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    • 专利摘要:
    METHOD FOR MANUFACTURING A CLEANABLE ITEM, CLEANABLE ITEM AND METHOD FOR USING A CLEANABLE ITEM. The finishing coating with hydrophilic front surfaces and which are attached to the siloxane to an underlying body element. Also, methods for making and using such articles.
    公开号:BR112014016062B1
    申请号:R112014016062-7
    申请日:2012-12-28
    公开日:2021-03-30
    发明作者:David M. Mahli；Caleb T. Nelson；Frederick J. Gustafson；Justin A. Riddle；Lan H. Liu；Mitchell A. F. Johnson；Moses M. David；Naiyong Jing；Robert A. Yapel；Yu Yang
    申请人:3M Innovative Properties Company；
    IPC主号:
    专利说明:

    FIELD OF THE INVENTION
    [001] The present invention relates to articles with cleanable surfaces, methods for making them and methods for using them. BACKGROUND OF THE INVENTION
    [002] The easy cleanability of surfaces, for example, removal of dirt and soot, graffiti or erasable surfaces, has long been a desired feature. Illustrative applications where easy cleanability is desired include windows, electronic device screens, work surfaces, appliances, door and wall surfaces, signs, etc. Other illustrative applications include writing surfaces such as whiteboards, file folders, notebooks, etc. where effective gravity coupled with easy later removal of writing is desired.
    [003] Articles having cleanable surfaces have been produced from a variety of materials offering various combinations of properties. Commonly recognized modalities include certain marker materials, dry erasable articles, note papers, file folders with clean tabs, etc.
    [004] Dry erasable boards have been used as writing surfaces for years due to their convenience and versatility. The tables provide a means of expression that eliminates the dirt and hassle of a blackboard.
    [005] A permanent challenge for dry erasable articles is to find surfaces that can be easily cleaned, resist stains when permanent markers are used for writing, can be easily erased when conventional dry erasable markers are used for writing, whether durable, etc. Glass and porcelain surfaces have long been used on the writing surfaces of dry erasable articles, but improved performance is desired, for example, because although their non-porous surfaces are easily engravable with dry erasable markers and then easily erased after a day, the writing sticks to the board over time, making it difficult or even impossible to remove by cleaning with a dry eraser. Dry erasable writing that is not removable by a dry eraser is commonly referred to as ghosting. In addition, permanent markers tend to adhere well and cannot be removed easily. For example, such writing is often removable only with solvents such as isopropanol. Solvent-based cleaners are being replaced on the market with cleaners containing water, surfactant, and a small percentage of a less volatile organic solvent. Such cleaning agents are not always able to remove permanent marker writing from dry erasable boards. Other common dry erasable surfaces with the same cleaning problems include coated films, melamine and painted plastic and steel.
    [006] A continuing need exists for cleanable writing surfaces that exhibit durable and robust performance; improved receptivity to writing with a variety of writing instruments under a variety of conditions; and improved wipability and cleanability, exhibiting low ghosting properties. DESCRIPTION OF THE INVENTION
    [007] The present invention relates to cleanable articles that provide surprising performance. It is also related to methods for making such articles and methods for using such articles.
    [008] Briefly summarizing, the method of the invention for making cleanable articles comprises: (a) providing a body element having a front surface on which at least a portion of the front surface is bondable to siloxane; (b) applying an outer coating composition to at least a portion of the siloxane-bondable surface, the outer coating composition comprising a siloxane-binding component; and (c) curing the outer coating composition to form a hydrophilic outer coating having a siloxane bond with the front surface of the body element, thereby producing a cleanable article.
    [009] In short, cleanable articles of the invention comprise: (a) a body element having a front surface; and (b) a hydrophilic outer coating attached to the front surface of the body element by siloxane bonds.
    [010] Briefly summarizing, an illustrative method of the invention for using such cleanable articles comprises, for example: (a) providing a cleanable article as described in the present invention; (b) write on the hydrophilic outer coating to generate a caption about it; and (c) rubbing, optionally with water or another solvent, to remove at least a portion of such a caption.
    [011] Cleanable articles manufactured as described here have been found to exhibit surprising performance, that is, they can be easily and effectively cleaned, repeatedly. The articles of the invention can be used in various demanding applications, for example, they are particularly suitable for use as dry erasable surfaces. They exhibit excellent gravity with conventional dry erasable markers and, in addition, the writing of permanent markers can be readily removed from them with water and a cloth or eraser. Solvents or special tools do not need to be used. The articles of the invention have so far provided usefulness and durability that have not been achieved. For convenience, the invention is described with reference to rewritable articles. It will be understood, however, that the advantageous benefits of the invention are achieved in several other applications. BRIEF DESCRIPTION OF THE DRAWINGS
    [012] The invention is further explained with reference to the drawings, in which:
    [013] Figure 1 is a schematic view of an illustrative embodiment of a cleanable article of the invention.
    [014] These figures are not to scale and are intended to be illustrative and not limiting. KEYWORDS AND GLOSSARY
    [015] It should be understood that several terms used here will be defined according to their normal meaning, as known to those skilled in the art. However, it should be understood that the following terms have the meanings described herein.
    [016] The terms "a / o" "one, one" "at least one," and "one or more" are used interchangeably.
    [017] For use in the present invention, it is assumed that all numbers are modified by the term "about" and, preferably, by the term "exactly". Although the numerical ranges and parameters that define the broad scope of the invention are approximations, the numerical values stated in the specific examples are recorded as precisely as possible. All numerical values, however, inherently contain certain errors that necessarily result from the standard deviation found in their respective test measurements.
    [018] The term "coatable material" means a non-solid material (for example, liquid or gel-like) that is capable of being coated on a surface.
    [019] The term "comprises" and variations thereof do not have a limiting meaning where such terms appear in the description and in the claims.
    [020] The term "whiteboard" includes dry erasing surfaces known as glass, porcelain steel, painted steel, painted metal, painted hard panels, melamine, coated film, coated paper, coated fiber board sheets and other coated surfaces. known dry erasers currently marketed.
    [021] The phrases "in the range" and "within a range" (and similar statements) include the end points of the indicated range.
    [022] The term "matte finish" means a surface with a rough or granular finish or texture that has no high gloss or luster. The matte finish can be smooth to the touch, but it is usually free of glare or significant highlights.
    [023] The term "optically transparent" refers to the transparency of a material, typically allowing for a high level (for example, greater than about 99% corrected for reflection losses) of light transmission and low opacity (for example, less than about 1%).
    [024] The term "polymer" will be understood to include polymers, copolymers (for example, polymers formed using two or more different monomers), oligomers and combinations thereof, as well as polymers, oligomers, or copolymers that can be formed in a miscible blend, for example, by coextrusion or reaction, including transesterification. Both block copolymers and random copolymers are included, except where indicated otherwise.
