阅读说明：本技术 补充可书写可清洁制品的方法和套件 (Method and kit for replenishing writable cleanable articles ) 是由 扎卡里·J·马姆伯格 贾斯廷·A·里德尔 西乌德·M·艾哈迈德 德里克·A·亨特利 琳恩·E 于 2019-03-18 设计创作，主要内容包括：本发明公开了包括可书写可清洁制品的方法和套件,其中在一个实施方案中,提供了在可书写可清洁制品上补充亲水性表面的方法。所述方法包括：提供可书写可清洁制品,所述制品包括亲水性外覆层,所述亲水性外覆层具有至少部分被消耗(即,至少部分消失)的亲水性表面；以及将清洁和保护组合物施加到所述亲水性外覆层的至少一部分；以及干燥所述清洁和保护组合物以提供具有补充的亲水性表面的干燥表面。所述可书写可清洁制品包括：具有前表面的基底构件；面层,所述面层包括固化的聚合物基质和分散在所述聚合物基质中的多个无机纳米粒子,其中所述面层设置在所述基底构件前表面的至少一部分上；设置在所述面层的至少一部分上的任选底漆层；以及亲水性外覆层,所述亲水性外覆层通过硅氧烷键键合到所述面层和/或所述任选底漆层,从而提供可书写可清洁的亲水性表面。所述清洁和保护组合物包含：亲水性硅烷；表面活性剂；以及水。(Methods and kits comprising a writable cleanable article are disclosed, wherein in one embodiment, a method of supplementing a hydrophilic surface on a writable cleanable article is provided. The method comprises the following steps: providing a writable cleanable article comprising a hydrophilic outer cover having a hydrophilic surface that is at least partially consumed (i.e., at least partially disappeared); and applying a cleaning and protective composition to at least a portion of the hydrophilic overcoat layer; and drying the cleaning and protection composition to provide a dried surface having a complimentary hydrophilic surface. The writable cleanable article comprises: a base member having a front surface; a facing layer comprising a cured polymer matrix and a plurality of inorganic nanoparticles dispersed in the polymer matrix, wherein the facing layer is disposed on at least a portion of the front surface of the base member; an optional primer layer disposed on at least a portion of the face layer; and a hydrophilic overcoat layer bonded to the top layer and/or the optional primer layer by siloxane bonds, thereby providing a writable, cleanable hydrophilic surface. The cleaning and protection composition comprises: a hydrophilic silane; a surfactant; and water.)

1. A method of supplementing a hydrophilic surface on a writable cleanable article, the method comprising:

providing a writable, cleanable article comprising:

a base member having a front surface;

a facing layer comprising a cured polymer matrix and a plurality of inorganic nanoparticles dispersed in the polymer matrix, wherein the facing layer is disposed on at least a portion of a front surface of a base member;

an optional primer layer disposed on at least a portion of the face layer; and

a hydrophilic overcoat layer bonded to the top layer and/or the optional primer layer by siloxane bonds providing a writable, cleanable hydrophilic surface;

wherein the hydrophilic overcoat layer has a hydrophilic surface that is at least partially consumed;

applying a cleaning and protective composition to at least a portion of the hydrophilic overcoat layer; wherein the cleaning and protection composition comprises:

a hydrophilic silane;

a surfactant; and

water; and

drying the cleaning and protection composition to provide a dried surface having a complementary hydrophilic surface.

2. The method of claim 1, wherein the base member comprises a flexible substrate.

3. The method of claim 2, wherein the flexible substrate comprises a film.

4. The method of any one of claims 1 to 3, wherein the cured polymer matrix comprises an organic polymer matrix.

5. The method of claim 4, wherein the cured polymer matrix comprises a (meth) acrylate polymer.

6. The method of any one of claims 1 to 5, wherein the inorganic nanoparticles are selected from the group consisting of alumina, antimony tin oxide, bismuth subsalicylate, boehmite, calcium carbonate, calcium phosphate, ceria, graphene, halloysite, lanthanum boride, lithium carbonate, silver, amorphous silica, colloidal silica, titania, zinc oxide, zirconia, and combinations thereof.

