ARTICLES WITH REWRITABLE WRITING SURFACES AND METHODS FOR MAKING AND USING SAME

Abstract

Articles comprising a coating of hydrophilic silane. Also, methods for making such articles and methods for using such articles.

Claims

1. An article having a face and on the face a hydrophilic coating comprising one or more hydrophilic silanes selected from the group consisting of zwitterionic silanes, hydroxyl sulfonate silanes, phosphonate silanes, carboxylate silanes, glucanamide silanes, polyhydroxyl alkyl silanes, polyhydroxyl aryl silanes, hydroxyl polyethyleneoxide silanes, polyethyleneoxide silanes, and combinations thereof.

2. The article of claim 1 wherein the hydrophilic coating further comprises tetraalkoxysilane or oligomers thereof, lithium silicate, sodium silicate, potassium silicate, or combinations thereof.

3. The article of claim 1 wherein the hydrophilic coating further comprises nanosilica particles having particles sizes less than 100 nm.

4. The article of claim 1 wherein the one or more hydrophilic silane comprises one or more zwitterionic silanes.

5. The article of claim 4 wherein the zwitterionic silane is selected from the group consisting of: ##STR00005##

6. The article of claim 4 wherein the zwitterionic silane has the Formula (II):
(R.sup.1O).sub.p—Si(R.sup.2).sub.q—W—N.sup.+(R.sup.3)(R.sup.4)—(CH.sub.2).sub.m—SO.sub.3.sup.−  (II) wherein: each R.sup.1 is independently a hydrogen, methyl group, or ethyl group; each R.sup.2 is independently a methyl group or an ethyl group; each R.sup.3 and R.sup.4 is independently a saturated or unsaturated, straight chain, branched, or cyclic organic group, which may be joined together, optionally with atoms of the group W, to form a ring; W is an organic linking group; m is an integer of 1 to 4; p is an integer of 1 to 3; q is 0 or 1; and p+=3.

7. The article of claim 6 wherein the organic linking group W is selected from saturated or unsaturated, straight chain, branched, or cyclic organic groups.

8. The article of claim 4 wherein the zwitterionic silane has the Formula (III):
(R.sup.1O).sub.p—Si(R.sup.2).sub.q—CH.sub.2CH.sub.2CH.sub.2—N.sup.+(CH.sub.3).sub.2—(CH.sub.2).sub.m—SO.sub.3.sup.−  (III) wherein: each R.sup.1 is independently a hydrogen, methyl group, or ethyl group; each R.sup.2 is independently a methyl group or an ethyl group; m is an integer of 1 to 4; p is an integer of 1 to 3; q is 0 or 1; and p+=3.

9. The article of claim 1 wherein the face is hydrophobic.

10. The article of claim 9 wherein the face is selected from the group consisting of glass, porcelain, metal, polymeric material, and combinations thereof.

11. The article of claim 1 further comprising an .sup.−OH functional primer coating between the face and the hydrophilic coating.

12. The article of claim 11 wherein the primer coating is selected from the group consisting of tetraalkoxysilanes, oligomers thereof, lithium silicates, sodium silicates, potassium silicates, and combinations thereof.

13. The article of claim 11 wherein the primer coating comprises vapor deposited SiO, SiO.sub.2, and combinations thereof.

14. The article of claim 11 wherein the primer coating comprises one or more vapor deposited alkoxysilanes.

15. The article of claim 1 wherein the article if flexible.

16. The article of claim 1 further comprising adhesive coating on a side opposing the face having a hydrophilic coating thereon.

17. A method of using an article as a rewritable writing surface comprising (a) providing an article of claim 1, (b) writing an initial legend with a writing instrument on the face having a hydrophilic coating thereon, and then (c) removing the initial legend.

18. The method of claim 17 further comprising writing with a writing instrument on the face having a hydrophilic coating thereon after removing the initial legend.

19. The method of claim 17 wherein the writing instrument is selected from the group consisting of pencils, pens, and felt tip markers.

20. The method of claim 17 wherein removing the initial legend comprises one or more of the following: (1) wiping the face with the initial legend thereon, (2) treating the face with the initial legend with a liquid cleaning agent selected from the group consisting of water and organic solvents.

Description

DETAILED DESCRIPTION OF ILLUSTRATIVE EMBODIMENTS

[0054] The present invention is directed to articles with rewritable writing surfaces. As will be understood, articles of the invention can be made a variety of configurations depending upon the desired application. Illustrative examples include dry erase articles, file folders (e.g., having tabs with writing surfaces of the invention thereon), labels, name tags, notebook (e.g., on which the covers have a rewritable writing surface of the invention), tabs for hanging files, content labels on bins, informational legends on equipment, doors, storage units, etc.

[0055] The invention has particular utility in such articles as dry erase boards. It has been discovered that application of a hydrophilic coating as described herein to glass and porcelain substrates surprisingly improves their performance as writing surfaces for dry erase articles. The writing surfaces of dry erase articles of the invention exhibit excellent writability with conventional dry erase markers yet writing from permanent markers and ghosting from dry erase markers can be readily removed therefrom with water and a cloth or paper towel. No solvents or tools need be used. As a result, dry erase articles of the invention provide heretofore unattained utility and durability. In addition, the hydrophilic coating applied to a film provides a rewritable surface which could be used as a board or label. The surface accepts permanent marker writing which can subsequently be removed with water or a commercially available glass cleaner. In brief summary, illustrative examples of rewritable articles of the invention comprise a writing surface comprising glass, porcelain, painted steel, melamine or film and having a coating as described herein. In addition, dry erase articles of the invention can further comprise such other optional components as frames, means for storing materials and tools such as writing instruments, erasers, cloths, note paper, etc., handles for carrying, protective covers, means for hanging on vertical surfaces, easels, etc.

[0056] Illustrative examples also include a label surface comprising a flexible substrate such as a film, paper, coated paper, or paper film laminate having a coating as described herein. Label articles of the invention can further comprise an adhesive coating on the back of the substrate, a release liner, and a die cut pattern in the assembly allowing for the use of individual labels of the desired size.

[0057] Significantly, permanent marker writing and ghosting of dry erase markers can be easily removed from the hydrophilic-functional coating of the present invention with wiping after first applying water or a water based glass cleaner. A water based glass cleaner may contain a surfactant or a mixture of surfactants. The surfactants may be cationic, anionic or/and nonionic one or a mixture that are known in the art. Typically, methods of the present invention include removing permanent marker writing and ghosting from dry erase markers from the hydrophilic-functional surface by simply applying water (e.g., tap water at room temperature) and/or a water based glass cleaner and wiping. Herein, “wiping” refers to gentle wiping, typically by hand, with for example, a tissue, paper towel, or a cloth, without significant pressure (e.g., generally, no more than 800 grams) for one or more strokes or rubs (typically, only a few are needed). In particular, in one embodiment, there is provided a coated article that includes a substrate surface, a primer (preferably, a nanoparticle-containing primer) disposed on the substrate surface, and a hydrophilic-functional coating disposed on the primed surface.

[0058] The hydrophilic-functional coating is preferably applied in a monolayer thickness, but can be as thick as 10 microns. The preferred thickness for the hydrophilic functional coating is from 200 to 1000 nm. The primer coating is preferably within a range of 10 nm to 1,000 nm thick, and frequently 50 nm to 250 nm thick.

[0059] Siloxane (Si—O—Si) bonds are used to chemically bind the hydrophilic functionality to the surface, whether it be directly to the substrate surface or to a primer coating thereon. Preferably, the presence of three siloxane bonds for each surface hydrophilic group makes the chemical bond relatively more stable than if one or two siloxane bonds were formed.

[0060] In one particular embodiment, a coated article includes a substrate surface, a nanoparticle-containing primer disposed on the substrate surface, and a hydrophilic-functional coating bonded to the nanoparticle-containing primer through siloxane bonds. The nanoparticle-containing primer includes agglomerates of silica nanoparticles having average particle diameters of 40 nanometers or less, said agglomerates including a three-dimensional porous network of silica nanoparticles, and the silica nanoparticles are bonded to adjacent silica nanoparticles. The silica nanoparticles in the primer can be monodisperse particles of substantially uniform size or they can be mixtures of different sized nanoparticles.

[0061] In one embodiment, there is provided a method of treating a substrate surface. The method includes: applying a primer coating composition to the writing surface to form a primed surface having —OH groups thereon; contacting the primed surface having —OH groups thereon with a hydrophilic-functional coating composition, wherein the hydrophilic-functional coating composition includes an organic compound having hydrophilic-functional groups and alkoxysilane groups and/or silanol-functional groups. The method further includes drying the hydrophilic-functional coating composition to form a hydrophilic-functional coating including at least a monolayer of the hydrophilic-functional compound bonded to the primer coating through siloxane bonds; wherein dry erase and permanent markers are removable from the dried hydrophilic-functional coating by wiping, or preferably by applying water and/or a water based glass cleaner with wiping. In certain embodiments, the hydrophilic-functional organic compound is a zwitterionic compound and in certain embodiments, it is a non-zwitterionic compound. In certain embodiments the hydrophilic-functional coating composition includes a tetraalkoxysilane, lithium silicate, sodium silicate, potassium silicate, or combinations thereof.