    [025] It will be understood that the term "polymeric material" includes polymers, as defined above and other organic and inorganic additives such as, for example, antioxidants, stabilizers, anti-zonizers, plasticizers, dyes, UV absorbers, hindered amine photostabilizers (HALS) and pigments.
    [026] The words "preferential" and "preferably" refer to the modalities of the invention that may provide certain benefits, under certain circumstances. However, other modalities may also be preferred under the same or other circumstances. In addition, the mention of one or more preferred modalities does not imply that other modalities are not useful, and is not intended to exclude other modalities from the scope of the invention.
    [027] The term "or" is generally used in its sense including "and / or", unless the content clearly states otherwise. The term "and / or" means one or all of the listed elements or a combination of any two or more of the listed elements.
    [028] Numeric range quotes with extremes include all numbers contained within that range (for example, 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, 5, etc. ).
    [029] Groupings of alternative elements or modalities presented in the present invention should not be considered as limitations. Each element of the group can be designated and claimed individually or in any combination with other members of the group or other elements found in it. It is anticipated that one or more members of a group may be included, or may have been excluded, from a group for reasons of convenience and / or patentability. When any inclusion or deletion occurs, the specification is considered to contain the group, as modified, thus satisfying the written description of all Markush groups used in the attached claims.
    [030] When a group is present more than once in a formula described here, each group is "independently" selected, whether specifically declared or not. For example, when more than one group Y is present in a formula, each group Y is selected independently. In addition, the subgroups contained within these groups are also selected independently. For example, when each group Y contains an R, then each R is also selected independently.
    [031] For use in the present invention, the following terms have the meanings indicated: "organic group" means a hydrocarbon group (with optional elements in addition to carbon and hydrogen, such as oxygen, nitrogen, sulfur, and silicon) that is classified such as an aliphatic group, a cyclic group or a combination of aliphatic and cyclic groups (for example, alkaryl and aralkyl groups), in the context of the present invention, organic groups are those that do not interfere with the formation of an erasable marker surface at rub dry and permanent. "aliphatic group" means a straight or branched saturated or unsaturated hydrocarbon group, this term is used to cover alkyl, alkenyl and alkynyl groups, for example; "alkyl group" means a saturated, linear or branched hydrocarbon group, which includes, for example, methyl, ethyl, isopropyl, t-butyl, heptyla, dodecyl, octadecyl, amyl, 2-ethylhexyl and the like; "alkylene group" is a divalent alkyl group; "alkenyl group" means an unsaturated, linear or branched hydrocarbon group, with one or more carbon-carbon double bonds, such as a vinyl group; "alkynyl group" means an unsaturated, linear or branched hydrocarbon group, with one or more triple carbon-carbon bonds; "cyclic group" means a closed ring hydrocarbon group, which is classified as an alicyclic group, aromatic group or heterocyclic group; "alicyclic group" means a cyclic hydrocarbon group with properties similar to those of aliphatic groups; "aromatic group" or "aryl group" means a mono or polynuclear aromatic hydrocarbon group; and "heterocyclic group" means a closed ring hydrocarbon, where one or more of the atoms in the ring is an element other than carbon (for example, nitrogen, oxygen, sulfur, etc.). A group that can be the same or different is treated as something "independently".
    [032] A substitution is anticipated in the organic groups of the complexes of the present invention. As a means of simplifying the discussion and mention of certain terminology used throughout this application, the terms "group" and "portion" are used to differentiate between chemical species that allow substitution or that can be substituted and those that do not and cannot be replaced. Therefore, when the term "group" is used to describe a chemical substituent, the chemical material described includes the unsubstituted group and that group with atoms of O, N, Si or S, for example, in the chain (as in an alkoxy group ), as well as carbonyl groups or other conventional substitution. Where the term "portion" is used to describe a chemical or substituting compound, only an unsubstituted chemical material is intended to be included. For example, the term "alkyl group" is intended to include not only pure alkyl substituents of saturated open chain hydrocarbons, such as methyl, ethyl, propyl, t-butyl and the like, but also alkyl substituents that contain additional substituents known in the art. technique, such as hydroxy, alkoxy, alkylsulfonyl, halogen atoms, cyano, nitro, amino, carboxyl, etc. Therefore, the "alkyl group" includes ether, haloalkyls, nitroalkyls, carboxyalkyls, hydroxyalkyls, sulfoalkyls, etc. On the other hand, the term "alkyl moiety" is limited to the inclusion of only pure open chain saturated hydrocarbon alkyl substituents, such as methyl, ethyl, propyl, t-butyl and the like.
    [033] The term "primary particle size" refers to the average size of the single, unglued silica particles.
    [034] For use in the present invention, "hydrophilic" is used to refer to a surface that is wetted by aqueous solutions, and does not express whether the layer absorbs aqueous solutions or not. Surfaces on which water droplets or aqueous solutions show a static contact angle with water less than 50 ° are called "hydrophilic". Hydrophobic substrates have an angle of contact with water of 50 ° or more.
    [035] For use in the present invention, "at least one monolayer of a hydrophilic-functional compound" includes, for example (1) a monolayer or a thicker layer of molecules covalently linked (via siloxane bonds) to the surface or primer on the surface of a substrate, such molecules being derived from the hydrophilic-functional compound and (2) a monolayer or a thicker layer of a water-soluble polymer covalently attached to the surface or primer on the surface of a substrate. If the hydrophilic-functional compound includes dimers, trimers or other oligomers of individual molecules, then "at least one monolayer" would include a monolayer of these dimers, trimers or other oligomers, or a mixture of such oligomers with monomers.
    [036] The previous summary of the present invention is not intended to describe each of the embodiments presented or all implementations of the present invention. The description that follows illustrates more particularly the illustrative modalities. In several places, throughout the application, guidance is provided through lists of examples, in which the examples can be used in various combinations. In each instance, the list cited serves only as a representative group and should not be interpreted as an exclusive list. DESCRIPTION OF REALIZATIONS OF THE INVENTION
    [037] Figure 1 shows an illustrative embodiment of a cleanable article of the invention 10 comprising a body element 12 with external coating 14 connected to the siloxane at the front surface 16 thereof. In the embodiment shown, the body element 12 comprises a base element 15 with a cover layer 13 on the front surface thereof. The article 10 additionally comprises an optional adhesive layer 18 and an optional removable liner 20 on the rear surface 22 of the body element 12.
    [038] As described above, the method for making cleanable articles of the invention comprises: (a) providing a body element having a front surface on which at least a portion of the front surface is bondable to siloxane. (b) applying a coating composition to at least a portion of the front surface bondable to the siloxane, the coating composition comprising a component bondable to the siloxane. and (c) curing the coating composition to form an overlay coating having a siloxane bond with the front surface of the body element, producing a cleanable article. BODY ELEMENT
    [039] The body element typically constitutes substantially the main portion of the article for which the cleanable surface according to the invention is desired. For example, it could be a panel on a door, window, ceiling or other architectural surface, a cabinet surface or piece of furniture, a board or whiteboard surface, a surface on a personal item such as a notebook, clipboard, etc. Those skilled in the art will be able to carry out the invention using a variety of body elements, for example, of suitable configuration and construction for the intended application, according to the invention described herein.
