment before coming into contact with the detergent solution. The oxidizing environment / detergent solution is preferentially combined with scrubbing and factory cleaning. The oxidizing environment can be formed by corona discharge, by using ultraviolet rays to generate ozone, or by oxygen plasma. Ability to use ozone-containing water. Although less preferred, the coating film can be removed using its own oxidizing environment method. Other aspects of the invention are described in detail below. Brief description of the drawings: The first figure (Figure 1) shows the isothermal properties of ideal adsorption of ionic surfactants on a relatively charged surface under equilibrium conditions. The second figure (Figure 2) shows the isothermal nature of the general surfactant adsorption of long chain quaternary ammonium salts on silica under equilibrium conditions. The third figure (Figure 3) shows the amount of contact angle of the water droplets on the coated glass substrate. The fourth picture (Fig. 4) shows the cations in the cationic surfactant spray solution 593189 A7 ____ B7 Imprint of the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (poor) Surfactant dicocodimethylammonium gasification (Solid square data points) and didecyl dimethyl gasification (empty round data points). The relationship between the surfactant concentration and the contact angle of the fixed droplets. The fifth graph (Figure 5) is a graph showing the relationship between the bond length of different cationic surfactants and the contact angle. Empty data points are cleaned with water and solid data points are cleaned with CONTRAD 70. Surfactant technology: Surfactant adsorption on surfaces has been studied for many years, especially with regard to the dispersion and coagulation of inorganic powders in aqueous or non-aqueous systems. See Rosen, M.J. Surfacants and Interfacial Phenomena, 2nd Edition, Wiley-Interscience, New York, 1989, pages 337-361; Tadros, TF (Edition) Surfacants, Academic Press, Orlando, Florida, 1984, pages 197-220 ; Botre, C., De Marti is, F. and Solonas, M, J. Phys · Chem ·, 1964, 68, 3624; Zajac, JL, Trompette, JL ·, Partyka, S. Langmuir, 1996, 12, 1357; Goloub, T.P., Koopal, L.K., Bi jsterbosch, BH, Sidorova, MP Langmuir, 1996, 12, 3188; and Goloub, TP, Koopal, L.K. Langmuir, 1997, 13,673 The adsorption mechanism has been proposed, which depends on the solution concentration of the surfactant, the ionic strength, the presence of other molecules, and the temperature in a limited range. Among other things, the structure of surfactants coagulated in inorganic media has been studied for many years. The factors that affect the formation of a good coating film include the size and number of the ends of the hydrophobic chain. -------- · (--- ^-Office · — (Please read the precautions on the back before filling this page)

1. The paper size of the 1T line is applicable to China's national standard (CNS) A4 specification (210X297 mm) ((593189 A7 B7) V. Description of the invention (q) Central standard of the Ministry of Economics 扃 The printed target and length of the employee consumer cooperative, the chain is not saturated And branching, surfactant concentration, solution ionic strength, other substances present in the solution, and characteristics of the coated surface. Silica and silicate-based glass usually have a negatively charged surface at pH 7. See Zajac, J., Trompette, JL, Partyka, S. Langmuir, 1996, 12, 1357. Obviously related to the present invention. Studies in the literature reporting on the adsorption of surfactants in aqueous solutions are for equilibrium conditions and relatively low temperatures. The present invention Surfactant coatings are formed under non-equilibrium conditions and at high temperatures. Studies by Somasundaran and Fuerstenau (Somasundaran, P., Fuerstenau, D.W., J. Phys. Chem. 1966, 70, 90) have been shown The adsorption isotherm of ionic surfactants adsorbed on silica in impregnated solutions has three regions (see Rosen, M. J. Surfactants and Inter Facial Phenomena, 2nd Edition, Woley-Inter science, New York, 1989. Figure 1). In the first region, the surfactant is adsorbed by ion exchange. In the second region, the hydrophobic tail interacts The resulting stability leads to an increase in the rate of adsorption. The formation of molecules on the surface is called semi-glia adsorption. At the end of region 2, the surface charge is changed by the adsorption of the surfactant. In region 3, each additional molecule needs to be added Overcome electrostatic repulsion but obtain the stability of hydrophobic chain interactions. This reduces the adsorption rate. The starting point of region 3 and the critical colloid (that is, the concentration of surfactant molecules starting to form colloidal particles) are reported in the literature. See Griffith? MJ, Alexander , AEJ Colloid Interface Sci., 1967, 25, 311; Greenwood, FG ·, Parfitt, GD ·, Picton NH, Wharton, DG Adsorption from Aqueous Solution, ----- 1 ---.---_-- — (Please read the notes on the back before filling this page)

* 1T line This paper size applies to Chinese National Standards (CNs) A4 (210X 297 mm) 593189 A7 B7 V. Description of the invention () Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs

Adv. Chem. Series 79, American Chemical Society, Washington, D. C., 1968, 135; and Groot, R. C. 5th. Int. Cong. Surface-Active Substrances, Barcelona, Spain, September, 1968, II, p. 581. The equilibrium adsorption of long-chain quaternary ammonium salts on silica follows a curve similar to that in Fig. 1 but differs. Figure 2 shows the general curve. The graph is similar to Harell JH, Scamehorn, JF11 Adsorption form Mixed Surfacant System ", in Mixed Surfacant Systems, Surfacant Series Vol. 46, Ogino, K, and Abe, M, Ed .; Marcel Dekker, Inc.New York Figure 1992, pp. 263-281, shown in Figure 2, the initial region is a general diluted surfactant solution, which is far below the critical micelle concentration. Above this concentration, any addition of a surfactant produces higher density colloidal particles rather than higher density free molecules in solution. In region 1, the adsorbed molecules are separated to a considerable extent and usually do not bind to each other. Region 2 can see a fairly sharp increase in slope due to increased long-chain binding. In region 3, the surface charge has been neutralized and has lost its position to adsorb other surfactant molecules. As a result, the slope is significantly reduced. Finally, in zone 4, the surface is saturated and no surfactant can be adsorbed onto the original surface. The separation point between zones 3 and 4 is usually the critical micelle concentration of the surfactant. As shown in Figure 1, the curve in Figure 2 is an equilibrium condition. Although it provides a general framework, it is not directly applicable to the case where the surfactant of the present invention is coated on a glass surface. > Detailed description: This paper size applies to Chinese National Standard (CNS) A4 specification (21 (^ X297)) ---- (Please read the precautions on the back before filling this page) Line 593189 A7 _______ _B7 V. Invention Explanation (丨 丨) 12 1 ^ In n · Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economics, and specifically explained here, the present invention provides a method to temporarily protect glass by providing a removable film on the surface of an object The surface of the object. The thickness of the film is from one molecule forming the film material to ten molecules of the material. The film thickness of about one molecule is referred to herein as, a single layer, if a thicker film can be used if necessary, and priority Ground is used in many applications because it can withstand the water cleaning during the cutting, grinding, and edge modification of glass sheets. The glass object protected by the film of the present invention can be any glass object. In the embodiment of the present invention, the glass object is glass Sheet. In another embodiment, the glass object is a liquid crystal display (LCD) glass sheet. 'One application of the present invention is to protect glass The body is protected from external contamination. In the method of the present invention, one or more surfaces of the object are coated with a thin film of cationic, nonionic or trimethylammonium internal salt. The coated glass will be exposed to the outside during storage or transportation Contaminants, such as transport and storage in sealed plastic or glass containers. Coated surfaces are preferentially treated by their edges because the film cannot be designed to resist scratching. After unpacking, the film is easily removed in some ways It includes the following discussions · Cleaning process, cleaning by ultraviolet, ozone, or by using a solution containing or etching a glass surface and a wetting agent solution. The formed surface is clean, dry, and uniformly hydrophobic This method has the advantage of protecting the recording layer, the material, and the glass, and the glass body has a clean, dry, uniform and hydrophobic surface. Another special application of the method of the present invention is when cutting or grinding glass objects. Method to reduce the adhesion of debris. Cut as described previously (please read the precautions on the back before filling this page), 1T-line This paper size applies to China National Standards (CNS) 丨 Ten A 593189 A7 -_ B7 V. Description of the Invention (丨 2) The glass handle constitutes a serious problem in the process of cutting or grinding glass, especially in the manufacture of LCD glass. The invention provides a stable, removable, water-based film on the surface of glass objects to prevent the formation of debris. The term "removable" as used herein refers to the film that is adhered to the glass and is processed, stored and transported. The film is not removed or changed significantly, but it can be removed. The film adheres to the glass by interacting with silica on the glass surface and acts as a shield between the surface of the glass object and the glass fragments. Prevent glass fragments from coming into contact with the surface of glass objects, and the occurrence of wafer adhesion will be reduced. In addition, the hydrophobic film will reduce water condensation, which will cause permanent debris to adhere. In order to prevent debris from sticking, a stable and removable hydrophobic film is formed on the surface of the glass object, cutting or grinding the glass object, and removing the film. The protective glass is protected from contamination, and the film used to protect the wafer from sticking is composed of cationic, non-ionic, or trimethylammonium internal salt surfactants. The films printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs have different thicknesses, such as one molecule to two molecules, or less than several hundred molecules, or less than 100 nm, or from several nm to tens of nm. In order to be able to visually inspect the glass defects, the thickness of the first coated broken glass can be changed from being invisible to being visible after washing. It cannot be seen that the thickness of the coating film is 1 micrometer or less, and it is about one nanometer to several tens of nanometers, for example, one molecular size. This thickness enables the film to be removed using UV / ozone cleaning or thermal decomposition without significantly altering the glass surface or leaving significant residues, which can interfere with the final product, where the glass is coated with another material. The degree of film coating should be sufficient to completely cover the glass surface. For example, the paper size applies to the Chinese National Standard (CNS) A4 (210X297 mm) ΙΓ 593189 A7