[0062] The hydrophilic-functional coating compositions of the present invention can be used on a variety of substrate surfaces, including for example, glass surface, a porcelain surface, a metal surface, an organic polymeric surface, or a combination thereof. The method includes: contacting the glass, metal or organic polymeric surface with a hydrophilic-functional coating composition, wherein the hydrophilic-functional coating composition includes an organic compound having hydrophilic-functional groups and alkoxysilane groups and/or silanol-functional groups; and drying the hydrophilic-functional coating composition to form a hydrophilic-functional coating. The hydrophilic-functional coating includes at least a monolayer of the hydrophilic-functional compound bonded to the substrate surface through siloxane bonds. In certain embodiments, the hydrophilic-functional organic compound is a zwitterionic compound and in certain embodiments, it is a non-zwitterionic compound.

[0063] Advantageously, permanent marker writing and ghosting from dry erase markers is removable from the dried hydrophilic-functional coating by applying water and/or a water based glass cleaner and wiping.

[0064] Thus, the methods of the present invention can be used to prepare a hydrophilic article on a surface of a wide variety of substrates, thereby providing “wipe-away writing surfaces.” Such a surface is one having a hydrophilic-functional coating thereon that can be cleaned of conventional dry erase markings with a dry eraser and permanent markings by applying water or a commercially available glass cleaner to the surface followed by gentle wiping with a cloth, paper towel, tissue, or the like.

[0065] In certain embodiments of the coated article, the hydrophilic-functional coating includes at least a monolayer of a hydrophilic-functional compound bonded to the substrate surface through siloxane bonds. In certain embodiments, the hydrophilic coating composition also contains a tetraalkoxysilane, lithium silicate, sodium silicate, potassium silicate, or combinations thereof. In certain embodiments of the coated article, the hydrophilic-functional coating includes at least a monolayer of a hydrophilic-functional compound bonded to a primer through siloxane bonds. In certain embodiments of the coated article, the hydrophilic-functional coating includes at least a monolayer of a hydrophilic-functional compound bonded to a nanoparticle-containing primer through siloxane bonds. The present invention also provides a hydrophilic article prepared from a method of the invention.

Hydrophilic-Functional Coating

[0066] The hydrophilic-functional coating can be prepared from hydrophilic-functional compounds. These compounds have an alkoxysilane- and/or silanol-functional group for bonding to a substrate surface. They also include a hydrophilic group for rendering hydrophilicity to the substrate surface.

[0067] For certain embodiments, the hydrophilic-containing compounds are zwitterionic and for certain embodiments, they are non-zwitterionic.

[0068] Examples include non-zwitterionic sulfonate-organosilanol compounds such as those disclosed in U.S. Pat. No. 4,152,165 (Langager et al.) and 4,338,377 (Beck et al.).

[0069] In certain embodiments, the non-zwitterionic sulfonate-organosilanol compounds used in the solutions and compositions of the present invention have the following Formula (I):

[(MO)(Q.sub.n)Si(XCH.sub.2SO.sub.3.sup.−).sub.3-nY.sub.2/nr.sup.+r  (I)

wherein:

[0070] each Q is independently selected from hydroxyl, alkyl groups containing from 1 to 4 carbon atoms and alkoxy groups containing from 1 to 4 carbon atoms;

[0071] M is selected from hydrogen, alkali metals, and organic cations of strong organic bases having an average molecular weight of less than 150 and a pKa of greater than 11;

[0072] X is an organic linking group;

[0073] Y is selected from hydrogen, alkaline earth metals (e.g., magnesium, calcium, etc.), organic cations of protonated weak bases having an average molecular weight of less than 200 and a pKa of less than 11 (e.g., 4-aminopyridine, 2-methoxyethylamine, benzylamine, 2,4-dimethylimidazole, 3-[2-ethoxy(2-ethoxyethoxy)] propylamine), alkali metals, and organic cations of strong organic bases having an average molecular weight of less than 150 and a pKa of greater than 11 (e.g., .sup.+N(CH.sub.3).sub.4, .sup.+N(CH.sub.2CH.sub.3).sub.4), provided that M is hydrogen when Y is selected from hydrogen, alkaline earth metals and organic cations of said protonated weak bases;

[0074] r is equal to the valence of Y; and

[0075] n is 1 or 2.

[0076] Preferably, the non-zwitterionic compound of Formula (I) is an alkoxysilane compound (e.g., wherein Q is an alkoxy group containing from 1 to 4 carbon atoms).

[0077] The weight percentage of oxygen in these compounds of Formula (I) is at least 30%, and preferably at least 40%. Most preferably it is in the range of 45% to 55%. The weight percentage of silicon in these compounds is no greater than 15%. Each of these percentages is based on the weight of the compound in the water-free acid form.

[0078] The organic linking group X of Formula (I) is preferably selected from alkylene groups, cycloalkylene groups, alkyl-substituted cycloalkylene groups, hydroxy-substituted alkylene groups, hydroxy-substituted monooxa alkylene groups, divalent hydrocarbon groups having monooxa backbone substitution, divalent hydrocarbon groups having mono-thia backbone substitution, divalent hydrocarbon groups having monooxa-thia backbone substitution, divalent hydrocarbon groups having dioxo-thia backbone substitution, arylene groups, arylalkylene groups, alkylarylene groups and substituted alkylarylene groups. Most preferably X is selected from alkylene groups, hydroxy-substituted alkylene groups and hydroxy-substituted monooxa alkylene groups.

[0079] Suitable examples of non-zwitterionic compounds of Formula (I) are described in U.S. Pat. No. 4,152,165 (Langager et al.) and 4,338,377 (Beck et al.), and include, for example, the following: [0080] (HO).sub.3Si—CH.sub.2CH.sub.2CH.sub.2—O—CH.sub.2—CH(OH)—CH.sub.2SO.sub.3.sup.−H.sup.+; [0081] (HO).sub.3Si—CH.sub.2CH(OH)—CH.sub.2SO.sub.3−H.sup.+; [0082] (HO).sub.3Si—CH.sub.2CH.sub.2CH.sub.2SO.sub.3.sup.−H.sup.+; [0083] (HO).sub.3Si—C.sub.6H.sub.4-CH.sub.2CH.sub.2SO.sub.3−H.sup.+; [0084] (HO).sub.2Si—[CH.sub.2CH.sub.2SO.sub.3.sup.−H.sup.+].sub.2; [0085] (HO)—Si(CH.sub.3).sub.2—CH.sub.2CH.sub.2SO.sub.3.sup.−H.sup.+; [0086] (NaO)(HO).sub.2Si—CH.sub.2CH.sub.2CH.sub.2—O—CH.sub.2—CH(OH)—CH.sub.2SO.sub.3.sup.−Na.sup.+; and [0087] (HO).sub.3Si—CH.sub.2CH.sub.2SO.sub.3.sup.−K.sup.+.

[0088] Examples of zwitterionic sulfonate-functional compounds include those disclosed in U.S. Pat. No. 5,936,703 (Miyazaki et al.) and International Publication Nos. WO 2007/146680 and WO 2009/119690.

[0089] In certain embodiments, the zwitterionic sulfonate-organosilanol compounds used in the solutions and compositions of the present invention have the following Formula (II) wherein:

(R.sup.1O).sub.p—Si(R.sup.2).sub.q—W—N.sup.+(R.sup.3)(R.sup.4)—(CH.sub.2).sub.m—SO.sub.3.sup.−  (II)

wherein:

[0090] each R.sup.1 is independently a hydrogen, methyl group, or ethyl group;

[0091] each R.sup.2 is independently a methyl group or an ethyl group;

[0092] each R.sup.3 and R.sup.4 is independently a saturated or unsaturated, straight chain, branched, or cyclic organic group, which may be joined together, optionally with atoms of the group W, to form a ring;

[0093] W is an organic linking group;

[0094] p and m are integers of 1 to 3;

[0095] q is 0 or 1; and

[0096] p+q=3.

[0097] The organic linking group W of Formula (II) is preferably selected from saturated or unsaturated, straight chain, branched, or cyclic organic groups. The linking group W is preferably an alkylene group, which may include carbonyl groups, urethane groups, urea groups, heteroatoms such as oxygen, nitrogen, and sulfur, and combinations thereof. Examples of suitable linking groups W include alkylene groups, cycloalkylene groups, alkyl-substituted cycloalkylene groups, hydroxy-substituted alkylene groups, hydroxy-substituted monooxa alkylene groups, divalent hydrocarbon groups having mono-oxa backbone substitution, divalent hydrocarbon groups having mono-thia backbone substitution, divalent hydrocarbon groups having monooxo-thia backbone substitution, divalent hydrocarbon groups having dioxo-thia backbone substitution, arylene groups, arylalkylene groups, alkylarylene groups and substituted alkylarylene groups.