    [040] In addition to exhibiting other desired characteristics, the front surface of the body layer must exhibit a binding character to siloxane. In some embodiments, the siloxane-binding ability of the body element is achieved by incorporating a siloxane-bondable layer as the front surface of the body element, for example, forming a suitable layer on an underlying base element. In other embodiments, the siloxane-binding ability of the body element is achieved by incorporating siloxane-binding components within the body element on the front surface thereof, for example, suitable siloxane-binding nanoparticles projecting from it. FRONTAL BODY ELEMENT SURFACE
    [041] At least a portion of the front surface of the body element, and preferably essentially the entire front surface thereof, is bondable to siloxane, i.e., capable of forming siloxane bonds with the compatible formulated outer coating. This characteristic can be an inherent characteristic of the material of which the front portion of the body element is composed, for example, exposed siloxane-binding particles dragged in a polymeric matrix or by providing a "diamond-like glass" covering layer on the surface of a base element of polyester film.
    [042] In some illustrative embodiments, the body element comprises a layer of the reaction product of a mixture comprising at least one curable component selected from the group consisting of (meth) acrylate monomers, (meth) acrylate oligomers. Other curable materials will be selected for yet other embodiments in accordance with the present invention.
    [043] Coating materials suitable for use in the present invention can comprise any of a variety of film forming materials. In some embodiments, the coating material is a polymeric material composed of one or more polymers and / or oligomers in solvent. In some embodiments, the coating material is a mixture of one or more monomers, oligomers and / or polymers in one or more solvents. In other embodiments, the coating material includes the aforementioned oligomer (s), monomer (s) and / or polymer (s) in one or more solvents together with a volume of particles or nanoparticles.
    [044] In some embodiments, the body element comprises nanoparticles. Illustrative examples of nanoparticles that can be used in the body elements of the invention include aluminum oxides, tin oxide and antimony, bismuth subsalicylate, bohemite, calcium carbonate, calcium phosphate, cerium dioxide, graphene, haloisite, lanthanum boride , lithium carbonate, silver, amorphous silica, colloidal silica, silicon dioxide, titanium dioxide, zinc oxide, zirconium oxide or dioxide. Suitable nanoparticles can be of various shapes including irregular and regular shapes, nanotubes, nanoplatelets, cylindrical, etc.
    [045] In certain embodiments, applying a primer coating composition to a writing surface involves bringing the surface of the substrate into contact with a coating composition containing nanoparticles. The coating composition containing nanoparticles includes an aqueous dispersion having a pH less than about 5 including silica nanoparticles having an average diameter of about 40 nanometers or less, and an acid having a pKa of <about 3.5. The method further includes drying the coating composition containing nanoparticles to provide a silica nanoparticle primer coating on the substrate surface. In certain embodiments, if desired, the coating composition containing nanoparticles further includes a tetra-alkoxysilane. In certain embodiments of the coated article, the primer coating containing nanoparticles is about 100 angstroms (A) to about 10,000 A thick. In certain embodiments of the coated article, the functional sulfonate coating is no more than about 10 microns thick and is often no more than about 1 micron thick.
    [046] Nanoparticles can be modified on the surface, referring to the fact that the nanoparticles have a modified surface, so that they provide a stable dispersion. "Stable dispersion" refers to a dispersion in which colloidal nanoparticles do not agglomerate after standing for a period of time, such as about 24 hours, under ambient conditions, for example, at room temperature (about 20 to about 22 C) and atmospheric pressure, without extreme electromagnetic forces.
    [047] Surface-modified colloidal nanoparticles can optionally be present in a polymer coating used as a coating composition of the present invention with nanoparticles present in an amount effective to improve the durability of the finished or optical element. The surface-modified colloidal nanoparticles described herein can have a variety of desirable attributes, including, for example, compatibility of the nanoparticle with a coatable composition so that the nanoparticles form stable dispersions within the coatable composition, reactivity of the nanoparticle with the coatable composition making it more durable composite and a low impact or uncured composition viscosity. A combination of surface modifications can be used to manipulate the properties of the uncured and cured composition. The surface-modified nanoparticles can optimize the optical and physical properties of the coating composition, for example, greater mechanical resistance of the resin, minimized changes in viscosity with an increase in the volume load of solids in the coating composition and maintenance of the optical clarity with the increase of the volume loading of solids in the coating composition.
    [048] In some embodiments, nanoparticles are surface-modified nanoparticles. Suitable surface-modified colloidal nanoparticles can comprise oxide particles. Nanoparticles can comprise a range of particle sizes in relation to a known particle size distribution for a given material. In some embodiments, the average particle size can be in the range of about 1 nm to about 100 nm. Particle sizes and particle size distributions can be determined in a known manner including, for example, by transmission electron microscopy (TEM). Suitable nanoparticles can comprise any of a variety of materials such as metal oxides selected from alumina, tin oxide, antimony oxide, silica, zirconia, titanium oxide and combinations of two or more of the aforementioned items. Surface-modified colloidal nanoparticles can be substantial and fully condensed.
    [049] In some embodiments, silica nanoparticles can have a particle size ranging from about 5 to about 75 nm. In some embodiments, silica nanoparticles can have a particle size in the range of about 10 to about 30 nm. Silica nanoparticles can be present in the coating composition in an amount of about 10 to about 95 percent by weight. In some embodiments, silica nanoparticles may be present in the coating composition in an amount of about 25 to about 80 weight percent, and in other embodiments, silica nanoparticles may be present in a coating composition in an amount of about 30 to about 70 weight percent. Silica nanoparticles suitable for use in the coating compositions of the present invention are commercially available from Nalco Chemical Co. (Naperville, Ill.) Under the product designation NALCO ™ Colloidal Silicas. Suitable silica products include NALCO ™ 1040, 1042, 1050, 1060, 2327 and 2329 products. Suitable pyrolyzed silica products include, for example, products sold under the brand name AEROSIL ™ series OX-50, 130, 150 and 200, with Degussa AG, (Hanau, Germany), and CAB-O-SPERSE ™ 2095, CAB-O-SPERSE ™ A105, CAB-O-SIL ™ MS from Cabot Corp. (Tuscola, Ill.). The surface treatment of nanometer sized particles can provide a stable dispersion in the coatable composition (for example, a polymeric resin). Preferably, the surface treatment stabilizes the nanoparticles so that the particles are well dispersed in the coating composition, resulting in a substantially homogeneous composition. In addition, nanoparticles can be modified on at least a portion of their surface with a surface treatment agent, so that the stabilized particle can copolymerize or react with the coating composition during curing.