7. The method of any one of claims 1 to 6, wherein the hydrophilic overcoat comprises sulfonate functional groups, phosphate functional groups, phosphonate functional groups, carboxylate functional groups, or a combination thereof.

8. The method of any one of claims 1 to 7, wherein the hydrophilic overcoat layer is formed from a zwitterionic compound of formula (I) or formula (II) below:

(R¹O)_p-Si(R²)_q-W-N⁺(R³)(R⁴)-(CH₂)_m-SO₃ ^-(I)

(R¹O)_p-Si(R²)_q-CH₂CH₂CH₂-N⁺(CH₃)₂-(CH₂)_m-SO₃ ^-(II)

wherein:

each R¹Independently hydrogen, a methyl group or an ethyl group;

each R²Independently a hydroxyl group, (C1 to C4) an alkyl group, and (C1 to C4) an alkoxy group (preferably, a methyl group or an ethyl group);

each R³And R⁴Independently saturated or unsaturated, linear, branched or cyclic organic groups (preferably having 20 carbon atoms or less) which may be linked together, optionally together with atoms of the group W, to form a ring;

w is an organic linking group;

p is an integer of 1 to 3;

m is an integer of 1 to 10 (preferably 1 to 4);

q is 0 or 1; and is

p+q＝3。

9. The method of any one of claims 1 to 8, wherein the cleaning and protection composition has a weight ratio of the hydrophilic silane to the surfactant of at least 1: 1.

10. The method of any one of claims 1 to 9, wherein the cleaning and protection composition further comprises at least one of a water-soluble alkali metal silicate, a tetraalkoxysilane monomer, a tetraalkoxysilane oligomer, and an inorganic silica sol.

11. The method according to any one of claims 1 to 10, wherein the cleaning and protection composition comprises at least two different surfactants.

12. The method of any one of claims 1 to 11, wherein the hydrophilic silane is a sulfonate-functional zwitterionic silane having the following formula (I) or formula (II):

(R¹O)_p-Si(R²)_q-W-N⁺(R³)(R⁴)-(CH₂)_m-SO₃ ^-(I)

(R¹O)_p-Si(R²)_q-CH₂CH₂CH₂-N⁺(CH₃)₂-(CH₂)_m-SO₃ ^-(II)

wherein:

each R¹Independently hydrogen, a methyl group or an ethyl group;

each R²Independently a hydroxyl group, (C1 to C4) an alkyl group, and (C1 to C4) an alkoxy group (preferably, a methyl group or an ethyl group);

each R³And R⁴Independently saturated or unsaturated, linear, branched or cyclic organic groups (preferably having 20 carbon atoms or less) which may be linked together, optionally together with atoms of the group W, to form a ring;

w is an organic linking group;

p is an integer of 1 to 3;

m is an integer of 1 to 10 (preferably 1 to 4);

q is 0 or 1; and is

p+q＝3。

13. The method of any one of claims 1 to 12, wherein the cleaning and protection composition comprises two different hydrophilic silanes.

14. A method for cleaning and protecting a writable cleanable article, the method comprising:

providing a writable, cleanable article comprising:

a base member having a front surface;

a facing layer comprising a cured polymer matrix and a plurality of inorganic nanoparticles dispersed in the polymer matrix, wherein the facing layer is disposed on at least a portion of a front surface of a base member;

an optional primer layer disposed on at least a portion of the face layer; and

a hydrophilic overcoat layer bonded to the top layer and/or the optional primer layer by siloxane bonds providing a writable, cleanable hydrophilic surface;

applying a cleaning and protecting composition to at least a portion of the writable, cleanable, hydrophilic surface; wherein the cleaning and protection composition comprises:

a hydrophilic silane;

a surfactant; and

water; and

drying the cleaning and protection composition to provide a dry surface.