[0098] Suitable examples of zwitterionic compounds of Formula (II) are described in U.S. Pat. No. 5,936,703 (Miyazaki et al.) and International Publication Nos. WO 2007/146680 and WO 2009/119690, and include the following zwitterionic functional groups (—W—N.sup.+(R.sup.3)(R.sup.4)—(CH.sub.2).sub.m—SO.sub.3.sup.−):

##STR00001##

[0099] In certain embodiments, the sulfonate-organosilanol compounds used in the solutions and compositions of the present invention have the following Formula (III) wherein:

(R.sup.1O).sub.p—Si(R.sup.2).sub.q—CH.sub.2CH.sub.2CH.sub.2—N.sup.+(CH.sub.3).sub.2—(CH.sub.2).sub.m—SO.sub.3.sup.−  (III)

wherein:

[0100] each R.sup.1 is independently a hydrogen, methyl group, or ethyl group;

[0101] each R.sup.2 is independently a methyl group or an ethyl group;

[0102] p and m are integers of 1 to 3;

[0103] q is 0 or 1; and

[0104] p+q=3.

[0105] Suitable examples of zwitterionic compounds of Formula (III) are described in U.S. Pat. No. 5,936,703 (Miyazaki et al.), including, for example:

(CH.sub.3O).sub.3Si—CH.sub.2CH.sub.2CH.sub.2—N.sup.+(CH.sub.3).sub.2—CH.sub.2CH.sub.2CH.sub.2—SO.sub.3.sup.−; and

(CH.sub.3CH.sub.2O).sub.2Si(CH.sub.3)—CH.sub.2CH.sub.2CH.sub.2—N.sup.+(CH.sub.3).sub.2—CH.sub.2CH.sub.2CH.sub.2—SO.sub.3.sup.−.

[0106] Other examples of suitable zwitterionic compounds, which can be made using standard techniques that are exemplified in the Examples Section, include the following:

##STR00002##

[0107] Other suitable hydrophilic functional groups for silanes include but are not limited to phosphonate, carboxylate, gluconamide, sugar, polyvinyl alcohol, and quaternary ammonium. Preferred examples of suitable hydrophilic-functional compounds for use in preparing coating compositions and coatings of the present invention are described in the Experimental Section.

[0108] The hydrophilic-functional coating composition typically includes a hydrophilic-functional compound in an amount of at least 0.1 wt %, and often at least 1 wt %, based on the total weight of the coating composition. The hydrophilic-functional coating composition typically includes a hydrophilic-functional compound in an amount of no greater than 20 wt %, and often no greater than 5 wt %, based on the total weight of the coating composition. Generally, for monolayer coating thicknesses, relatively dilute coating compositions are used. Alternatively, relatively concentrated coating compositions can be used and subsequently rinsed.

[0109] The hydrophilic-functional coating composition preferably includes alcohol, water, or hydroalcoholic solutions (i.e., alcohol and/or water). Typically, such alcohols are lower alcohols (e.g., C.sub.1 to C.sub.8 alcohols, and more typically C.sub.1 to C.sub.4 alcohols), such as methanol, ethanol, propanol, 2-propanol, etc. Preferably, the hydrophilic-functional coating compositions are aqueous solutions. As it is used herein, 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 may also be included in the hydrophilic treatment compositions so as to improve their freeze-thaw stability. Typically, the solvents are present in an amount up to 50 wt % of the compositions and preferably in the range of 5 to 50 wt % of the compositions.

[0110] The hydrophilic-functional coating composition can be acidic, basic, or neutral. The performance durability of the coatings can be affected by pH. For example, coating compositions containing sulfonate-functional zwitterionic compounds are preferably neutral.

[0111] The hydrophilic-functional coating compositions may be provided in a variety of viscosities. Thus, for example, the viscosity may vary from a water-like thinness to a paste-like heaviness. They may also be provided in the form of gels. Additionally, a variety of other ingredients may be incorporated in the compositions.

[0112] Thus, for example, conventional surfactants, cationic, anionic, or nonionic 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 Primer Composition are also useful in the hydrophilic-functional coating compositions of the invention.

[0113] In certain embodiments, the hydrophilic-functional coating composition further includes a tetraalkoxysilane (e.g., tetraethylorthosilicate (“TEOS”)), oligomers thereof, such as alkyl polysilicates (e.g., poly(diethoxysiloxane)), lithium silicate, sodium silicate, potassium silicate, or combinations thereof, which can provide enhanced durability. The coupling agent(s), when present, are typically added to the composition at levels of 0.1 to 20 percent by weight of the coating composition, and more preferably 1 to 15 percent by weight of the coating composition. Optionally, strong acids such as nitric acid can be added to raise the pH to around 2.

[0114] Hydrophilic-functional coating compositions are preferably coated on the article using conventional techniques, such as bar, roll, curtain, rotogravure, spray, wipe or dip coating techniques. The preferred methods include spray, bar and roll coating.

[0115] Hydrophilic-functional coatings of the present invention can be coated on both sides of a substrate if desired. Alternatively, the coatings of the present invention may be coated on one side of the substrate. Once coated, the hydrophilic-functional article is typically dried at temperatures of 30° C. to 200° C. in a recirculating oven. An inert gas may be circulated. The temperature may be increased further to speed the drying process, but care must be exercised to avoid damage to the substrate. Drying drives a condensation reaction between the hydrophilic coating and —OH groups on the surface of the substrate.

Hydrophilic Polymer Coating

[0116] In certain embodiments of the present invention, a hydrophilic polymer coating is applied to a polymeric substrate in order to make a rewritable label, folder, container, etc.

[0117] The hydrophilic polymer coating can be prepared from water soluble polymers with hydroxyl groups. In the presence of acid, the hydroxyl groups on these polymers can condense to form a water insoluble coating. The hydroxyl groups can also react with silanol groups on a silica nanoparticle primer.

[0118] Suitable hydrophilic polymers with hydroxy groups include but are not limited to polyvinyl alcohol, hydroxy methyl cellulose, hydroxyethyl cellulose, dextran, guar gum and mixtures thereof.

[0119] The hydrophilic polymer coating composition typically includes a hydrophilic polymer in an amount of at least 0.1 wt %, and often at least 1 wt %, based on the total weight of the coating composition. The hydrophilic-functional coating composition typically includes a hydrophilic polymer compound in an amount of no greater than 20 wt %, and often no greater than 5 wt %, based on the total weight of the coating composition. Generally, for monolayer coating thicknesses, relatively dilute coating compositions are used. Alternatively, relatively concentrated coating compositions can be used and subsequently rinsed.

[0120] The hydrophilic polymer coating composition preferably includes alcohol, water, or hydroalcoholic solutions (i.e., alcohol and/or water). Typically, such alcohols are lower alcohols (e.g., C.sub.1 to C.sub.8 alcohols, and more typically C.sub.1 to C.sub.4 alcohols), such as methanol, ethanol, propanol, 2-propanol, etc. Preferably, the hydrophilic polymer coating compositions are aqueous solutions. As it is used herein, 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 may also be included in the hydrophilic treatment compositions so as to improve their freeze-thaw stability. Typically, the solvents are present in an amount up to 50 wt % of the compositions and preferably in the range of 5 to 50 wt % of the compositions.

[0121] The hydrophilic polymer coating composition is acidified to a pH≤3.5 in order to promote crosslinking and make the coating more durable. Useful acids include both organic and inorganic acids and may be exemplified by oxalic acid, citric acid, H.sub.2SO.sub.3, H.sub.3PO.sub.4, CF.sub.3CO.sub.2H, HCl, HBr, HI, HBrO.sub.3, HNO.sub.3, HClO.sub.4, H.sub.2SO.sub.4, CH.sub.3SO.sub.3H, CF.sub.3SO.sub.3H, CF.sub.3CO.sub.2H, and CH.sub.3SO.sub.2OH. Most preferred acids include HCl, HNO.sub.3, and H.sub.3PO.sub.4.

[0122] The hydrophilic polymer coating compositions may be provided in a variety of viscosities. Thus, for example, the viscosity may vary from a water-like thinness to a paste-like heaviness. They may also be provided in the form of gels. Additionally, a variety of other ingredients may be incorporated in the compositions. Thus, for example, conventional surfactants, cationic, anionic, or nonionic 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 Primer Composition are also useful in the hydrophilic polymer coating compositions of the invention.