    [050] Metal oxide nanoparticles can be treated with a surface treatment agent to make them suitable for use in the present invention. In general, a surface treatment agent has a first end that will attach to the surface of the particle (covalently, ionically or through strong physiosorption) and a second end that confers compatibility of a particle with the coating composition and / or reacts with the coating composition during curing. Examples of surface treatment agents include alcohols, amines, carboxylic acids, sulfonic acids, phosphonic acids, silanes and titanates. The type of treatment agent may depend on the nature of the metal oxide surface. For example, silanes are typically preferred over silica and other silica fillers. The surface modification can be carried out either after mixing with the coating composition or after mixing. It may be preferable in the case of silanes to react the silanes with the particle or nanoparticle surface before incorporation into the coating composition. The amount of surface modifier can depend on factors such as particle size, particle type, molecular weight of the modifier and type of the modifier. In general, a modifier monolayer is attached to the particle surface. The fixing procedure or reaction conditions required also depend on the surface modifier used. For silanes, surface treatment can take place at elevated temperatures under acidic or basic conditions for a period of about 1 hour to about 24 hours.
    [051] Suitable surface treatment agents for particles to be included in the coating position include compounds such as, for example, isooctyltrimethoxysilane, N- (3-triethoxysilylpropyl) methoxyethoxyethoxyethyl (PEG3TES), SILQUEST ™ A1230, N- carbamate (3-triethoxysilylpropyl) metoxietoxietoxietila (PEG2TES), 3- (methacryloyloxy) propyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3- (methacryloyloxy) propyltriethoxysilane, propilmetildimetoxissilano, 3- (acriloiloxipropil) metildimetoxissilano (methacryloyloxy) propildimetiletoxissilano (methacryloyloxy) propildimetiletoxissilano, phenyltrimethoxysilane, n -octiltrimethoxysilane, octadecyltrimethoxysilane, propyltrimethoxysilane, vinylmethyldiethoxysilane, vinylmethyldiethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, 3- (methacryloyloxy), 3-vinylldimethylethoxylsilane, dichlorohexyl, hexane year, vinyltris-isobutoxysilane, vinyltrisopropenoxysilane, vinyltris (2-methoxyethoxy) silane, styrylethyltrimethoxysilane, mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, acrylic acid, methacrylic acid, 2- acid, 2-acid, stearic acid methoxyethoxy) ethoxy] acetic (MEEAA), beta-carboxyethylacrylate, 2- (2-methoxyethoxy) acetic acid, methoxyphenylacetic acid and mixtures of two or more of the above items.
    [052] The surface modification of the particles in a colloidal dispersion can be achieved in several ways. The process involves mixing an inorganic dispersion with surface modifying agents and, optionally, a co-solvent such as, for example, 1-methoxy-2-propanol, ethanol, isopropanol, ethylene glycol, N, N-dimethylacetamide and 1-methyl-2 -pyrrolidinone. Co-solvent can be added to improve the solubility of surface modifying agents, as well as the modified particles on the surface. Subsequently, the mixture comprising the inorganic solution and the surface modifying agents is reacted at room or elevated temperature, with or without mixing. In one method, the mixture can react at about 85 C for about 24 hours, resulting in a surface-modified solution. In one method, where metal oxides are modified on the surface, the surface treatment of the metal oxide may involve the adsorption of acid molecules to the particle surface. The surface modification of the heavy metal oxide occurs preferably at room temperature.
    [053] In some embodiments, the average particle sizes (for example, particle diameter) can be within the range of about 0.05 microns to about 60 microns. In addition to the aforementioned particle sizes, the present invention also contemplates the use of smaller and larger average particle sizes. In embodiments of the invention, at least a portion of the aforementioned particles can be surface-modified in the manner described above. In other embodiments, all particles are surface-modified. In yet other embodiments, none of the particles is surface-modified.
    [054] Depending on the desired application, the front surface of the body element may have an opaque finish or a glossy finish.
    [055] In some embodiments, the body element is formed by applying a coating composition suitable to at least one potion on the front surface of a substrate and curing the composition to produce a body element locally on the substrate, for example, the surface of the substrate. piece of furniture, door, window, etc. In other embodiments, a preformed body element or preformed cleanable article of the invention is attached to at least a portion of the front surface of the substrate, for example, self-adhesive lamination or use of a bonding adhesive or other layer of fixation.
    [056] At least a portion of the front surface of the body element, and in some cases essentially the entire front surface of the body element, is bondable to siloxane, that is, capable of forming siloxane bonds with an externally formulated coating layer compatible. This ability may be an inherent characteristic of the material from which the front portion of the body element is composed, for example, exposed siloxane-binding particles trapped in a polymeric matrix or providing a siloxane-binding composition as the front surface of the body element, for example, formation of a "diamond-like glass" covering layer on the surface of a polyester film.
    [057] In some embodiments, the siloxane-binding ability of the body element is achieved by exposing siloxane-binding particles in the polymer matrix. Illustrative examples of methods of achieving this are treatment of the frontal surface with chemical attack by plasma, corona, etc.
    [058] US patent No. 6,696,157 (David et al.) Discloses diamond-type glass films (sometimes called "DLG") and methods for making them that can be used in the present invention. An advantage of such materials is that, in addition to providing siloxane-bondable front surface in the body element that provides strong bonding to the outer coating, such layers can, in addition, provide hardness and dimensional stability that serves to support the overlying outer coating, making the resulting most durable and damage resistant cleanable article. This is particularly useful when the underlying components of the base element can be relatively softer.
    [059] Illustrative diamond-like glass materials suitable for use here comprise an amorphous covalent, carbon-rich diamond-type system containing carbon, silicon, hydrogen and oxygen. DLG is created by depositing a dense random covalent system comprising carbon, silicon, hydrogen and oxygen under ion bombardment conditions by locating a substrate on an electrode energized in a chemical radiofrequency ("RF") reactor. In specific implementations, DLG is deposited under conditions of intense ion bombardment of mixtures of tetramethylsilane and oxygen. Typically, DLG shows negligible optical absorption in the visible and ultraviolet regions, that is, about 250 to 800 nm. Also, DLG typically shows improved resistance to bending break compared to some of the other types of carbonaceous films and excellent adhesion to various substrates, including ceramics, glass, metals and polymers.
    [060] DLG contains at least about 30 percent atomic carbon, at least about 25 percent atomic silicon, and less than or equal to about 45 percent atomic oxygen. DLG typically contains about 30 to about 50 percent atomic carbon. In specific implementations, DLG can include about 25 to about 35 in atomic percentage of silicon. Also, in certain implementations, DLG includes about 20 to about 40 in an atomic percentage of oxygen. In specific advantageous implementations the DLG comprises about 30 to about 36 in atomic percentage of carbon, about 26 to about 32 in atomic percentage of silicon and about 35 to about 41 in atomic percentage of oxygen on free base of hydrogen. "Hydrogen free base" refers to the atomic composition of a material as established by a method such as electron spectroscopy for chemical analysis (ESCA), which does not detect hydrogen even if large quantities are present in the thin films. BASE ELEMENT OF THE BODY ELEMENT
    [061] Typically the base element essentially consists of or has a surface comprising a sheet of glass, ceramic, porcelain, paper, metal or plastic. In some embodiments, the base element is a polymeric film. Illustrative examples include polymeric films selected from the group consisting of polyester (for example, polyethylene terephthalate, polyethylene terephthalate), olefin (for example, polypropylene, polyethylene), polyvinyl chloride, polycarbonate, allyl diglycol carbonate, polyacrylates, such as methacrylate polymethyl, polystyrene, polysulfone, polyether sulfone, homo-epoxy polymers, polymers with epoxy addition with polydiamines, polydithols, polyethylene copolymers, fluorinated surfaces, cellulose esters such as acetate and butyrate, biopolymers, polylactic acid and mixtures thereof.