593189 5. Description of the invention (丨 +) Calculate the number of adhered fragments. The method for reducing the adhesion of the film-containing debris is to coat the broken powder with / 85. (: Lower glass plate, and then stored in _I_Ϊ humidity cleaning and debris calculation. In determining the adhesion value of debris, his method is known to those skilled in the art. Surfactant film: Nuxian Besuo 5 Erming, The coating film of the present invention is composed of a surfactant. In particular, the hair film essentially contains a secretive agent. The "substantially contained" herein does not include other components that will affect the film. Therefore, "film" The texture contains at least one kind of surfactant, including at least one kind of interfacial active agent, and may contain other components, which does not actually affect the film, such as adhesives, solvents, etc. Some examples of suitable surfactants include cationic interfaces Active agents, non-ionic agents, and tris-ammonium-based internal salts. So-called here, at the time of interfacial activity, I includes compounds that are active because the surface of the bifunctional group is active. Sexual ends and at least one insoluble hydrophobic end. As known in the industry, trimethylammonium internal salts are polar molecules (when working in the Central Standards Bureau of the Ministry of Economics, Consumer Consumption Cooperative) The zwitterionic ion in the system has a ρΗ equivalent or higher than the isoelectric point of the molecule) and usually has an acid and a quaternary ammonium end. The cationic surfactant has a hydrophobic tail and a positively charged end. The ammonium bromide (CTAB) is used in the present invention. The cationic surfactant film is due to the positive charge on the head and on the glass surface; the gravitational attraction between charges tends to adhere to the glass surface, and it can be sprayed on the glass object by spraying the surfactant aqueous solution Coated on top of the paper while the object is at a higher temperature (referred to as Cong Jianzhe (21〇 × 297 male thin (7 W189 A7 ------------ B7 V. Description of the invention (丨 〇6 11 Ministry of Economic Affairs) Although printed by the Consumer Standards Cooperative of the Central Bureau of Standards, although the priority is lower, the interface can also be applied by dipping, spin coating, or any other process, which can bring the surfactant solution into contact with the glass surface. Additionally The coating step may be followed by a cleaning step. The surface may additionally include a surface-active agent or a mixture of surface-active agents, such as a mixture of two, three, «kinds of interfacial activity. The film may include% ionic boundary φ • Agents & compounds, mixtures of non-ionic surfactants, trimethylsuccinates, or combinations thereof, such as cationic and / or non-ionic surfactants. Can be varied and include different interfaces Multiple films of the active agent can be applied to the surface in sequence. For example, it contains a cationic interface / tongue agent, different non-ionic surfactants, different triammonium-based internal salts, or different compositions. _ Can be applied to silk. When age-covered glass surface; does not have a uniform negative surface charge or has a different (positive, negative or neutral) charge. It is beneficial to use interface-active hemp compounds or -groups of individual _. When the interface-active framework used is concentrated in solution, it is preferred to use the component as a sequential coating film to avoid agglomeration (for example, to avoid attraction more than its hydrophilicity), which would occur if it existed in a single solution. For some surfactants, they do not irreversibly build up in the solution. The surfactants can be mixed and the aqueous mixture can be directly applied to the glass using the techniques described above. Cationic surfactants are preferably used as quaternary ammonium salts, which have 1 to 2 alkyl (or mixed alkyl / alkenyl) chains and have an average length of 8 to 18 carbon atoms. This is a compound part, its molecular formula is (Ri) a (R2) bNX, where R1 is saturated or unsaturated, straight or branched chain, which contains 8-24 carbon atoms, and r2 is saturated, which contains 1-6 carbon atoms Or unsaturated group, a = i, 2 or 3, b = (4-1), n This paper size is applicable to China National Standard (CNS) A4 specification (21 〇 297 revolutions) (Please read the back Note for this page, please fill out this page) Order 593189, invention description (A)

7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs as nitrogen and X as anions (including fluoride, gaseous, bromide, iodide, and acetic acid but not limited to this compound). In addition to carbon, long chains can contain heteroatoms. R2 is usually fluorenyl, but can be ethyl, propyl (n- or iso), or butyl (η-, 2 ~, or di-). However, as these groups become larger, the ends will limit the density and stability of the bulking surfactant on the surface due to the reduced chain-to-chain interaction. The quaternary ammonium surfactant raw material is a synthetic or natural material such as vegetable (such as coconut or soybean) or (such as animal, marten, pig) oil. Natural materials usually have a chain length distribution (see Table 丨 examples) c. Solutions of known concentration and quantity are sprayed onto the surface, and a continuous layer of surfactant is formed on the glass surface. The surface is initially fully charged, with the cationic end of the cationic surfactant at the surface and a hydrophobic tail facing away from the surface. Washing with tap water or deionized water will remove the surfactant leaving a single layer of surfactant on the surface. The contact angle between water droplets and a single layer of this series of surfactants on the surface is in the range of 60-75 degrees. A good coating depends on the surfactant concentration, purity, and chain length. A chain length of less than 8 carbon atoms does not form a coating film, which causes hydrophobicity on the glass surface after washing in water. That is, the contact angle after cleaning is less than 8 degrees, which means that there is no substance on the surface. When the chain length is increased, the internal chain interaction will produce greater stability to the surface coating film. : Cationic surfactants with one or more long-fired base chains usually form the best coating film. ‘It is also possible to use a surfactant with three long chains, but it is difficult to get into an aqueous solution. Similarly, paper scales with 6 carbon atoms or longer are applicable to China National Transfer (CNS) A4 · (21 (^ 297mm ---- *-; ---; -I— (please first Read the notes on the back and fill in this page} 、 11 line 593189 A7 B7 V. Description of the invention ((f)) Surfactants printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs enter the aqueous solution with great difficulty. Coating Film: Film It is preferred to coat the surface by spraying a solution of a surfactant and a hydrolysis solvent (such as deionized water) on the surface and evaporate the hydrolysis solvent to form a thin film. As previously explained, the thin film is preferentially formed during the forming process. After coating on the newly formed glass sheet, in particular, the aqueous solution is applied to the glass when the glass surface temperature is higher than 175 ° C and preferably higher than 200 ° C, wherein the glass temperature is measured by an infrared sensor commonly used in the industry The glass temperature is preferably less than 400 ° C at the beginning of the coating process, for example, 300. It is beneficial to apply the film at this temperature during the manufacturing process because the glass is clean and during the rest of the manufacturing process The medium film will protect the glass. Coating the film to the glass at this temperature means that the coating time is relatively short, which is determined by the rate of glass formation and the lowest glass temperature at the end of the coating process. The glass consists of several different processes Manufactured, which includes a floating process, a slit drawing process, and a fusion drawing process. See, for example, US Patent No. 338696, 3682609, the description of which is incorporated herein by reference. During the fusion drawing process, the newly formed glass sheet is pointed in a vertical direction. In these cases, the aqueous solution should be applied in some cases without droplets, because the droplets will interfere with the glass's solidity, for example, the droplets will cause Glass has cracks. Generally, droplets can be avoided by adjusting the spray size throughout the coating process to keep the glass temperature above 150 ° C. When adjusting the spray size, for example to reduce it, the interfacial activity in the solution The concentration of the agent must be adjusted, for example, to increase the appropriate amount (please read the notes on the back before filling this page) Zhang scale is applicable to China National Standard (CNS) A4 specification (210X297 mm) > 〇593189 A7-------- ___B7 V. Description of invention (丨 publication) 19 Printed interface of the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs The active agent reaches the surface to completely coat the glass surface. Without spraying, the coating film can also be coated with a soft material filled with a solution containing a thin film material. Other possible methods include dipping, liquid bay coating, rolling Sprayers, brushes, etc. Spraying is preferred because it can cooperate with glass movement during the glass manufacturing process. Usually the glass on both sides is coated simultaneously, if necessary, it can be coated on each side sequentially. Interface in aqueous solution The concentration of the active agent is usually between 1 mol / L and 0.5 mol / L. Preference is given to using concentrations in the range of 0-4 mol / liter to 10 mol / liter. Coated glass can be cured after film coating. The curing step will increase the hydrophobicity of the film. Curing can be achieved by any means, such as curing by heating or the formation of free radicals by exposure to dissociative light, plasma treatment, or exposure to ultraviolet light, which is sufficient to achieve curing but not too high to change the required coating film characteristics Poor or cause the coating film to be removed. Heat treatment is preferred. The glass can be cleaned after the coating material is applied. Cleaning can use ultrasound to improve film removal. This cleaning will remove the entire excess film material, leaving a single layer of molecules attached to the glass surface. Cutting and / or grinding the glass sheet typically involves adding moisture to the glass sheet. Water causes the coating to be washed away to remove excess film material. In some cases, the moisture used in the cutting / grinding process will remove too much material. In these cases, instead of using water, an aqueous surfactant solution will be used, which will reduce the amount of surfactant removed from the surface. In the case where the coating film contains more than one surfactant, the solution used in cutting / grinding contains all or some of the surfactants constituting the coating film. J.. ^-^^ 丨 (Please read the notes on the back before filling this page)