[0123] In certain embodiments, the hydrophilic polymer coating composition further includes a tetraalkoxysilane (e.g., tetraethylorthosilicate (“TEOS”)), oligomers thereof, such as alkyl polysilicates (e.g., poly(diethoxysiloxane)), lithium silicate, sodium silicate, potassium silicate, or combinations thereof, which can provide enhanced durability. The coupling agent(s), when present, are typically added to the composition at levels of 0.1 to 20 wt % of the coating composition, and more preferably 1 to 15 wt % of the coating composition. Optionally, strong acids such as nitric acid can be added to raise the pH to around 2.

[0124] Hydrophilic polymer coating compositions are preferably coated on the article using conventional techniques, such as bar, roll, curtain, rotogravure, spray, wipe or dip coating techniques. The preferred methods include spray, bar and roll coating.

[0125] Hydrophilic polymer coatings of the present invention can be coated on both sides of a substrate if desired. Alternatively, the coatings of the present invention may be coated on one side of the substrate. Once coated, the hydrophilic polymer article is typically dried at temperatures of 30° C. to 200° C. in a recirculating oven. An inert gas may be circulated. The temperature may be increased further to speed the drying process, but care must be exercised to avoid damage to the substrate. Drying drives a condensation reaction between the hydrophilic coating and —OH groups on the surface of the substrate.

Primer Coating

[0126] In certain embodiments of the present invention, a primer coating is formed on a substrate surface. Such primer coating provides —OH groups on the substrate surface. Preferably, such primer coating is formed from a nanoparticle-containing coating composition that is coated and dried on a substrate surface.

[0127] Other primer compositions or processes can be used to provide —OH groups. Examples of such compositions include a tetraalkoxysilane, oligomers thereof, lithium silicate, sodium silicate, potassium silicate, or combinations thereof. In certain embodiments, the described surface in this invention can be surface modified by the conventional vapor coating or vapor deposition process to create SiO or SiO.sub.2 thin layer primers described in U.S. Pat. No. 4,338,377 (Beck et al.). Surface modification of substrates may also include vapor coating or vapor deposition of alkoxysilanes. Although the following discussion focuses on nanoparticle-containing primer coatings, various features described (e.g., coating thickness) apply to other primer coatings.

[0128] In certain embodiments, the nanoparticle-containing primer coating composition includes an aqueous dispersion having a pH of less than 5 comprising silica nanoparticles having average particle diameters of 40 nanometers or less, and an acid having a pKa of ≤3.5 (preferably <2.5, most preferably less than 1).

[0129] These acidified silica nanoparticle primer coating compositions, can be coated directly onto hydrophobic organic and inorganic substrates without either organic solvents or surfactants. The wetting property of these inorganic nanoparticle aqueous dispersions on hydrophobic surfaces such as polyethylene terephthalate (“PET”) or polycarbonate (“PC”) is a function of the pH of the dispersions and the pKa of the acid. The primer coating compositions are coatable on hydrophobic organic substrates when they are acidified with HCl to pH of 2 to 3, and even to 5 in some embodiments. In contrast, the primer coating compositions bead up on the organic substrates at neutral or basic pH.

[0130] The silica nanoparticles used in this primer composition are dispersions of submicron size silica nanoparticles in an aqueous or in a water/organic solvent mixture. Generally, the silica nanoparticles have an average primary particle diameter of 40 nanometers or less, preferably 20 nanometers or less, and more preferably 10 nanometers or less. The average particle size may be determined using transmission electron microscopy. The nanosilica described in this invention may be spherical or nonspherical. The silica nanoparticles are preferably not surface modified.

[0131] The smaller nanoparticles, those of 20 nanometers or less, generally provide better primer coatings, when acidified, without the need for additives such as tetraalkoxysilanes, surfactants or organic solvents. Further, the nanoparticles generally have a surface area greater than 150 m.sup.2/gram, preferably greater than 200 m.sup.2/gram, and more preferably greater than 400 m.sup.2/gram. The particles preferably have narrow particle size distributions, that is, a polydispersity (i.e., particle size distribution) of 2.0 or less, preferably 1.5 or less. If desired, larger silica particles may be added, in amounts that do not deleteriously decrease the coatability of the composition on a selected substrate, and do not reduce the hydrophilicity.

[0132] Inorganic silica sols in aqueous media are well known in the art and available commercially. Silica sols in water or water-alcohol solutions are available commercially under such trade names as LUDOX (from E.I. duPont de Nemours and Co., Inc., Wilmington, Del.), NYACOL (from Nyacol Co., Ashland, Mass.), or NALCO (from Ondea Nalco Chemical Co., Oak Brook, Ill.). One useful silica sol is NALCO™ 2326, silica sol with mean particle size of 5 nanometers, pH 10.5, and solid content 15% by weight. Other commercially available silica nanoparticles suitable for use in the present invention include NALCO™ 1115 and NALCO™ 1130 from NALCO Chemical Co., REMASOL™ SP30 from Remet Corp., and LUDOX SM from E.I. Du Pont de Nemours Co., Inc., and SNOWTEX™ ST-OUP, SNOWTEX™ ST-UP, SNOWTEX™ ST-PS-S from Nissan Chemical Co, and Li518 from Silco International Inc.

[0133] Non-aqueous silica sols (also called silica organosols) may also be used and are silica sol dispersions wherein the liquid phase is an organic solvent, or an aqueous organic solvent. In the practice of this invention, the silica sol is chosen so that its liquid phase is typically aqueous or an aqueous organic solvent. However, it has been observed that sodium stabilized silica nanoparticles should first be acidified prior to dilution with an organic solvent such as ethanol. Dilution prior to acidification may yield poor or non-uniform coatings. Ammonium stabilized silica nanoparticles may generally be diluted and acidified in any order.

[0134] The primer coating composition contains an acid or combination of acids, each having a pKa (H.sub.2O) of ≤3.5, preferably <2.5, most preferably less than 1. Useful acids include both organic and inorganic acids and may be exemplified by oxalic acid, citric acid, H.sub.2SO.sub.3, H.sub.3PO.sub.4, CF.sub.3CO.sub.2H, HCl, HBr, HI, HBrO.sub.3, HNO.sub.3, HClO.sub.4, H.sub.2SO.sub.4, CH.sub.3SO.sub.3H, CF.sub.3SO.sub.3H, CF.sub.3CO.sub.2H, and CH.sub.3SO.sub.2OH. Most preferred acids include HCl, HNO.sub.3, and H.sub.3PO.sub.4. In some embodiments, it is desirable to provide a mixture of an organic and inorganic acid. In some embodiments one may use a mixture of acids comprising those having a pKa≤3.5 (preferably <2.5, most preferably less than 1), optionally with minor amounts of other acids having pKa's>0. It has been found that weaker acids having a pKa of >4, such as acetic acid, do not provide a uniform coatings having the desirable properties of transmissivity, cleanability, and/or durability. In particular, primer coating compositions with weaker acids such as acetic acid typically bead up on the surface of a substrate.

[0135] The primer coating composition generally contains sufficient acid to provide a pH of less than 5, preferably less than 4, most preferably less than 3. In some embodiments, it has been found that the pH of the coating composition can be adjusted to pH from 5 to 6 after reducing the pH to less than 5. This allows one to coat pH-sensitive substrates.

[0136] Tetraalkoxy coupling agents, particularly tetraalkoxysilanes, such as tetraethylorthosilicate (“TEOS”), and oligomeric forms of tetraalkoxysilane, such as alkyl polysilicates (e.g., poly(diethoxysiloxane)), may also be useful to improve binding between silica nanoparticles. The optimal amount of coupling agent is determined experimentally and is dependent on the coupling agent's identity, molecular weight and refractive index. The coupling agent(s), when present, are typically added to the composition at levels of 0.1 to 50 percent by weight (wt-%) of the silica nanoparticle concentration, and more preferably 1 to 15 percent by weight of the silica nanoparticles.

[0137] The primed article includes a substrate surface bearing a continuous network of silica nanoparticles agglomerates. The particles preferably have an average primary particle size of 40 nanometers or less. The average particle size may be determined using transmission electron microscopy. As used herein, the term “continuous” refers to covering the surface of the substrate with virtually no discontinuities or gaps in the areas where the gelled network is applied. The term “network” refers to an aggregation or agglomeration of nanoparticles linked together to form a porous three dimensional network. The term “primary particle size” refers to the average size of unagglomerated single particles of silica.

[0138] The primer coating layer thicknesses may be higher, e.g., as high as a few microns thick, depending on the application. The mechanical properties may be expected to be improved when the coating thickness is increased.