    [062] As desired, the base element can be opaque, translucent, transparent or clear. In some modalities, the basic element will be retroreflective. The term transparent means to transmit at least about 85% of the incident light in the visible spectrum (wavelength from about 400 to about 700 nm). Substrates can be colored.
    [063] Basic elements used here can be flexible or inflexible, as desired.
    [064] In some embodiments, the base element will be substantially self-supporting, that is, sufficiently dimensionally stable to maintain its shape as it is moved, used and otherwise manipulated. In some embodiments, the article will additionally be supported in some way, for example, with a reinforcement structure, adhered to a support surface, etc.
    [065] If desired, the body element can be provided with graphics on its surface or embedded in it, such as words or symbols, as known in the art, which will be visible through the overlying outer covering.
    [066] In several modalities, the base element will be substantially flat but, as will be understood, it can also be configured in curved or complex shapes.
    [067] Any variety of materials may be suitable for use as a base element 15 including flexible materials such as woven materials, mesh materials, films (for example, polymeric films), non-woven, sheet metal, laminates metal, glass and the like. In some modalities where the final product of the film is intended for use in optical applications such as an optical screen, the substrate material will be chosen based in part on the desired optical and mechanical properties for the intended use. Mechanical properties can include flexibility, dimensional stability and impact resistance. In some embodiments, an optically clear material (for example, transparent) may be desired. Examples of clear optically suitable materials include optically clear polyester film, triacetate film (TAC), polyethylene naphthalate, polycarbonate, cellulose acetate, (poly) methyl methacrylate, polyolefins such as biaxially oriented polypropylene (BOPP) and simultaneously biaxially oriented polypropylene. (S-BOPP). The base element can comprise or consist of polyamides, polyimides, phenolic resins, polystyrene, styrene-acrylonitrile copolymers, epoxies and the like.
    [068] The thickness of the base element may vary and will typically depend on the intended use of the final article. In some embodiments, the thickness of the substrate is less than about 0.5 mm and typically between about 0.02 and about 0.2 mm. Polymeric materials can be formed using conventional filmmaking techniques (for example, extrusion and uniaxial or biaxial orientation of the extruded film) The base element 15 can be treated to improve adhesion with the covering layer, if any. Exemplifiers of such treatments include chemical treatment, corona treatment (eg, corona with air or nitrogen), plasma, flames or actinic radiation. Adhesion between layers can also be improved with the use of an optional fixing layer or applied primer.
    [069] Where the finished articles are intended for use on display panels, the base element 15 and the other components of article 10 are typically transmissible to light, meaning that light can be transmitted so that the screen can be viewed . Suitable light transmissive optical films include, without limitation, multilayer optical films, microstructured films such as retroreflective lamination and gloss enhancement films (for example, reflective or absorbent), polarizing films, diffusive films, as well as retardant films (for example biaxial) and compensating films as described in US Patent No. 7,099,083 (Johnson et al.).
    [070] As described, for example, in US Patent No. 6,991,695 (Tait et al.), Multilayer optical films are films that provide desirable transmission and / or reflection properties at least partially by an arrangement of the microlayers having different refractive indices. Each of the microlayers is thin enough, so that the light reflected from a plurality of such interfaces undergoes constructive or destructive interference to give the film its reflective or transmissive properties. For optical films designed to reflect ultraviolet, visible or near-infrared wavelengths, each microlayer generally has an optical thickness (that is, a physical thickness multiplied by its refractive index) less than about 1 micron. Thicker layers can also be included as layers of film on the outer surfaces of the film, or protective boundary layers arranged within the film that separate microlayer packs. Multilayer optical film bodies may also comprise one or more thick adhesive layers to bond two or more sheets of multilayer optical film to a laminate.
    [071] The transmission reflection properties of the multilayer optical film are functions of the refractive indices of the respective microlayers. Each microlayer can be characterized at least in positions located on the film by refractive indices in the nx, ny plane and a refractive index nz associated with an axis of film thickness. These indices represent the index of refraction of the material subject to polarized light along the mutually orthogonal x, y and z axes. In practice, the refractive indexes are controlled by conditions of selection and processing of judicious materials. Suitable films can be made by coextruding multiple layers, typically tens or hundreds of layers, of two alternating polymers (polymers A, B) followed by the optional passage of the multilayer extrudate through one or more multiplication matrices and then stretching or, otherwise, orientation of the extrudate to form a final film. The resulting film is made up of multiple microlayers (for example, tens or hundreds) whose thickness and refractive index are customized to provide one or more reflection bands in desired regions of the spectrum, such as in the near or near infrared.
    [072] Exemplary materials that can be used in the manufacture of the multilayer polymeric optical film can be found in PCT publication No. WO 99/36248 (Neavin et al.). Desirably, at least one of the materials is a polymer with an optical stress coefficient having a large absolute value. In other words, the polymer preferably develops a large birefringence (at least about 0.05, more preferably about 0.1 or even 0.2) when extended. Depending on the order of the multilayer film, birefringence can be developed between two orthogonal directions on the film plane, between one or more directions on the plane and the direction perpendicular to the film plane, or a combination of them. In special cases where the isotropic refractive indices between non-extended layers of polymer are widely separated, the preference for large birefringence in at least one of the polymers can be relaxed, although birefringence is still often desirable. Such special cases can arise in the selection of polymers for mirrored films and for polarizing films formed using a biaxial process, which pulls the film in two directions orthogonal in the plane. In addition, the polymer is desirably capable of maintaining birefringence after stretching, so that the desired optical properties are imparted to the finished film. A second polymer can be chosen for other layers of the multilayer film so that, in the finished film, the refractive index of the second polymer, in at least one direction, differs significantly from the refractive index of the first polymer in the same direction. For convenience, films can be manufactured using only two distinct polymer materials, and interleaving those materials during the extrusion process to produce alternating layers A, B, A, B, etc. Merging only two distinct polymeric materials, however, is not necessary. Instead, each layer of a multilayer optical film can be composed of a unique material or blend not found elsewhere in the film. Preferably, the polymers being coextruded have the same or similar melting temperatures.