、 1T line This paper size applies to Chinese national standard (CNS> A4 size (210X297 mm) > 1 593189

20. Description of invention (door) Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs In the coating film, flammable liquids should be avoided even as a common solvent. Special ship, _ refined or _ as a sugar agent should be avoided, because it tends to adsorb silanol on the surface of new glass. It is a dirt heart that will interfere with the adsorption of the surfactant on the newly formed glass surface. 'Removal of the film: The main key to a successful protective coating is that it will be retained during the manufacturing process and can be removed if necessary. The secret explained that the surfactant-coated red coating was difficult to apply before the first nick and was quite strong enough to remain in the rest of the manufacturing process. It can be removed individually or collectively using brushing and / or ultrasonic cleaning using commercially available detergent formulations. Detergent formulations typically include anionic surfactants and non-ionic surfactants. Variations can be made. The detergent formulation can contain only a non-ionic surfactant at a high pH, for example, a pH value of about 12. It can be changed and can be removed by oxidizing a coating film. In one embodiment of the present invention, the thin film is removed by exposure to ultraviolet rays, such as short-wavelength ultraviolet rays, to produce ozone that oxidizes the coating film. UV / ozone oxidation technology can be implemented using a low-pressure mercury bulb, which converts oxygen to the short-wavelength UV of ozone. Ultraviolet light having a wavelength of less than 300 nm is particularly suitable, for example, 184.9 nm and 253.7 nm emitted from low-pressure mercury vapor bulbs. Traces of carbon dioxide and water are by-products of the UV removal process. Due to the low-density coating, the amount of carbon dioxide and water is minimized. The removal process takes one minute to one hour, and restores the glass surface to its original state, which is similar to the initial situation after the glass is formed. This paper size applies to Chinese National Standard (CNS) A4 specification (210X297 mm) -------.-- ^-I 丨 (Please read the precautions on the back before filling this page) Order line 21591189 A7 ______B7 V. Description of the Invention (10) Other oxidation methods printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs include (1) the use of corona discharge to generate ozone, and (2) the use of ozone-containing water Dissolved in water). Use oxidation and detergent formulations and / or brushing and / or ultrasonic cleaning, where the oxidation needs to reach a strength and last a period of time (for example, 30 seconds) enough to attack the outer surface of the coating film. It is known that coating film removal can be removed by a glass manufacturer or shipped to an end glass user, such as a liquid crystal display manufacturer, and that users can remove the coating film from glass. Surface treatment of glass: As previously explained, the coating film of the present invention can be preferentially directly applied to newly formed glass that is still hot and minimizes the chance of contamination. However, if this is not possible (eg in a laboratory setting to test the coating film), the glass surface needs to be cleaned before the coating film is applied. The cleaning may be performed by various methods including chemical cleaning methods known in the industry and thermal decomposition. The example below reveals a cleaning method that can treat glass surfaces. The following cleaning techniques are designed to remove adsorbed organic molecules from the glass surface. The main goal of these methods is to expose the hydroxyl groups and siloxane bonds in the glass molecules. Two priority methods for environmentally harmless and non-toxic cleaning of glass substrates are ultraviolet / ozone cleaning and thermal decomposition. Use low-pressure mercury bulbs for UV / ozone cleaning in an atmosphere containing oxygen. It has been described in J. Vac. Sci. Technol. A3, 1027, (1985) by Vig et al., Which is incorporated herein by reference. A low-pressure mercury grid bulb manufactured by BHK (88-9102-20) in an air-filled stainless steel enclosure is suitable for this cleaning method. After the surface is cleaned, place the cleaned surface at a distance of 2 cm from the bulb (please read the precautions on the back before filling this page). The paper size applies to China National Standard (CNS) A4 (210X297 mm) 593189