[0139] In order to uniformly coat a primer composition onto a hydrophobic substrate from an aqueous system it may be desirable to increase the surface energy of the substrate and/or reduce the surface tension of the coating composition. The surface energy may be increased by oxidizing the substrate surface prior to coating using corona discharge, actinic radiation, or flame treatment methods. These methods may also improve adhesion of the coating to the substrate. Other methods capable of increasing the surface energy of the article include the use of organic polymeric primers such as thin coatings of polyvinylidene chloride (PVDC). Alternatively, the surface tension of the coating composition may be decreased by addition of lower alcohols (C.sub.1 to C.sub.8). In some instances, however, in order to improve the coating hydrophilicity for desired properties and to ensure uniform coating of the article from an aqueous or hydroalcoholic solution, it may be beneficial to add a wetting agent, which is typically a surfactant, to the primer composition.

[0140] The term “surfactant” as used herein describes molecules comprising 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 may include those disclosed in U.S. Pat. No. 6,040,053 (Scholz et al.).

[0141] For typical concentrations of silica nanoparticles (e.g., 0.2 to 15 percent by weight relative to the total coating composition) most surfactants comprise less than 0.1 percent by weight of the coating composition, preferably 0.003 to 0.05 percent by weight, in order to preserve the anti-reflective properties of the coating. It should be noted that with some surfactants a spotty coating is attained at concentrations in excess of what is needed to achieve the anti-fog property.

[0142] Anionic surfactants in the primer coating composition are preferred when added to improve 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 C.sub.6 to C.sub.20 alkyl, alkylaryl, and/or alkenyl groups, (2) at least one anionic group, such as sulfate, hydrophilic, phosphate, polyoxyethylene sulfate, polyoxyethylene hydrophilic, 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 the like. Representative commercial examples of useful anionic surfactants include sodium lauryl sulfate, e.g., TEXAPON™ L-100 from Henkel Inc., Wilmington, Del., or POLYSTEP™ B-3 from Stepan Chemical Co, Northfield, Ill.; sodium lauryl ether sulfate, e.g., POLYSTEP™ B-12 from Stepan Chemical Co., Northfield, Ill.; ammonium lauryl sulfate, e.g., STANDAPOL™ A from Henkel Inc., Wilmington, Del.; and sodium dodecyl benzene hydrophilic, e.g., SIPONATE™ DS-10 from Rhone-Poulenc, Inc., Cranberry, N.J.

[0143] Where the primer coating composition does not include a surfactant or when improved coating uniformity is desirable, it may be beneficial to add another wetting agent, including those that do not impart durable anti-fog properties, in order to ensure uniform coating of the article from an aqueous or hydroalcoholic solution. Examples of useful wetting agents include polyethoxylated alkyl alcohols (e.g., BRIJ™ 30 and BRIJ™ 35 from ICI Americas, Inc., and TERGITOL™ TMN-6™ Specialty Surfactant from Union Carbide Chemical and Plastics Co., polyethoxylated alkylphenols (e.g., TRITON™ X-100 from Union Carbide Chemical and Plastics Co., ICONOL™ NP-70 from BASF Corp.) and polyethylene glycol/polypropylene glycol block copolymer (e.g., TETRONIC™ 1502 Block Copolymer Surfactant, TETRONIC™ 908 Block Copolymer Surfactant, and PLURONIC™ F38 Block Copolymer Surfactant all from BASF, Corp.). Of course, any added wetting agent must be included at a level which will not destroy the anti-reflective or anti-fog properties of the coating, if such features are desired. Generally the wetting agent is used in amounts of less than 0.1 percent by weight of the coating composition, preferably 0.003 to 0.05 percent by weight of the coating composition depending on the amount of silica nanoparticles. Rinsing or steeping the coated article in water may be desirable to remove excess surfactant or wetting agent.

[0144] Primer coating compositions are preferably coated on the article using conventional techniques, such as bar, roll, curtain, rotogravure, spray, or dip coating techniques. In order to ensure uniform coating and wetting of the film, it may be desirable to oxidize the substrate surface prior to coating using corona discharge, plasma, actinic radiation or flame treatment methods. Other methods capable of increasing the surface energy of the article include the use of primers such as polyvinylidene chloride (“PVDC”).

[0145] The primer coatings of the present invention are preferably applied in uniform average thicknesses varying by less than 20 nm and more preferably by less than 10 nm in order to avoid visible interference color variations in the coating. The optimal average dry coating thickness is dependent upon the particular primer coating composition, but in general the average thickness of the coating is 10 nm to 1,000 nm, preferably 50 nm to 250 nm, more preferably 75 nm to 200 nm, and even more preferably 100 to 150 nm. The primer thickness can be measured with an ellipsometer such as a Gaertner Scientific Corp. Model No. L115C Ellipsometer.

[0146] Primer coatings of the present invention can be coated on both sides of a substrate if desired. Alternatively, the coatings of the present invention may be coated on one side of the substrate.

[0147] Once coated, the primed article is typically dried at temperatures of 20° C. to 150° C. in a recirculating oven. An inert gas may be circulated. The temperature may be increased further to speed the drying process, but care must be exercised to avoid damage to the substrate. For inorganic substrates, the cure temperature can be above 200° C. After the primer coating composition is applied to the substrate and dried, the coating comprises preferably from 60 to 95 percent by weight (more preferably from 70 to 92 percent by weight) of silica nanoparticles (typically agglomerated), from 0.1 to 20 percent by weight (more preferably from 10 to 25 percent by weight) tetraalkoxysilanes and optionally 0 to 5 percent by weight (more preferably from 0.5 to 2 percent by weight) surfactant, and optionally up to 5 percent by weight (preferably 0.1 to 2 percent by weight) wetting agent.

[0148] In some embodiments the primer coating composition itself provides a tough, abrasion resistant layer that protects the substrate and the underlying substrate from damage from causes such as scratches, abrasion and solvents.

[0149] In many embodiments, the primer coating compositions of the present invention are shelf stable, e.g., they do not gel, opacify, or otherwise deteriorate significantly. Further, in many embodiments, the primed articles are durable and abrasion resistant.

Surface Treatment

[0150] In some embodiments, the rewritable article is treated with energizing radiation in order to produce —OH or similar functional groups on the surface. Such radiation includes corona, plasma, actinic radiation, flashlamp, and flame treatment. In some embodiments, the treatment with energizing radiation is done before priming in order to get the primer to bond to the rewritable article.

Coated Articles

[0151] In some embodiments, writing surfaces of dry erase articles of the invention comprise a substrate containing hydroxyl groups such as porcelain, ceramic, and glass. In other embodiments, writing surfaces of dry erase articles comprise a substrate preferably having a primed surface, which may be of virtually any construction, transparent to opaque, polymeric, paper or metal, having a flat, curved, or complex shape, and preferably having formed thereon a continuous network of agglomerated silica nanoparticles.

[0152] In some embodiments, the writing surface of the dry erase articles include dry erase surfaces such as glass, porcelain steel, painted steel, painted metal, painted hardboard, melamine, coated film, coated paper, coated fiberboard sheets, and other dry erase surfaces known in current commerce. In other embodiments, the writing surface is a coated film or coated paper for use as a face stock for labels, as file folders, and so forth. In both embodiments, polymeric substrates may comprise polymeric sheet, film, or molded material.

[0153] Preferred primer, hydrophilic-functional, and hydrophilic polymeric coating compositions of the present invention provide hydrophilicity to a substrate.

[0154] In other embodiments, where increased hydrophilicity is desired, the substrate may be initially hydrophobic. The compositions may be applied to a wide variety of substrates by a variety of coating methods. As used herein, “hydrophilic” is used to refer to a surface that it is wet by aqueous solutions, and does not express whether or not the layer absorbs aqueous solutions. Surfaces on which drops of water or aqueous solutions exhibit a static water contact angle of less than 50° are referred to as “hydrophilic.” Hydrophobic substrates have a water contact angle of 50° or greater.

[0155] Substrates that can be used to make rewritable articles of the invention may, if desired, be transparent or translucent to visible light. Substrates used herein may be flexible or inflexible as desired. Illustrative examples of suitable substrates include polyester (e.g., polyethylene terephthalate, polybutyleneterephthalate), polycarbonate, allyldiglycolcarbonate, polyacrylates, such as polymethylmethacrylate, polystyrene, polysulfone, polyethersulfone, homo-epoxy polymers, epoxy addition polymers with polydiamines, polydithiols, polyethylene copolymers, fluorinated surfaces, cellulose esters such as acetate and butyrate, glass, ceramic, porcelain, coated paper, metal, organic and inorganic composite surfaces and the like, including blends and laminates thereof.

[0156] In other embodiments, the substrate need not be transparent. It has been found that the composition provides easily cleanable surfaces to substrates such as flexible films used label applications. Flexible films may be made from polyesters such as PET or polyolefins such as PP (polypropylene), PE (polyethylene) and PVC (polyvinyl chloride). The substrate can be formed into a film using conventional filmmaking techniques such as extrusion of the substrate resin into a film and optional uniaxial or biaxial orientation of the extruded film. The substrate can be treated to improve adhesion between the substrate and the primer coating, using, e.g., chemical treatment, corona treatment such as air or nitrogen corona, plasma, flame, or actinic radiation. If desired, an optional tie layer can also be applied between the substrate and the primer coating composition to increase the interlayer adhesion. The other side of the substrate may also be treated using the above-described treatments to improve adhesion between the substrate and an adhesive. The substrate may be provided with graphics, such as words or symbols as known in the art.