    [073] Combinations of two exemplary polymers that provide adequate refractive index differences and adequate interlayer adhesion include: (1) to polarize multilayer optical films manufactured using a predominantly uniaxial stretch process, polyester PEN / coPEN, PET / coPET , PEN / sPS, PET / sPS, PEN / EastarTM and PET / EastarTM polyester, where "PEN" refers to polyethylene naphthalate, "coPEN" refers to a copolymer or mixture based on naphthalenedicarboxylic acid, "PET" refers to if polyethylene terephthalate is used, "coPET" refers to a copolymer or mixture based on terephthalic acid, "sPS" refers to syndiotactic polystyrene and its derivatives and EastarTM is a trade name for a polyester or copolyester (believed comprising cyclohexanedimethylene diol units and terephthalate units) commercially available from Eastman Chemical Co .; (2) for polarizing multilayer optical film made by manipulating the processing conditions of a biaxial extension process, PEN / coPEN, PEN / PET, PEN / PBT, PEN / PETG and PEN / PETcoPBT, where "PBT" refers to if polybutylene terephthalate, "PETG" refers to a PET copolymer employing a second glycol (usually cyclohexanedimethanol) and "PETcoPBT" refers to a terephthalic acid copolyester or an ester thereof with a mixture of ethylene glycol and 1,4-butanediol; (3) for mirror films (including colored mirror films), PEN / PMMA thermoplastic polyester, coPEN / PMMA, PET / PMMA, PEN / EcdelTM, PET / EcdelTM thermoplastic polyester, PEN / sPS, PET / sPS, PEN / coPET, PEN / PETG and PEN / THVTM fluopolymers, where "PMMA" refers to polymethyl methacrylate, EcdelTM is a trade name for a thermoplastic polyester or copolyester (believed to comprise cyclohexanedicarboxylate units, polytetramethylene ether glycol units and cyclohexanedimethanol) commercially available from Eastman Chemical Co., and THVTM is a trademark of a commercially available fluorofluoropolymer from 3M Company.
    [074] Additional details of multilayer optical films and related constructions can be found in US Patent No. 5,882,774 (Jonza et al.) And in PCT publications WO 95/17303 (Ouderkirk et al.) And WO 99 / 39224 (Ouderkirk et al.). Polymeric multilayer optical films and film bodies may comprise additional layers and coatings selected for their optical, mechanical and / or chemical properties. Polymeric films and film bodies can also comprise inorganic layers, such as coatings or layers of metal or metal oxide.
    [075] In other embodiments, the base element 15 may comprise or consist of any of a variety of non-polymeric materials, such as glass, metal lamination, paper, cardboard, mesh materials, fabrics or the like. EXTERNAL COATING
    [076] The outer coating 14 is formed by applying a curable liquid outer coating composition comprising a siloxane-binding component to at least a portion of the front surface 16 of the body element 12. The coating composition is then cured so that a solid outer shell 14 that is bonded to the siloxane, to the body element, is formed.
    [077] The resulting outer coating is hydrophilic, preferably highly hydrophilic. In illustrative embodiments, the resulting outer coating is about 0.3 to about 1 micron thick and the underlying diamond-like glass covering layer of the body element is about 0.1 to about 2 microns thick. Such combinations provide a useful combination of durable cleanability and resistance to damage. It will be understood that articles of the invention can be manufactured using other thicknesses of component layers.
    [078] In some embodiments, the outer coating comprises at least one zwitterionic silane of the group consisting of phosphate silanes and sulfonate silanes. Such silanes include at least one phosphate group (PO4-3) or sulfonate group (SO3-) to impart the desired high hydrophilic capacity to the cleanable surface.
    [079] Illustrative examples of functional zwitterionic sulfonate compounds include those described in US Patent No. 5,936,703 (Miyazaki et al.) And PCT Applications numbers WO 2007/146680 (Schlenoff) and WO 2009/119690 (Yamazaki et al. ).
    [080] In certain embodiments, the zwitterionic sulfonate-organosilanol compounds used in the solutions and compositions of the present invention have the following formula (I) where: (R1O) p-Si (R2) qW-N + (R3) (R4) - (CH2) m-SO3- (I) where: each R1 is independently a hydrogen, methyl group or ethyl group; each R2 is independently a methyl group or an ethyl group; each R3 and R4 is independently a saturated or unsaturated organic group, linear, branched, or cyclic, which can be optionally joined with group W atoms to form a ring; W is an organic bonding group; p and m are integers equal to 1 to 3; q is 0 or 1; and p + q = 3.
    [081] The organic linking group W of the formula (I) is preferably selected from saturated or unsaturated organic, chain-linear, branched or cyclic groups. The linking group W is preferably an alkylene group, which may include carbonyl groups, urethane groups, urea groups, heteroatoms such as oxygen, nitrogen and sulfur, and combinations thereof. Examples of suitable W-linking groups include alkylene groups, cycloalkylene groups, cycloalkylene groups with alkyl substituted, alkylene groups substituted with hydroxyl, mono-oxa alkylene groups substituted with hydroxyl, divalent hydrocarbon groups having mono-oxa substitution in the main chain, groups of divalent hydrocarbons having mono-thio substitution in the main chain, divalent hydrocarbon groups having mono-oxo-thio substitution in the main chain, divalent hydrocarbon groups having dioxo-thio substitution in the main chain, arylene groups, alkylene alkylene groups and substituted alkyl alkylene groups.
    [082] Suitable examples of zwitterionic compounds of formula (I) are described in US Patent No. 5,936,703 (Miyazaki et al.) And in PCT Application numbers WO 2007/146680 and WO 2009/119690, and include the following functional groups zwiterionics (-W-N + (R3) (R4) - (CH2) m-SO3-):

    [083] In certain embodiments, the sulfonate-organosilanol compounds used in the solutions and compositions of the present invention have the following formula (II) where: (R1O) p-Si (R2) q-CH2CH2CH2-N + (CH3) 2- ( CH2) m-SO3- (II) where: each R1 is independently a hydrogen, methyl group or ethyl group; each R2 is independently a methyl group or an ethyl group; p and m are integers equal to 1 to 3; q is 0 or 1; and p + q = 3.
    [084] Suitable examples of zwitterionic compounds of formula (II) are described in US Patent No. 5,936,703 (Miyazaki et al.), Including, for example: (CH3O) 3Si-CH2CH2CH2-N + (CH3) 2-CH2CH2CH2- SO3-; and (CH3CH2O) 2Si (CH3) -CH2CH2CH2-N + (CH3) 2-CH2CH2CH2-SO3-.
    [085] Other examples of suitable zwitterionic compounds, which can be produced using standard techniques that are exemplified in the examples section, include the following:


    [086] The sulfonate functional coating composition typically includes a sulfonate functional compound in an amount of at least about 0.1% by weight, and often at least about 1% by weight, based on weight. total of the coating composition. The sulfonate functional coating composition typically includes a sulfonate functional compound in an amount not greater than about 20, by weight, and often not greater than about 5%, by weight, based on the total weight of the coating composition. . In general, for monolayer coating thicknesses, relatively diluted coating compositions are used. Alternatively, relatively concentrated coating compositions can be used and subsequently rinsed.