22 The Central Office of the Ministry of Economic Affairs, Feng Yuanhuan, printed the printing office of the Consumer Cooperative for 30 minutes. The second method is high-temperature pyrolysis, in which the surface is slowly heated to about 500 ° C, maintained at this temperature for 4 hours, and slowly cooled. Generally, the high temperature treatment includes heating and cooling time of about 5 hours. Other cleaning techniques include laser volatilization and flames passing through the surface. Two acid cleaning techniques can also be used to clean the glass. It is less preferred because it contains harmful liquids. These techniques use strong acids with oxidants to remove organic molecules adsorbed on the glass surface. A technique using 3 units of hydrogen peroxide and 7 units of concentrated sulfuric acid (the ratio is not fixed and can be changed from 1: 9 to 1: 1) uses pure and high temperature (above 90 ° C) . Other methods use saturated potassium dichromate in concentrated sulfuric acid, which can be completely dissolved by dissolving 20 grams of dichromic acid in 90 grams of water and slowly adding 900 grams of concentrated sulfuric acid. The glass is first cleaned by removing all visible dirt and then washed with a surfactant solution. It was immersed in the oxidizing acidic solution for 20 minutes and washed with water. If using chromic acid, try # dipping again in 6N hydrochloric acid for 20 minutes and washing again with water. Preference is given to using double distilled or fairly purified water without organics. In order to check cleanliness, the water film on the surface should be quite thin, which will form optical interference fringes, as explained in the example below. If the surface loses water, it needs to be cleaned again. These acidic cleaning processes dissolve the glass surface and improve the longevity of glass. Examples: The following examples will provide a detailed description of the invention, and are not intended to limit the scope of the invention to the specific embodiments described. Caiguanjia 2) 0X797 ^) j --- r --.-- 丨 · -IMMφ! (Please read the notes on the back before filling out this page) Line 593189 Printed by A7 of the Consumer Cooperatives of the Central Labeling Bureau of the Ministry of Economic Affairs B7 V. Description of the Invention (> V) Example 1: This example shows the formation of a cationic surfactant film on the glass surface, which protects the surface from external pollution. 1. Prepare a piece of glass by immersing it in Chromerge solution at room temperature or freshly preparing Pirani Etch. Chromerge contains a saturated solution of potassium dichromate in concentrated sulfuric acid over 20 minutes. It is cleaned by applying 20 grams of heavy chromium Potassium acid (prOiab0, France 94120 reagent grade) was formulated in 90 grams of water. 900 grams of reagent grade concentrated sulfuric acid was used as the final solution cooled to room temperature. It was then cleaned in Chromerge. The glass was washed with sufficient water and placed in 6N hydrochloric acid solution (Fusher Science, 78996 France analysis grade) for 20 minutes. A hydrochloric acid bath designed to remove any chromium ions remaining on the silica surface was prepared by adding a portion of water to a portion of reagent grade concentrated hydrochloric acid. The glass is finally washed with water to complete the cleaning process. Pirani Etch is formulated by adding 7 parts of concentrated sulfuric acid (Prolabo, France 94120-grade) to three parts of hydrogen peroxide ((Prolabo, France 94120-grade)). When the solution is mixed it will heat up quickly and immediately Use it. The cleaning is then fully cleaned with very pure water (resistance higher than 18M ohms and organic pollutants less than 10 ppm). This process produces a clean, wet glass surface with negatively charged hydrophilic silica. When exposed to the outside air The surface remained clean after a few days, which meant that external contaminants would not be strongly adsorbed to the glass. In order to verify that the surface was hydrophilic, the water film was very thin after the final cleaning to show optical interference fringes. These streaks occurred On the entire surface 3 2 (Please read the precautions on the back before filling in this page) The paper size of the book is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) 24593189 A7 B7 V. Description of the invention (>) If it does not happen, dehydration caused by surface contamination of the film and repeated cleaning processes are repeated. The glass surface should be immediately covered with water to prevent contamination by external contamination. 2. Coating the glass surface with a cationic surfactant. A clean glass sheet is immersed in 0.4 mmol / L (mM) hexadecyltrimethyl. Syrian Desert Compound (CTAB) surfactant. It is a surfactant that is adsorbed to the glass surface by a charge (its front end is positively charged and the surface of the stone slab is negatively charged in water, and the pH value in water is greater than 2). The glass plate is then pulled out of the solution vertically and dried to leave a single layer of film. 3. Store and ship the protected glass glass in a rigid plastic or glass container that is secured at the edges and sealed to prevent Dust and other pollutants. 4_Removal of surfactant film After unpacking, the cationic film previously described was removed from the glass sheet by placing a low-pressure mercury light bulb with low wavelength ultraviolet rays placed at a distance from the glass containing the coating surface 6-8 It takes 45 minutes to generate centimeters and generate ozone. Example 2: Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs ------ ^ --- ^-I ^^ 1 (Please read the note on the back first Please fill in this page again.) This example shows the use of the cationic surfactant dicocodimethylammonium vaporized to form a stable hydrophobic removable coating on the glass surface. Dicocodimethylammonium vaporized is made from coconut oil. It contains tri-glycemic glycerol J3, glyceryl hexadecanoate, and glyceryl stearate. See The Merck Index, Tenth Edition, Merck & Co., Inc., Rahway NJ 1983. It has two Each long fatty chain is on each nitrogen atom, and the chain usually has a different length on any known molecule. Table 1 shows ARQijAI) 2C- This paper is in accordance with China National Standard (CNS) A4 (2! 0X297) 25) 593189 A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs. 5. Description of the invention (outside) 75. The length distribution of the dicocobifluorenyl ammonium gas chain, which is sold by Akzo Nobel. As shown in the table, approximately 20% of the molecules have at least one 16 or more carbon atom chain. Some 18 carbon chains have divalent bonds.