[0157] In still other embodiments, the substrate can be a metal or have a metal surface (e.g., vapor deposited metals) such as aluminum or stainless steel.

EXAMPLES

[0158] The invention will be further explained with the following illustrative, non-limiting examples. All amounts are by weight unless otherwise indicated.

Test Methods

[0159] The following test methods were used in the examples.

[0160] Permanent Marker Removal with Water and Glass Cleaner: Surfaces were marked with 6 permanent markers (3 brands, 2 colors of each brand), i.e., AVERY™ MARKS-A-LOT™, BIC™ permanent markers, and SHARPIE™ markers as indicated. One color of each brand was black. The second color was blue for the BIC™ marker and red for the AVERY™ MARKS-A-LOT™ and SHARPIE™ markers. The name of the marker was written on each surface. After aging for 24 hours at room temperature, a stream of water was applied to the writing with a spray bottle with the sample in horizontal orientation on a lab bench. After 20 seconds, a clean paper towel was used to remove as much of the writing as possible by wiping several times. This procedure was repeated once for a total of two washings with water.

[0161] The surface was examined for removal of permanent marker writing. The percent of the permanent marker writing completely removed by water was estimated visually. If a light or ghost image of the entire marker line remained on the surface, it was recorded as 0% removed.

[0162] If any writing remained on the surface, i.e., less than 100% was removed by water wipe as described above, then WINDEX™ glass cleaner was sprayed on the writing. After 20 seconds, the wet surface was wiped with a paper towel. The WINDEX™ wash and wipe was done twice before the percent of marker writing removed was estimated visually.

[0163] Dry Erase Marker Writability: Several surfaces were marked with 14 different dry erase markers (7 brands of dry erase markers), i.e., AVERY™ MARKS-A-LOT™, BEIFA™ private label markers, BIC™ Dry Erase markers, DIXON™ Dry Erase Markers, EXPO™ Bold, EXPO™ Low Odor and QUARTET™ Markers as indicated. Two colors of marker from each brand were chosen, one black and the other red, green, or blue. A typical dry erase material sample was about the size of a sheet of paper. For each marker brand, a horizontal space about 2.5 cm high on the sample was reserved for that marker brand. The first marker was used to write the marker brand name on the left hand side of the 2.5 cm high space and the second marker was used to write the same marker brand name on the right hand side of the 2.5 cm high space. In this manner, all the writing from each marker brand is lined up in one erasable horizontal line.

[0164] After marking on the inventive dry erase surface, each ink line was examined for dewetting. Dewetting or beading up of the dry erase ink was evidenced by the appearance of gaps in the ink line or a shrinking of the ink line. The total number of markers that dewet was recorded. Fourteen individual markers were utilized in the writing test, the range of possible dewetting scores is 0 to 14. If no markers dewet, the dewetting score was zero. If 10 markers dewet, the score was 10.

[0165] Dry Erase Marker Writing Removal: The dry erase marker writing was erased after 24 hours of dwell time on the surface with an EXPO™ dry eraser. A 2.5 kg flat brass weight was put on top of the eraser. This weight was the same length and width as the eraser. The weighted eraser was placed just before the first line of marker writing. The eraser was pushed over the entire line of that marker without additional hand pressure on the eraser. If enough writing was removed so that the name of the marker was not readable, then the marker was considered to have been erased with one stroke. If not, the eraser was passed over the writing again. This was continued until the name of the marker is no longer readable. The total number of eraser strokes required to erase each of the seven lines of dry erase marker writing was recorded. The minimum dry erase score is seven strokes.

[0166] Abrasion Test: A mechanical device was constructed capable of passing a standard EXPO™ dry eraser over a surface multiple times at a rate of 93 passes per minute. The housing for the eraser had a weight of about 250 g. This housing also held a 5 lb weight so that the total weight on the eraser was about 2.5 kg. The number of eraser passes over the sample was controlled by a countdown timer attached to the power cord of the instrument. After a present time, the instrument shut off. The timer was programmed to stop after 1000 passes of the eraser.

Materials

[0167] Markers, materials, and stock solutions utilized in the examples and comparative examples are identified in Tables 1, 2, and 3, respectively.

TABLE-US-00001 TABLE 1 Permanent and Dry Erase Markers Brand Marker Type Source AVERY ™ MARKS-A-LOT ™ markers, chisel Permanent Avery-Dennison Corp., Pasadena, point CA BIC ™ markers, chisel point Permanent BIC Corporation, Milford, CN SHARPIE ™ markers, fine point Permanent Sanford Corp., Bellwood, IL AVERY ™ MARKS-A-LOT ™ markers, chisel Dry erase Avery-Dennison Corp. point BIC ™ markers, chisel point Dry erase BIC Corporation TICONDEROGA ™ markers, chisel point Dry erase Dixon Ticonderoga Co., Heathrow, FL BEIFA ™ markers, chisel point Dry erase Beifa Corp, Tokyo, Japan EXPO ™ Bold markers, chisel point Dry erase Sanford Corp. EXPO ™ Low Odor markers Dry erase Sanford Corp. QUARTET ™ markers, chisel point Dry erase Acco, Inc., Lincolnshire, IL

TABLE-US-00002 TABLE 2 Materials Material Description Source SILCO ™ Li518 5 nm lithium SILCO2 stabilized silica, 18 International Inc, wt % in water Portland, OR POLYSTEP ™ B-430S sodium lauryl ether Stepan Company, sulfate, 4eo Northfield, IL. LITHISIL ™ Lithium silicate, 23 PQ Corp, Valley wt % in water Forge, PA 3-(N,N-dimethylaminopropyl) trimethoxysilane Gelest, Morrisville, PA 1,4-butane sultone Aldrich Chemical, St. Louis, MO. LSS-75 Lithium silicate, 22 Nissan Chemical wt % in water America Corp, Huston, TX 3-(trihydroxysilyl)propyl methyl-phosphonate, 42 wt % in water Aldrich Chemical monosodium salt Carboxyethylsilanetriol, sodium salt 25 wt % in water Gelest 3-(trihydroxysilyl)-1-propanesulfonic acid 30 to 35 wt % in water Gelest N-(3-triethoxysilylpropyl)gluconamide 50 wt % in ethanol Gelest N-trimethoxysilylpropyl-N,N,N-trimethylammonium 50 wt % in ethanol Gelest chloride 2-[methoxy(polyethylenoxy)propyl]trimethoxysilane WAMW 460 to 590 Gelest Nitric acid EMD Chemicals, Gibbstown, NJ KIMWIPES ™ paper tissues Lint free tissues Kimberly Clark, Roswell, GA ALCONOX ™ detergent Powdered detergent Alconox Inc., White Plains, NJ Porcelain steel sheet Porcelain coated steel JFE Corp., Tokyo, Japan Glass plate Float glass Cardinal Glass Co., Eden Prairie, MN Clear polyester film, 2 mil thick, one side primed with Polyethylene 3M Company, St. PVDC terephthalate film Paul, MN Painted steel panel Dry erase painted Data Zone, Shen steel Zhen, China 2 mil white polyester film with a UV cured Dry erase film Protect-all Corp., multifunctional acrylate coating Darien, WI WINDEX ™ glass cleaner Water based cleaner SC Johnson Co., Racine, WI EXPO ™ dry eraser Eraser with felt fibers Sanford Corp., Bellwood, IL 3M ™ Whiteboard Eraser Melamine fiber pad 3M Company POVAL ™ R-1130 Silane functional Kuraray America polyvinyl alcohol Inc., Houston, TX POVAL ™ R-2105 Silane functional Kuraray America polyvinyl alcohol Inc. POVAL ™ R-3109 Silane functional Kuraray America polyvinyl alcohol Inc.

TABLE-US-00003 TABLE 3 Stock Solutions Name Preparation NPS1 SILCO ™ Li518 diluted to 1% solids in water, acidified to pH 1.5 with 1.5M nitric acid NPS2 A 5 wt % solution of [SILCO ™ Li518: Polystep B-430S (99:1 w/w)] in water and was acidified with 0.8M HNO.sub.3 to pH of 2. NPS3 A 2 wt % solutions of SILCO ™ Li518 in water LS1 A 2 wt % solution of LITHISIL ™ 25 in water LS2 A 2 wt % solution of LSS-75 in water

[0168] Coating compositions were prepared as follows, all amounts are expressed in parts w by weight unless otherwise indicated.