    [087] The sulfonate functional coating composition preferably includes alcohol, water or hydroalcoholic solutions (i.e., alcohol and / or water). Typically, such alcohols are lower alcohols (for example, C1 to C8 alcohols, and more typically C1 to C4 alcohols), such as methanol, ethanol, propanol, 2-propanol, etc. Preferably, the sulfonate functional coating compositions are aqueous solutions. As used in the present invention, the term "aqueous solution" refers to solutions containing water. Such solutions may employ water as the only solvent or they may employ combinations of water and organic solvents such as alcohol and acetone. Organic solvents can also be included in hydrophilic treatment compositions in order to improve their freeze-thaw stability. Typically, the solvents are present in an amount of up to about 50 weight percent of the compositions and preferably in the range of about 5 to about 50 weight percent of the compositions.
    [088] The sulphonate functional coating composition can be acidic, basic or neutral. The durability of coatings performance can be affected by pH. For example, coating compositions containing sulfonate-functional zwitterionic compounds are preferably neutral.
    [089] Sulfonate functional coating compositions can be supplied in a variety of viscosities. In this way, for example, the viscosity can vary from a water-like fineness to a paste-like weight. They can also be supplied in the form of gels. In addition, several other ingredients can be incorporated into the compositions.
    [090] In this way, for example, conventional surfactants, cationic, anionic, or non-ionic surfactants can be used. Detergents and wetting agents can also be used. Typically, anionic surfactants, detergents and wetting agents such as those described below for the base composition are also useful in the functional sulfonate coating compositions of the invention. The term "surfactant", as used here, describes molecules that comprise hydrophilic (polar) and hydrophobic (non-polar) regions on the same molecule, which are capable of reducing the surface tension of the coating solution. Useful surfactants can include those disclosed in US Patent No. 6,040,053 (Scholz et al.).
    [091] For typical concentrations of silica nanoparticles (for example, about 0.2 to about 15 weight percent of the total coating composition) most surfactants comprise less than about 0.1 weight percent of coating composition, preferably about 0.003 to about 0.05 weight percent, in order to preserve the anti-reflective properties of the coating. It should be noted that, with some surfactants, an irregular coating is achieved in concentrations higher than that which is necessary to obtain the anti-curl property.
    [092] Anionic surfactants in the primer coating composition are preferred when added to optimize the uniformity of the resulting coatings. Useful anionic surfactants include, but are not limited to, those with molecular structures comprising (1) at least one hydrophobic moiety, such as C6 to C20 alkyl, alkylaryl and / or alkenyl groups, (2) at least one anionic group, such as sulfate, sulfonate, phosphate, polyoxyethylene sulfate, polyoxyethylene sulfonate, polyoxyethylene phosphate and the like, and / or (3) the salts of such anionic groups, wherein said salts include alkali metal salts, ammonium salts, tertiary amino salts and similar. Representative commercial examples of useful anionic surfactants include sodium lauryl sulfate, for example, TEXAPON ™ L-100 available from Henkel Inc., Wilmington, DE, USA, or POLYSTEP ™ B-3 available from Stepan Chemical Co, Northfield, IL , USA; sodium lauryl ether sulfate, POLYSTEP ™ B-12, available from Stepan Chemical Co., Northfield, IL; ammonium lauryl sulfate, for example, STANDAPOL ™ A available from Henkel Inc., Wilmington, DE, USA; and sodium dodecylbenzenesulfonate, for example, SIPONATE ™ DS-10 available from Rhone-Poulenc, Inc., Cranberry, NJ.
    [093] When the primer coating composition does not include a surfactant or when improved uniformity of the coating is desirable, it may be beneficial to add another wetting agent, including those that do not impart durable anti-caking properties, to ensure uniform coating of the article from of an aqueous or hydroalcoholic solution. Examples of useful wetting agents include polyethoxylated alkyl alcohols (for example, BRIJ ™ 30 and BRIJ ™ 35, by ICI Americas, Inc., and TERGITOL ™ TMN-6 ™ Specialty Surfactant, by Union Carbide Chemical and Plastics Co., polyethoxylated alkylphenols (eg example, TRITON ™ X-100 from Union Carbide Chemical and Plastics Co., ICONOL ™ NP-70 obtained from BASF Corp.) and polyethylene glycol / polypropylene block copolymer (TETRONIC ™ 1502 BLOCK COPOLYMER SURFACTANT, copolymer surfactant in block TETRONIC ™ 908 and COPOLYMER SURFACE IN BLOCK PLURONIC ™ F38, all obtained from BASF Corp.). Logically, any wetting agent added must be included in a level that will not destroy the antireflective or anti-curl properties of the coating, if such characteristics are Generally, the wetting agent is used in amounts of less than about 0.1 weight percent of the coating composition, preferably about 0.003 to about 0.05 weight percent. eso, the coating composition depending on the amount of silica nanoparticles. It may be desirable to rinse or macerate the coated article in water to remove excess surfactant or wetting agent.
    [094] Sulfonate functional coating compositions are preferably coated on the article using conventional coating techniques such as bar, cylinder, curtain, gravure, spray or dip coating techniques. Preferred methods include cylinder and bar coating, or air foil coating to adjust the thickness.
    [095] The sulfonate functional coatings of the present invention are preferably applied to a monolayer thickness. Typically, the functional sulfonate coating is not greater than about 10 microns in thickness, and preferably is not greater than about 1 micron in thickness, as measured using an ellipsometer such as a Gaertner Scientific Corp model No. L115C.
    [096] Functional sulfonate coatings of the present invention can be coated on both sides of a substrate, if desired. Alternatively, the coatings of the present invention can be applied as a coating on the side of the substrate. Once coated, the sulfonate functional article is typically dried at temperatures of about 20 ° C to about 150 ° C in a recirculating oven. An inert gas can be circulated. The temperature can be increased further to speed up the drying process, but care must be taken to avoid damage to the substrate.
    [097] Sulfonate functional coating compositions provide anti-fog properties for surfaces coated with it. The property against fogging is demonstrated by the tendency of coatings to resist the formation of water droplets that tend to significantly reduce the transparency of the coated substrate. Water vapor, for example, from human respiration, tends to condense on the coated substrate in the form of a thin, uniform film of water, instead of droplets of water. Such a uniform film does not significantly reduce the clarity or transparency of the substrate. ARTICLE
    [098] In addition, the cleanable articles of the invention, for example, dry-erase articles, may additionally comprise such other optional components as structures, forms for storing materials and tools such as writing instruments, erasers, fabrics, note papers , etc. carrying handles, protective covers, means for hanging on vertical surfaces, easels, etc. METHODS OF USE
    [099] The cleanable articles of the invention can be readily cleaned, for example, simply by rubbing with a dry cloth, paper towel, etc. or in some cases, rubbing with a tissue, paper towel, etc. using water.