15. A kit, the kit comprising:

a writable cleanable article, the article comprising:

a base member having a front surface;

a facing layer comprising a cured polymer matrix and a plurality of inorganic nanoparticles dispersed in the polymer matrix, wherein the facing layer is disposed on at least a portion of a front surface of a base member;

an optional primer layer disposed on at least a portion of the face layer; and

a hydrophilic overcoat layer bonded to the top layer and/or the optional primer layer by siloxane bonds providing a writable, cleanable hydrophilic surface; and

a cleaning and protective composition comprising:

a hydrophilic silane;

a surfactant; and

and (3) water.

Background

The ease of cleaning of surfaces, such as dust and dirt removal, graffiti, or erasable surfaces is a long-desired feature. Exemplary applications where ease of cleaning is desirable include windows, electronic device screens, countertop surfaces, appliances, door and wall surfaces, signs, vehicle surfaces such as those on trains or buses, and the like. Other exemplary applications include writable surfaces such as dry erase boards, folders, notebooks, etc., where efficient writing and subsequent ease of removal of the writing is desired.

Articles having writable clean surfaces are prepared from a variety of materials that provide various combinations of properties. Commonly recognized examples include certain label materials, dry erase articles, letter paper, file folders with cleanable tabs, and the like.

Dry erase boards have been used as writing surfaces for many years due to their convenience and versatility. The plate provides an expression means which eliminates the mess and inconvenience of a chalk plate.

A continuing challenge faced by dry erase articles is to find surfaces that can be easily cleaned, resist staining when written with permanent markers, can be easily erased when written with conventional dry erase markers, are durable, and the like. Glass and porcelain surfaces have long been used as writing surfaces for dry erase articles, but improved performance is still desired. For example, although their non-porous surfaces are easy to write with dry erase markers and then easily erased after a day, over time, the adhesion of the writing to the board becomes difficult or even impossible to remove by wiping with a dry wiper. Dry erase scripts that cannot be removed with a dry eraser are commonly referred to as ghosting (ghost). In addition, permanent markers tend to adhere well to such surfaces and are not easily removed. For example, such writing is typically only removable with a solvent such as isopropyl alcohol. Solvent-based cleaners are being replaced on the market by cleaners containing water, surfactant and a small percentage of low volatility organic solvents. However, such cleaners are not always able to remove permanent marker writing from dry erase boards. Other common dry-erase surfaces with the same cleaning problems include coated films, melamine, and painted plastics and steel.

There is a continuing need for methods of cleaning, protecting and restoring writable and cleanable surfaces.

Disclosure of Invention

The writable cleanable articles described herein can be easily and effectively cleaned repeatedly. Such articles can therefore be used in a variety of desirable applications, for example, they are particularly useful for dry wiping surfaces. These articles exhibit excellent writability with dry erase markers, while the writing of permanent markers can be easily removed with water and cloth or wipes. No special solvents or tools are required. However, over time, even such advantageous properties that make them writable and cleanable disappear as a result of the consumption of the surface layer. The compositions used in the methods described herein can improve the performance of writable, cleanable articles, particularly in terms of cleanability. The compositions used in the methods described herein may also complement performance (particularly in terms of cleanability, and in certain embodiments, in terms of writability) to that of (or close to that of) the original, unused, writable, cleanable article.

In one embodiment, a method of supplementing a hydrophilic surface on a writable cleanable article is provided. The method comprises the following steps: providing a writable cleanable article comprising a hydrophilic outer cover having a hydrophilic surface that is at least partially consumed (i.e., at least partially disappeared); and applying a cleaning and protective composition to at least a portion of the hydrophilic overcoat layer; and drying the cleaning and protection composition to provide a dried surface having a complimentary hydrophilic surface. The writable cleanable article comprises: a base member having a front surface; a facing layer comprising a cured polymer matrix and a plurality of inorganic nanoparticles dispersed in the polymer matrix, wherein the facing layer is disposed on at least a portion of the front surface of the base member; an optional primer layer disposed on at least a portion of the face layer; and a hydrophilic overcoat layer bonded to the top layer and/or the optional primer layer by siloxane bonds, thereby providing a writable, cleanable hydrophilic surface. The cleaning and protective composition comprises a hydrophilic silane, a surfactant, and water, and can supplement performance (especially in terms of cleanability, and in certain embodiments, in terms of writability) to (or approach) that of an original, unused, writable, cleanable article.