[0169] Coating Composition 1, a solution of

##STR00003##

a zwitterionic silane, was prepared as follows. 3-(N,N-dimethylaminopropyl)trimethoxysilane (49.7 g, 239 mmol) was added to a screw-top jar followed by deionized (“DI”) water (82.2 g) and 1,4-butane sultone (32.6 g, 239 mmol). The reaction mixture was heated to 75° C. and mixed for 14 hours. After heating, the reaction mixture was diluted to 2 wt % in water to obtain the final coating solution.

[0170] Coating Composition 2 was prepared as a 2 wt % solution of a blend of Coating Composition 1: LS1: NPS3 (61:19:20 w/w) in water.

[0171] Coating Composition 3 was prepared as a 2 wt % solution of a blend of Coating Composition 1: NPS3 (80:20 w/w) in water.

[0172] Coating Composition 4: Preparation of

##STR00004##

coating solution, hydroxy sulfonate silane, was prepared as described in U.S. Pat. No. 4,338,377 and diluted to 2 wt %.

[0173] Coating Composition 5 (phosphonate silane) was prepared by dilution of 3-(trihydroxysilyl)-propyl methyl-phosphonate, monosodium salt with water to a 2 wt % solution.

[0174] Coating Composition 6 (carboxylate silane) was prepared by dilution of carboxy-ethylsilanetriol, sodium salt with water to a 2 wt-% solution.

[0175] Coating Composition 7 (propane sulfonic acid) was prepared by dilution of 3-(trihydroxysilyl)-1-propanesulfonic acid with water to a 2 wt % solution.

[0176] Coating Composition 8 (sugar silane) was prepared by dilution of N-(3-triethoxy-silylpropyl)gluconamide with water to a 2 wt % solution.

[0177] Coating Composition 9 (ammonium silane) was prepared by dilution of N-trimethoxy-silylpropyl-N,N,N-trimethylammonium chloride with water to a 2 wt % solution.

[0178] Coating Composition 10 (polyethylene glycol silane) was prepared by dilution of 2-[methoxy-(polyethylenoxy) propyl]trimethoxysilane with water to a 2 wt % solution.

[0179] Coating Composition 11 was prepared as a 2 wt % solution of a blend of Coating Composition 4: LS2 (65:35 w/w) in water.

[0180] Coating Composition 12 was prepared as a 2 wt % solution of a blend of Coating Composition 5: LS2 (65:35 w/w) in water.

[0181] Coating Composition 13 was prepared as a 2 wt % solution of a blend of Coating Composition 6: LS2 (65:35 w/w) in water.

[0182] Coating Composition 14 was prepared as a 2 wt % solution of a blend of Coating Composition 7: LS2 (65:35 w/w) in water.

[0183] Coating Composition 15 was prepared as a 2 wt % solution of a blend compound of Coating Composition 8: LS2 (65:35 w/w) in water.

[0184] Coating Composition 16 was prepared as a 2 wt % solution of a blend of Coating Composition 9: LS2 (65:35 w/w) in water.

[0185] Coating Composition 17 was prepared as a 2 wt % solution of a blend of Coating Composition 10: LS2 (65:35 w/w) in water.

[0186] Coating Composition 18 was prepared as a 2 wt % solution of a blend of Coating Composition 1: LS2 (65:35 w/w) in water.

[0187] Coating Composition 19 was prepared as a 2 wt % solution of a blend of Coating Composition 1: LS2 (65:35 w/w) in water and was acidified with 0.8 M HNO.sub.3 to a pH of 5.

[0188] Coating Composition 20 was prepared as a 2 wt % solution of a blend of Coating Composition 8: LS2 (65:35 w/w) in water and was acidified with 0.8 M HNO.sub.3 to a pH of 4.5.

[0189] Coating Composition 21 was prepared as a 2 wt % solution of a blend of Coating Composition 6: LS2 (65:35 w/w) in water and was acidified with 0.8 M HNO.sub.3 to a pH 4.5.

[0190] Coating Composition 22 was prepared as a 2 wt % solution of a blend of Coating Composition 5: LS2 (65:35 w/w) in water and was acidified with 0.8 M HNO.sub.3 to a pH of 3.

[0191] Coating Composition 23 was prepared as a 2 wt % solution of POVAL™ R3109 in water and was acidified with 0.8 M HNO.sub.3 to a pH of 3.

[0192] Coating Composition 24 was prepared as a 2 wt % solution of POVAL™ R1130 in water and was acidified with 0.8 M HNO.sub.3 to a pH of 3.

[0193] Coating Composition 25 was prepared as a 2 wt % solution of POVAL™ R2105 in water and was acidified with 0.8 M HNO.sub.3 to a pH of 3.

Example 1

[0194] Before coating with the indicated coating composition, porcelain steel sheets were cleaned to remove adsorbed organic matter from the surface, exposing free OH groups. A paste of ALCONOX™ detergent was rubbed on each porcelain sheet with a wet paper towel. Then the sheet was rinsed with water. The sheet was considered clean if water ran off the sheet without beading up.

[0195] A clean porcelain steel sheet about 20.3 cm×25 cm was coated with three coats of solution NPS1 using a KIMWIPE™ paper tissue. The samples were dried at room temperature, and then were heated at 150° C. for 15 minutes. The samples were subsequently coated with three coats of Coating Composition 2 using a KIMWIPE™ paper tissue. The samples were dried at room temperature, and then were heated at 150° C. for 15 minutes. After cooling the samples to room temperature, they were rinsed with DI water (600 mL/minute) for 60 seconds.

Example 2

[0196] For Example 2, a 20.3 cm×20.3 cm float glass plate was cleaned with a paste of ALCONOX™ detergent so that water ran off the plate without beading up. The clean glass plate was coated with Coating Composition 2 using a KIMWIPE™ paper tissue. The coated glass plate was dried at room temperature in an air stream and then heated for 10 minutes at 150° C. After cooling the sample to room temperature, it was rinsed with DI water (600 mL/minute) for 60 seconds and then dried with a paper towel.

Example 3

[0197] Before coating, the painted steel sheets were cleaned using ALCONOX™ detergent. Then the sheet was coated with three coats of NPS1 using a KIMWIPE™ paper tissue. The samples were dried at room temperature in an air stream and then were heated at 150° C. for 15 minutes. The samples were subsequently coated with three coats of Coating Composition 2 using a KIMWIPE™ paper tissue. The sample was dried at room temperature and then was heated at 150° C. for 15 minutes. After cooling, the sample to room temperature, it was rinsed with DI water (600 mL/minute) for 60 seconds and dried with a paper towel.

Example 4

[0198] The film in this example was a 4 mil PVDC primed clear polyester (PET) film from 3M Company. The PET film was coated with silica nanoparticles by using NPS2 solution and a Meyer rod (#6). The coated film was dried at room temperature before heating for 5 minutes at 120° C. These films were coated with Coating Composition 3 in the same manner as that used for forming silica nanoparticle coatings. The coated films were dried at room temperature before being heated at 120° C. for 10 minutes. After cooling the samples to room temperature, they were rinsed with DI water (600 mL/minute) for 60 seconds and dried with a paper towel.

Example 5

[0199] The base film for this example was 2 mil (0.05 mm) white polyester from with a UV cured acrylic coating obtained from Protect-all, Inc. The dry erase film was flame treated by the method described in example 8 of U.S. Pat. No. 5,244,780 (Strobel et al.). After flame treatment, the film was coated with silica nanoparticles in NPS2 solution using a #7 Mayer rod. The coated film was dried at room temperature before being heated for 15 minutes at 120° C. The dried film was then coated with Coating Composition 3 with a #7 Mayer rod. The coated film was dried at room temperature before being heated at 150° C. for 15 minutes. After cooling the film to room temperature, it was rinsed with DI water (600 mL/minute) for 60 seconds and then dried with a paper towel.

Comparative Example C1

[0200] Porcelain steel panel as received.

Comparative Example C2

[0201] Float glass plate as received.

Comparative Example C3

[0202] Painted steel panel as received.

Comparative Example C4

[0203] Clear polyester film, 2 side primed with PVDC, as received.

Comparative Example C5

[0204] White polyester dry erase film as received.

TABLE-US-00004 TABLE 4 Examples 1 to 5 and Comparative Examples C1 to C5 Permanent 24 hr Marker Permanent Marker Dry % Removed % Removed with Erase Example Base with Water WINDEX ™ Strokes 1 Porcelain steel 100 100 7 C1 Porcelain steel 13 72 7 2 Glass 100 100 7 C2 Glass 21 87 7 3 Painted steel 98 100 8 C3 Painted steel 0 5 9 4 PET film 100 100 9 C4 PET film 0 8 85 5 Dry erase film 93 95 77 C5 Dry erase film 0 8 12

[0205] Example 1 was tested for abrasion resistance with two dry erasers, an EXPO™ dry eraser and a 3M™ whiteboard eraser. The erasers were passed over the sample 5000 times as shown in Table 5 with the abrasion tester described in the Test Methods section. After abrasion, each sample was tested for permanent marker removal by water and Windex brand window cleaner.