    [0100] For example, in modalities where the article is a dry-erase article, the surface of the outer coating can be readily written, and then easily cleaned. Significantly, even permanent marker writing can be easily removed with rubbing, preferably after first applying water and / or water vapor (for example, by breathing). Typically, the methods of the present invention include removing permanent marker writing from the surface simply by applying water (e.g., tap water at room temperature) and / or water vapor (e.g., a person's breath) and scrubbing. As used here, "rubbing" refers to gentle scrubbing, typically with your hands with, for example, a cloth, paper towel or cloth, without significant pressure (for example, generally, no more than about 350 grams) to one or more movements or rubs (typically, only a few are needed).
    [0101] In some cases, cleaning the surface, for example, erasing the whiteboard, is facilitated using a cleaning composition, preferably a water-based glass cleaner like Windex ™ Glass Cleaner (SC Johnson Co., Racine, WI ). EXAMPLES
    [0102] The invention will be further explained with the following illustrative non-limiting examples.
    [0103] The materials used in the examples included:

    [0104] The following test method for assessing handwriting removal with permanent marker was used.
    [0105] Write on the test surface with the SHARPIE ™ Black permanent marker. After 24 hours at room temperature, apply water to the surface. Then rub the writing on the surface with a wet paper towel. Continue rubbing until there is no change in the amount of marker remaining on the board. Note whether the writing is removed or not by the action of the wet paper towel. For permanent markers that are difficult to remove with just water, apply a little WINDEX ™ glass cleaner by spraying over the writing and then rub with a paper towel to remove.
    [0106] A rewritable article with a body element having a high-gloss front surface (example 1) and one with an opaque front surface (example 2) were coated with diamond-type glass to form cover layers over them followed by the application of zwitterionic silane composition described below to form external coatings according to the invention. The removability of the SHARPIE ™ permanent marker was tested after drying times of 24 hours. The opaque finish article of example 2 was more resistant to abrasion than the glossy article of example 1, as indicated by the markings observed after the seventh use.
    [0107] The outer coating in example 1 was formed by a composition prepared by adding 3- (N, N-dimethylaminopropyl) trimethoxysilane (49.7 g, 239 mmol) to a pot with a screw cap followed by deionized water (DI) ( 82.2 g) and 1,4-butanesultone (32.6 g, 239 mmol). The combined reaction mixture was heated to 75 ° C and mixed for a period of 14 hours. The resulting reaction mixture was diluted to 2% by weight in water to obtain the final coating composition which was then applied to the front surface of the body element.
    [0108] In example 2, the outer coating was formed from a composition prepared as a 2% solution, by weight, of lithium silicate [LITHISILTM 25: Preparatory composition of example 1 (23:77 w / w)] in water.
    [0109] After 10 uses, 100% of the black SHARPIE ™ permanent marker was additionally promptly removed. The marker classified the samples with brightness after the 7th use, but the sample with opaque optical structure induced by a cylinder was not marked by the marker. Therefore, durability is improved by microstructuring the surface of the hard coating by any suitable process.

    [0110] Although the present invention has been completely described together with its preferred modalities with reference to the attached drawing, it should be noted that several changes and modifications are evident to those skilled in the art. These changes and modifications are to be understood to be included within the scope of the present invention as defined by the appended claims, except where otherwise indicated. The complete description of all patents, patent documents and publications mentioned herein are incorporated by reference.
    权利要求:
    Claims (12)
    [0001]
    1. METHOD FOR MANUFACTURING A CLEANABLE ARTICLE (10), characterized by comprising: (a) providing a body element (12) having a front surface (16), at least a portion of the front surface (16) is connectable to siloxane, in which the body element (12) comprises a polymeric matrix comprising nanoparticles and in which the matrix has been treated by exposing at least a portion of the front surface (16) thereof to at least one of the following: plasma treatment , corona, and flame in order to expose nanoparticles that can be linked to siloxane; and then; (b) applying an outer coating composition to at least a portion of the siloxane-bondable surface, the outer coating composition comprising a siloxane-binding component; and (c) curing the outer coating composition to form a hydrophilic outer coating (14) having a siloxane bond with the front surface (16) of the body element (12).
    [0002]
    2. METHOD according to claim 1, characterized in that the body element (12) comprises the reaction product of a curable mixture, comprising at least one curable component selected from the group consisting of (meth) acrylate monomers, oligomers of (met) acrylate.
    [0003]
    METHOD according to claim 2, characterized in that the curable mixture further comprises a plurality of surface-modified nanoparticles.
    [0004]
    4. METHOD, according to claim 3, characterized by the nanoparticles being selected from the group consisting of aluminum oxides, tin oxide and antimony, bismuth subsalicylate, bohemite, calcium carbonate, calcium phosphate, cerium dioxide, graphene , haloisite, lanthanum boride, lithium carbonate, silver, amorphous silica, colloidal silica, silicon dioxide, titanium dioxide, zinc oxide, zirconium oxide and zirconium dioxide.
    [0005]
    5. METHOD according to claim 3, characterized in that the nanoparticles comprise a plurality of silica nanoparticles.
    [0006]
    6. METHOD according to claim 1, characterized in that the front surface of the body element (12) has an opaque finish before the coating composition is applied to it.
    [0007]
    7. METHOD according to claim 1, characterized in that the front surface of the body element (12) has a glossy finish before the coating composition is applied to it.
    [0008]
    METHOD according to claim 1, characterized in that the body element (12) comprises a cover layer (13) connectable to the siloxane.
    [0009]
    9. METHOD according to claim 8, characterized in that the cover layer (13) is a diamond-type glass film.
    [0010]
    10. CLEANABLE ARTICLE (10), characterized by comprising: (a) a body element (12) having a front surface (16), in which said front surface (16) is connectable to siloxane, in which the body element ( 12) comprises a polymeric matrix comprising nanoparticles and in which the matrix has been treated by exposing at least a portion of the front surface (16) thereof to at least one of the following treatments: plasma, corona, and flame in order to expose the nanoparticles bondable to siloxane; and (b) an external coating (14) connected by siloxane bonds to the front surface (16), in which the external coating (14) connected to the body element (12) after the polymeric matrix is treated in order to expose the nanoparticles bondable to the siloxane.
    [0011]
    11. METHOD FOR USING A CLEANABLE ITEM (10), characterized by comprising: (a) providing a cleanable article (10), as defined in claim 10; and (b) writing signs on the front surface (16) thereof.
    [0012]
    METHOD according to claim 11, characterized in that it further comprises (c) erasing at least a portion of said signal.
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    同族专利:
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    US201161581536P| true| 2011-12-29|2011-12-29|
    US61/581,536|2011-12-29|
    PCT/US2012/072097|WO2013102099A1|2011-12-29|2012-12-28|Cleanable articles and methods for making and using same|
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