In one embodiment, a method of cleaning and protecting a writable cleanable article is provided. The method comprises the following steps: providing a writable, cleanable article, applying a cleaning and protecting composition to at least a portion of the writable, cleanable hydrophilic surface; and drying the cleaning and protection composition to provide a dry surface. The writable cleanable article comprises: a base member having a front surface; a facing layer comprising a cured polymer matrix and a plurality of inorganic nanoparticles dispersed in the polymer matrix, wherein the facing layer is disposed on at least a portion of the front surface of the base member; an optional primer layer disposed on at least a portion of the face layer; and a hydrophilic overcoat layer bonded to the top layer and/or the optional primer layer by siloxane bonds, thereby providing a writable, cleanable hydrophilic surface. The cleaning and protective composition comprises a hydrophilic silane, a surfactant and water and improves the performance of the writable cleanable article, in particular in terms of cleanability.

In one embodiment, a kit is provided, the kit comprising: a writable cleanable article; and cleaning and protective compositions. The writable cleanable article comprises: a base member having a front surface; a facing layer comprising a cured polymer matrix and a plurality of inorganic nanoparticles dispersed in the polymer matrix, wherein the facing layer is disposed on at least a portion of the front surface of the base member; an optional primer layer disposed on at least a portion of the face layer; and a hydrophilic overcoat layer bonded to the top layer and/or the optional primer layer by siloxane bonds, thereby providing a writable, cleanable hydrophilic surface. The cleaning and protection composition comprises a hydrophilic silane, a surfactant, and water, and may be provided for impregnation in an absorbent substrate. Any embodiment of a writable cleanable article as described herein may be used in combination with any embodiment of a cleaning and protecting composition as described herein.

The term "surfactant" refers to a molecule that includes hydrophilic (i.e., polar) and hydrophobic (i.e., non-polar) regions on the same molecule.

The term "aqueous" refers to the presence of water.

The term "water-soluble" refers to a compound, composition, or material that forms a solution in water.

The term "solution" refers to a homogeneous composition in which the solute is dissolved in a solvent and cannot be separated from the solvent by filtration or physical means.

As used herein, the following terms have the indicated meanings: "organic group" means a hydrocarbon group (with optional elements other than carbon and hydrogen, such as oxygen, nitrogen, sulfur, and silicon) that is classified as an aliphatic group, a cyclic group, or a combination of aliphatic and cyclic groups (e.g., alkaryl and aralkyl groups), an organic group, in the context of this disclosure, being a group that does not interfere with the dry erase and permanent marker surface formation; "aliphatic group" means a saturated or unsaturated straight or branched chain hydrocarbon group, which term is used to encompass, for example, alkyl, alkenyl, and alkynyl groups; "alkyl" means a saturated straight or branched chain hydrocarbon group including, for example, methyl, ethyl, isopropyl, t-butyl, heptyl, dodecyl, octadecyl, pentyl, 2-ethylhexyl, and the like. "alkylene" is a divalent alkyl group; "alkenyl" means an unsaturated straight or branched chain hydrocarbon group having one or more carbon-carbon double bonds, such as a vinyl group; "alkynyl" refers to an unsaturated straight or branched hydrocarbon group having one or more carbon-carbon triple bonds; "cyclic group" means a closed ring hydrocarbon group that is classified as an alicyclic group, aromatic group, or heterocyclic group; "cycloaliphatic radical" refers to a cyclic hydrocarbon radical having properties similar to those of an aliphatic radical; "aromatic group" or "aryl group" means a monocyclic or polycyclic aromatic hydrocarbon group; and "heterocyclic group" means a closed ring hydrocarbon group in which one or more atoms are an element other than carbon (e.g., nitrogen, oxygen, sulfur, etc.). Groups that may be the same or different are sometimes referred to as "independent" groups.