TABLE-US-00005 TABLE 5 Abrasion test on Example 1. % Removed % Removed with Example Eraser with Water WINDEX ™ 1 EXPO ™ dry eraser 100 100 1 3M ™ whiteboard eraser 100 100

Examples 6 to 17

[0206] For Examples 6 to 17, a series of 20.3 cm×20.3 cm float glass plates first cleaned with a paste of ALCONOX™ detergent so that water no longer beaded up on the glass plate. The clean glass plates were each coated with Coating Composition 1 and 4 to 10, respectively, using a KIMWIPE™ paper tissue. The coated glass plates were dried at room temperature and heated for 10 minutes at 150° C. After cooling the samples to room temperature, they were rinsed with DI water (600 mL/minute) for 60 seconds and dried at room temperature before testing.

TABLE-US-00006 TABLE 6 Examples 6 to 17 Permanent Permanent Dry Erase Dewet of marker marker Strokes markers removal removal 24 hr Coating 24 hr 24 hr 24 hr EXPO ™ Example Composition Substrate Silane score Water WINDEX ™ eraser 6 4 Glass Hydroxy 0 70 96 7 sulfonate 7 5 Glass Phosphonate 0 92 100 7 8 6 Glass Carboxylate 0 100 100 7 9 8 Glass Gluconamide 0 77 100 7 10 1 Glass Zwitterion 0 100 100 7 11 11 Glass Hydroxy 0 100 100 7 sulfonate 12 12 Glass Phosphonate 0 100 100 7 13 13 Glass Carboxylate 0 100 100 7 14 14 Glass Sulfonate 0 100 100 7 15 15 Glass Gluconamide 0 100 100 7 16 18 Glass Zwitterion 0 100 100 7

Comparative Examples C6 to C11

[0207] A series of 20.3 cm×20.3 cm float glass plates were first cleaned with a paste of ALCONOX™ detergent. The plates were rinsed with water and dried in an air stream. After cleaning and drying, they were coated with Coating Compositions 7, 9, 10, 16, and 17, respectively, using a KIMWIPE™ paper tissue. The coated glass plates were dried at room temperature and then heated for 10 minutes at 150° C. After cooling the samples to room temperature, they were rinsed with DI water (600 mL/minute) for 60 seconds and dried before marker testing. Results are indicated in Table 7.

TABLE-US-00007 TABLE 7 Comparative Examples C6 to C11 Permanent Permanent Dry Erase Dewet of marker marker Strokes markers removal removal 24 hr Coating 24 hr 24 hr 24 hr EXPO ™ Example Composition Substrate Surface score Water WINDEX ™ eraser C6 None Glass Cleaned 0 67 83 7 C7 7 Glass Sulfonate silane 0 58 85 7 C8 9 Glass Quaternary 0 52 57 7 ammonium silane C9 10 Glass Polyethylene 0 35 83 7 oxide silane  C10 16 Glass Quaternary 0 70 70 7 ammonium silane  C11 17 Glass Polyethylene 0 60 84 7 oxide silane

Examples 17 to 22

[0208] A series of 20 cm×25 cm porcelain steel panels were first cleaned with a paste of ALCONOX™ detergent. The plates were rinsed with water and dried in an air stream. After cleaning and drying, they were coated with coating compositions as indicated in Table 7 and using a KIMWIPE™ paper tissue. The coated porcelain plates were dried at room temperature and then heated for 10 minutes at 150° C. After cooling the samples to room temperature, they were rinsed with DI water (600 mL/minute) for 60 seconds and dried before marker testing.

TABLE-US-00008 TABLE 8 Examples 17 to 22 Permanent Permanent Dry Erase Dewet of marker marker Strokes markers removal removal 24 hr Coating 24 hr 24 hr 24 hr EXPO ™ Example Composition Substrate Silane score Water WINDEX ™ eraser 17 18 Porcelain Zwitterion 0 100 100 7 18 11 Porcelain Hydroxy 0 100 100 7 Sulfonate 19 15 Porcelain Sugar silane 0 100 100 7 20 13 Porcelain Carboxylate 0 100 100 8 21 12 Porcelain Phosphonate 0 100 100 7 22 25 Porcelain PVA silane 0 98 100 12

[0209] Examples 17 to 22 were tested for abrasion resistance to a dry eraser. The EXPO™ dry eraser was passed over each sample 1000 times with the abrasion tester described in the Test Methods section. After abrasion, each sample was tested for permanent marker removal by water and Windex.

TABLE-US-00009 TABLE 9 Abrasion results for Examples 17 to 22. Percent removed Percent removed with Example with water WINDEX ™ 17 100 100 18 100 100 19 100 100 20 90 100 21 91 100 22 100 100

[0210] Examples 17 to 22 were tested for the effects of repeated writing and erasing in the same place. The black SHARPIE™, AVERY™, and BIC™ markers were written on each example. After the writing was dry, the sample was sprayed with WINDEX™ brand window cleaner and wiped clean with a paper towel. The writing and cleaning was performed 100 times on each example. Then the permanent marker removal test was done on each example.

TABLE-US-00010 TABLE 10 Write and erase results for Examples 17 to 22. Percent removed Percent removed with Example with water WINDEX ™ 17 100 100 18 100 100 19 83 100 20 83 98 21 100 100 22 100 100

Examples 23 to 30

[0211] The film in this example was a 4 mil PVDC primed clear polyester (PET) film from 3M Company. The PET film was coated with silica nanoparticles by using NPS2 solution and a Meyer rod (#6). The coated film was dried at room temperature before heating for 5 minutes at 120° C. These films were coated with Coating Composition 3 in the same manner as that used for forming silica nanoparticle coatings. The coated films were dried at room temperature before being heated at 120° C. for 10 minutes. After cooling the samples to room temperature, they were rinsed with DI water (600 mL/minute) for 60 seconds and dried with a paper towel.

TABLE-US-00011 TABLE 11 Examples 23 to 30. Permanent Permanent Dry Erase Dewet of marker marker Strokes markers removal removal 24 hr Coating 24 hr 24 hr 24 hr EXPO ™ Example Composition Substrate Silane score Water WINDEX ™ eraser 23 19 Primed Zwitterion 0 70 99 13 PET 24 11 Primed Sulfonate 0 65 100 9 PET 25 20 Primed Sugar silane 0 23 98 10 PET 26 21 Primed Carboxylate 0 2 98 10 PET 27 22 Primed Phosphonate 0 73 100 8 PET 28 23 Primed Polyvinyl 0 50 98 11 PET alcohol 29 24 Primed Polyvinyl 0 44 99 16 PET alcohol 30 25 Primed Polyvinyl 0 59 97 15 PET alcohol

Example 31

[0212] An aqueous solution of polyvinyl alcohol (98 mole % hydrolyzed, weight average molecular weight (“WAMW”) of about 31,000 to 50,000) was prepared by dissolving 3 g of the PVA in 97 g D.I water and stirring at 60° C. overnight. The solution was subsequently acidified with concentrated HNO.sub.3 to a pH of 3. Polyester film was primed with silica nanoparticles according to the procedure in Examples 23 to 30. The acidified solution of PVA was coated on the silica nanoparticle primed polyester from with a #6 Mayer bar. The coated film was cured at 120 C for 5 to 10 minutes.

Example 32

[0213] An aqueous solution of polyvinyl alcohol (98 mole % hydrolyzed, WAMW of about 31,000 to 50,000) was prepared by dissolving 3 g of the PVA in 97 g DI water and stirring at 60° C. overnight. The solution was subsequently acidified with concentrated HNO.sub.3 to a pH of 3. The acidified solution of PVA was coated on polyester film having no silica nanoparticle primer with a #6 Mayer bar. The coated film was cured at 120° C. for 5 to 10 minutes.

TABLE-US-00012 TABLE 12 Examples 31 and 32 Dewet of Permanent Permanent marker markers marker removal removal Coating 24 hr 24 hr 24 hr Example Composition Substrate Solution score Water WINDEX ™ 23 19 Primed PET Acidified 0 57 100 PVA 24 11 Unprimed Acidified 0 33 98 PET PVA

[0214] The complete inventions of the patents, patent documents, and publications cited herein are incorporated by reference in their entirety as if each were individually incorporated.

[0215] Various modifications and alterations to this invention will become apparent to those skilled in the art without departing from the scope and spirit of this invention. It should be understood that this invention is not intended to be unduly limited by the illustrative embodiments and examples set forth herein and that such examples and embodiments are presented by way of example only with the scope of the invention intended to be limited only by the claims set forth herein as follows.