Isopropanol (5% by weight) of ARQUAD 2C-75 sold by Akzo Nobel is diluted with water to form an emulsion. When ARQUAD 2C-75 is diluted 100-10000 times and sprayed on 15-400X: glass, the glass surface is not wetted. Spray with BINKS 115 spray gun. Higher concentrations can be used, but they are not required and they will waste material. When the coating film was removed, ESCA showed no change in the composition of the glass surface without the coating film. The samples were a) coated, b) contaminated with glass powder, and c) stored at 85 ° / 0 humidity / 85. (: Case and d) cleaned up, which shows that the coating film will prevent glass fragments from adhering to the substrate. Sample 3: In this example, different cationic, nonionic, and amphoteric surfactants were tested for their ability to improve removable, hydrophobic coatings on LCD glass. The test objective is to confirm that the coating film can reduce the adhesion of debris to produce a scratch-resistant coating film. The glass preparation and coating processes described below can be performed immediately to provide data to predict the characteristics of the coating film in a manufacturing environment. The glass used in the test was our 1737 LCD glass. The samples were made in a 2% detergent solution (CA05, Semiclean or CONTRAD 70) at 60 ° C in a 40 kHz ultrasonic solution for 15 minutes. The samples were washed in water to remove ions, and placed in a second 40kHz ultrasonic deionized water at 60 ° C for 15 minutes. The sample is then placed in deionized water and dried in the air. 0 I, ------.-- ^-IΦ ----- 1T ------ (Please read the precautions on the back first (Fill in this page again)

> 7 593189 A7 B7 26 V. Description of the Invention (zf) The Central Ministry of Economic Affairs and the Peasant Consumer Cooperative Co., Ltd. printed surfactants to remove ionic water for dilution and complete mixing. All samples were sprayed onto 5 " χ5π flake 1737 glass slides, which were preheated on a 300 ° C hot plate. The coating film was spray-coated with BINKS 115. The coating film is applied until water vapor forms on the glass surface. After drying under atmospheric conditions, the samples were washed with deionized water to remove excess surfactant and allowed to dry. Contact angle measurement is performed on a microscope stage with NEC CCD connected to a monitor and a lister. An 18 million ohm drop was formed using a Gilmont GS -1200 micron syringe. The formation of water droplet images and angles are measured manually using an indexer. Four drops of water were placed on each of the 515 " sample glass slides and measurements were performed and the measured contact angles were averaged. Can be changed, can be measured using a COLi ELLY contact angle analyzer. The device uses a CCD camera to take pictures, analyzes the images with a computer, and measures the contact angle. When the contact angle value can be measured to degrees, the measurement change is ± 3 degrees. Therefore, the recorded value is the closest angle. All measurements were performed on the same day as the coating film was formed or removed to eliminate the problem of adsorbing organic matter in the air. Due to the heating of glass to 300 ° C and the use of spray coating, coating film coating cannot be accurately achieved under equilibrium. However, coating film consistency can be measured by measuring angles. After cleaning the glass excess material, the measured angle is a function of the surfactant concentration in the coating film. Figure 4 shows the titration curve (also known as the "isotherm") of the dicocodimethylammonium vaporization and BTC 1010 (didecyldimethylammonium vaporization). Lower limit concentrations can never be established in these graphs. The curve shows that the concentration of the spray solution is much higher than the amount needed to obtain good consistency on the glass. A-Gong 97 (Please read the notes on the back before filling this page) Line 593189 A7 __B7 V. Description of invention t) 27 Comparison printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs Figures 2 and 4 show coating these cations The isotherm, in which water evaporates in seconds, is similar to the isotherm of equilibrium low temperature. Prior to the present invention, it was understood that these surfactants can be successfully formed on hot glass surfaces in a short time. As shown in Figure 4, BTC 1010 shows a single-layer coverage at low concentrations, which is 2 to 3 times lower than that of a coconut dihydrazone base gas. Generally, longer aliphatic chains result in lower critical micelle concentrations. In some studies, two surfactants with different chain lengths were mixed under a controlled ratio. The isotherm slope did not change when the relative concentration of the longer chain surfactant was increased, but the isotherm shifted to a lower solution. concentration. See Harell JH., Scamehom, JF, Adsorption from Mixed Surfacant Systems ", in Mixed Surfacant Systems, Surfacant Series Vol. 46, Ogin〇, K., and Abe, M, Ed .; Marcel Dekker, lnc. New York, 1992, pp. 263-28. Due to the average chain length of dicocobifluorenyl ammonium vaporized and BTC 1010 are about 13 carbon atoms and 10 carbon atoms, respectively, the isotherm of dicocodifluorenyl ammonium vaporized is expected to be in BTC and so on. To the left of the temperature line. In Figure 4, the isotherm is inverted, which indicates that some impurities are present in ARQUAD 2075, which will inhibit the initial surface coverage. However, the slope of the dicocodimethylammonium gasification zone 2 shows It is steeper than BTC 1010, which is consistent with the difference in bond length between the two materials. As shown in Figure 4, for these two materials, there is a wide range of solution concentrations that produce a good coating film. Some other surfactants are evaluated as shown in Table 2- Figure 5. The effect of chain length on contact angle is shown in Figure 5. In this curve, it is shown that

The paper size applies the Chinese National Standard (CNS) from the specifications (210x 29 * 7 male I

Ji n —1 n n n I I n I t Please read the notes on the back before filling in this page)

* 1T line 28593189 A7 B7 V. Description of the invention (V)) The contact angle of the base (long-chain) ammonium salt coating film printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. The 6 carbon atom chains form a very stable coating film, which produces a contact angle of 60 degrees or more. The contact angle is usually -40 degrees, preferably -50 degrees after the excess surfactant is washed off, and the coating film is considered good. The graph also shows that the CONTRAD 70 is easier to clean. Quaternary ammonium salts having a chain length of 14 carbon atoms or more cannot leave the surface as easily as shorter chain lengths. The contact angle after removal should be $ 10 degrees and priority. The AFM data of ARQUAD 2C-75 coated glass washed at 2% CONTRAD 70 showed that the surface sugar content showed a return to the original value. The ESCA data show that the surface composition is substantially the same as the uncoated glass. Since residual carbon is usually found on the glass surface when ESCA is manufactured, TOF-SIMS is formed on the coated sample. No cleaner was formed on the adhered surface. As shown in Table 2-5, cationic surfactants are not the most successful in forming appropriate coatings. Some nonionic and some amphoteric surfactants are also acceptable. At the same time, anionic surfactants do not form a layer, which is stable. The use of water for further cleaning is not appropriate. The above examples are not intended to limit the scope of the invention. Those skilled in the art can make various changes and modifications to the present invention. Therefore, the following patent application scope will cover various changes and modifications of the present invention. Table 1 Number of carbons distributed in the length of the ARQUAD 2C-75 chain 8 10 12 14 16 18 m% 5 Fly 50 19 10 10 (Please read the notes on the back before filling this page) The size of the paper is based on Chinese national standards ( CNS) A4 specification (210X297 mm) * 5 ° 593189 A7 B7 29 V. Description of invention (%) Table 2 Forms a good coating film material and it is easy to use the market to supply aqueous cleaning compounds to remove the brand name manufacturer Ammonyx MO Stepan Amphosol CDB Stepan

Arquad 2C-75 Akzo Nobel Cation

Arquad DMCB-80 BRIJ 35 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (Please read the precautions on the back before filling this page) Form Contact Angle (degrees) / Description of Amine Oxide 62 Degrees / Using 2% Contrad 70OJ / S ) Removal of cationic poly 67 ° C / 2% Contrad 70OJ / S) Removal of complex 70 ° C / 2% Contrad 70OI / S) Removal without 2% CA05 or 2% Semiclean KG 60 ° C / 2% Contrad 70OI / S) Remove 55 degrees / Use 2% Contrad 70OJ / S) to remove cations

Akzo Nobel ICI Americas Anion Inc. Didecyl Difluorenyl Stepan Ammonium (BTC 1010) Di-dodecyldi Aldrich Ammonium Bromide Dodecyl Tri Aldrich Ammonium Ammonium Bromide Aldrich Ammonium Bromide Rewoteric am WITCO B-14 LSU Rewoteric 'am WITCO HC Tween 85 Cation 82 degrees / 2% Contrad 70CU / S) removal and 2% CA05 and 2% Semiclean Cation 67 degrees / 2¾ Contrad 70CU / S) Removal of cations 55 degrees / 2% Contrad TO0J / S) Removal of cations 62 degrees / Removal of internal ammonium salts with 2% CA05 (ϋ / S) 64 degrees / Removal of internal ammonium salts with 2% Contrad 70 (U / S) 68 degrees / Using 2% CA05 (U / S) to remove ICI Americas non-ionic 42 degrees / Using 2% Contrad 70 to remove Inc. WITCO amine oxide 62.5 degrees / Using 2% CA05 to remove CA05, and Semiclean KG is Decon Cleaners sold by Labs, Inc. (Bryn Mawr. PA), SPC Electronics America, Inc. (Norcross, Georgia), and Yokohama Oil and Fats Industry Co. Ltd. (Yokohama-Shi Kana Gawa-Ken, Japan). U / S = 40kHz Ultrasonic cleaning at 5CTC. The amine oxide dissociates in the solution · and thus becomes a cationic detergent.

Varox 1. Contrad 70, 2. 3.-on paper A Ns 6 / fv quasi-standard home country one country | Chinese one use I suitable

9 2 X zy line-593189 A7 B7 V. Description of the invention (1) Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Table 3 Forms a good coating film material but is difficult to remove using water-soluble market cleaning compounds. Although not tested, these materials are expected to be removed first by oxidation treatment and by water-soluble cleaning compounds. Trademark name Manufacturer form Contact angle (degrees) / Description Di-hexacyldecyl Aldrich cation 77 degrees / Contrad 70 cleaned dimethyl ammonium bromide 17 degrees dimethyl ditetradecyl Aldrich cation 76 degrees / Contrad 70 cleansing base bromide 1A 18 ° Ethomeen C / 12 Akzo Nobel amine ethoxylate 68 ° / Contrad 70 clean up 16 ° Ethomeen T / 25 Akzo Nobel 50 ° acetic acid 50 ° C / Contrad 70 clean up 17 ° Ethoquad C / 12 Akzo Nobel cationic 50 degrees / NIT 15 degrees after cleaning with Contrad 70 Incroquat-26 Croda cationic 58 degrees / 20 degrees after cleaning with Contrad 70 Poly Acid BASF cationic 67 degrees / polymer 13 degrees after cleaning with Contrad 70 Rewoteric am WITCO 49% betaine / 9% after cleaning with 2% CA05 UCARE polymer Amercho 1 cationic poly after initial cleaning 23 degree contact LR-30M 96 degrees after cleaning with Contrad UCARE polymer Amercho 1 cationic poly after cleaning The initial contact angle was 17 degrees. The LR-shed was 83 degrees after cleaning with Contrad. 1. The ethoxylated amine dissociated in the solution and became a cationic detergent. f 碕 Please read the notes on the back before filling in this page. j Order- ----- line one paper size applies to China National Standard (CNS) A4 specification (210 X 297 public holidays) 31 593189 A7 B7 V. Description of the invention Π〇) Table 4 Materials that do not have high water solubility to form effective coatings Brand name Manufacturer form Contact angle (degrees) / Description Octadecyltrifluorenyl ammonium bromide Aldrich Cation 80 degrees / Isoacetone solvent required to make stable Solution

Arquad 2HT-75 Akzo Nobel cations are too soluble in water. Dissolve in isopropanol / water to form a solution. -------: ---;-^ 9 — (Please read the notes on the back before filling in this page) Threading printed by the Central Consumers Bureau of the Ministry of Economic Affairs, the Consumers' Cooperatives, the paper is printed in accordance with Chinese national standards (CNS) A4 size (210X297 mm)

Claims (1)

593189 6. Scope of patent application The glass breaking temperature is at least 15 ° C. Solution method and water method :: = ^ 1 method, in which the beneficial side of the aqueous solution contains at least 8 and no more than _ carbon atoms; knife chain, the average page = shot patent surface No. 6 slave method The method of cationic interfacial activity or carbon sequestration is included in the method, and the method is not to exceed the scope of the scope, wherein the surfactant is dicocoaikyidimethw ammonium salt. 9. The method according to item 7 of the application, wherein the active agent is didecyldimethylammonium salt. ", 10. The method according to item 1 of the scope of the patent application, wherein the concentration of the surfactant in the aqueous solution is between 10-6 mol / liter and 0.5 mol / liter. Printed by the Employees' Cooperative of the Central Government Bureau of the Ministry of Economic Affairs11. The method according to item 1 of the scope of patent application, in which the number of glass fragments that are adhered to the surface of the non-coated film is compared under the comparison conditions, and the coated film will reduce glass fragments Adhere to at least 80% of the surface. 12. The method according to item η of the scope of patent application, wherein the number of glass fragments adhered to the surface is reduced by at least 90%. 13. The method according to item 1 of the scope of patent application, wherein step (d) comprises applying an aqueous solution containing a cleaning agent to the coating film. The private paper scale applies the Chinese National Standards (CNS) M specification (2 × 0 × 297 mm). The scope of the patent application = the second method: _3 methods, the paste contains washing. The method for declaring item 13 of the patent, wherein step ⑷ includes brushing the method of item 13 of the patent, wherein the step of adding ultrasonic energy to the coating film and brushing the surface. = The method of claim, wherein step (i) includes oxidizing the M surface and (19). (Special fiber and tender method), the injection method d) includes the outer surface of the J oxide coating film. 20. The method according to item 15 of the patent application, wherein step (i) includes at least oxidizing the outer surface of the coating film. 21. The method according to item 16 of the scope of patent application, which reduces oxidation of the outer surface of the coating film. The method according to item 17 of the scope of patent application, wherein ozone is used to oxidize the outer surface of the coating medium. Printed by the Workers' Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs. 23. The method according to item 22 of Shenyan's patent scope, in which ozone is formed by corona discharge. 24. The method according to item 22 of the patent application, wherein ozone is formed using ultraviolet rays. 25. The method according to item 1 of the patent application, in which ozone-containing water is used to oxidize the outer surface of the coating film. This paper size is suitable for »Two Standards (CNS) A4 (210X297 mm) 593189 A8 26. According to the scope of the patent application, the rear coating film has a fixed droplet contact. 27. According to the application standard _ ^^ = abruptly, the surface has a fixed droplet contact angle of less than 10 degrees. t8. According to the first item of the detailed scope, "Zhongzai Buyi Station and ⑹3 :::: contains a water solution containing the cleaning agent used in Step 涂覆 on the surface containing the coating film. = According to the application In the method of item 1, the towel is in the _moisture cleaning 4 and step ⑷, the surface is relatively thin, and the glass can be inspected by careful inspection. 30. The method according to the first item of the patent application, wherein the glass has at least two flat flat surfaces. ㈣ and Tu Qingyu on both surfaces of step (a). 31. The method according to item 范围 of the scope of patent application, in which the glass is used after step 制造 to manufacture a liquid crystal display. (Please read the note on the back before reading (Fill in this tile), the standard of printed wood paper used by the Shell Standard Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs of the People's Republic of China (CNS > A4 size (21 × 297 mm) (The above columns are filled out by this bureau.) '' Μ 二 i; :: i _ί n ， :::, _ Invention Patent Saying Spoof ~~ J 593189 Chinese Method of Temporarily Protecting Glass Objects Invention Name English Method For Temporarily Protecting Glass Articles Name (Chinese) 1. Willian Bock 2. Aaron Rob Amycare 3. Anaklebband 4. Name of the Inventor (English) 1. Wiiliam Birch 2. Alain RE Carre 3. Dana C. Bookbinder 4. David L. Tennent Nationality 1. France 2. France 3. United States 4. U.S. Residence and Residence 1. 28 Sullo Road, Marousy, Sousse, France 2. Chateaure, France 313 Bata Coran Road 3. 2261 David Road, Corning, New York, USA 4. 4748 Carson Road, Canberl, New York, USA Name (Name) (Chinese) 1. Corning Company Name (Name) (English) 1. Corning Incorporated Nationality 1. U.S. Applicant's Residence and Domicile (Office) 1. Name of Representative (Chinese) of Howden Park, Corning District, New York, USA 1. Name of Representative (English) of Alfred Michelson 1.Alfred L. Michaelsen C: \ ProgramFiles \ Patent \ p423.ptd Page 1 593189 Scope of patent application 1. A method of treating glass, the glass having at least one flat surface, the method comprising: (a) forming a hydrophobic coating film on the surface by applying a water-soluble solution onto the surface, the solution including at least one interface The active agent is part of the glass manufacturing process, among which (1) the manufacturing process produces newly formed glass at high temperature, · The newly formed glass is at a temperature higher than 175t (preferably higher than fine. 0 in contact with the solution;) (3) Surfactants are selected from cationic surfactants, non-ionic surfactants, and salts within trimethyl anchor groups; and (4) the coating film reduces the adhesion of glass fragments to the surface; (b) cuts glass; (c) grinding and / or polishing at the edges where the touch is light; and (d) removing the film from the surface; where (i) water or water is contained in at least one of steps (b) and (c) Part of the solution is coated on the surface of the coating film; and (ii) after steps (b) and (c), the contact angle of the fixing film droplets is at least 40 degrees, which is printed by the Central Laboratories of the Ministry of Economy Non-ionic surfactant refers to the surfactant The interfacial active part does not carry an ionic charge. 2. The method according to item No. of the patent application scope, wherein the glass in step 垂直 is vertical and the glass temperature is kept high throughout step a) so that the droplets Does not form on the palate. 3. According to the oldest method in the scope of patent application, in the step of the terminal, the paper is used by the two companies in China (CNS) A4 (21〇297 mm)