Substitutions on the organic groups of the complexes of the present disclosure are contemplated. As a means of simplifying the discussion and recitation of certain terms used throughout this patent application, the terms "group" and "moiety" are used to distinguish between chemical species that are permitted to be substituted or that may be substituted and chemical species that are not permitted to be, or that cannot be, so substituted. Thus, when the term "group" is used to describe a chemical substituent, the chemical material being described includes the unsubstituted group as well as, for example, a group having O, N, Si or an S atom in the chain (as in an alkoxy group) as well as a carbonyl group or other conventional substitution. When the term "moiety" is used to describe a compound or chemical substituent, it is intended to include only unsubstituted chemical species. For example, the phrase "alkyl" is intended to include not only pure open-chain saturated hydrocarbon alkyl substituents, such as methyl, ethyl, propyl, t-butyl, and the like, but also alkyl substituents bearing other substituents known in the art, such as hydroxy, alkoxy, alkylsulfonyl, halogen atoms, cyano, nitro, amino, carboxyl, and the like. Thus, "alkyl" includes ether groups, haloalkyl groups, nitroalkyl groups, carboxyalkyl groups, hydroxyalkyl groups, sulfoalkyl groups, and the like. On the other hand, the phrase "alkyl moiety" is limited to inclusion of only pure open-chain saturated hydrocarbon alkyl substituents, such as methyl, ethyl, propyl, t-butyl, and the like.

In this document, the terms "comprise" and its derivatives, are used in the specification and claims, and not to be construed in a limiting sense. Such terms are to be understood to imply the inclusion of a stated step or element or group of steps or elements but not the exclusion of any other step or element or group of steps or elements. By "consisting of … …" is meant to include and be limited to the following of the phrase "consisting of … …". Thus, the phrase "consisting of … …" indicates that the listed elements are required or mandatory, and that no other elements may be present. By "consisting essentially of … …," it is meant to include any elements listed after the phrase, and is not limited to other elements that do not interfere with or contribute to the activity or effect specified in the disclosure for the listed elements. Thus, the phrase "consisting essentially of … …" indicates that the listed elements are required or mandatory, but that other elements are optional and may or may not be present, depending on whether they substantially affect the activity or effect of the listed elements. Any element or combination of elements in the specification that is referred to in an open language (e.g., including derivatives thereof) is intended to be encompassed by the enclosed language (e.g., consisting of … … and derivatives thereof) and is otherwise referred to in the partially enclosed language (e.g., consisting essentially of … … and derivatives thereof).

The words "preferred" and "preferably" refer to embodiments of the disclosure that may provide certain benefits under certain circumstances. However, other claims may also be preferred, under the same or other circumstances. Furthermore, the recitation of one or more preferred claims does not imply that other claims are not useful, and is not intended to exclude other claims from the scope of the disclosure.

In this application, terms such as "a," "an," "the," and "said" are not intended to refer to only a single entity, but include the general class of which a specific example may be used for illustration. The terms "a", "an", "the" and "the" are used interchangeably with the term "at least one". The phrases "at least one (kind) in … …" and "at least one (kind) comprising … …" in the following list refer to any one of the items in the list and any combination of two or more of the items in the list.

As used herein, the term "or" is generally employed in its ordinary sense, including "and/or" unless the context clearly dictates 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.

Also herein, all numerical values are assumed to be modified by the term "about" and, in certain embodiments, are preferably modified by the term "exactly. As used herein, with respect to a measured quantity, the term "about" refers to a deviation in the measured quantity that is commensurate with the objective of the measurement and the accuracy of the measurement equipment used, as would be expected by a skilled artisan taking the measurement with some degree of care. Herein, "at most" a number (e.g., at most 50) includes the number (e.g., 50).

Also herein, the recitations of numerical ranges by endpoints include all numbers subsumed within that range and the endpoints (e.g., 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, 5, etc.).

As used herein, the term "ambient temperature" or "room temperature" refers to a temperature of 20 ℃ to 25 ℃, or 22 ℃ to 25 ℃.

The term "in a range" or "within a range" (and similar expressions) includes the end points of the range.

Groupings of alternative elements or embodiments disclosed herein are not to be construed as limiting. Each group member may be referred to and claimed individually or in any combination with other members of the group or other elements found therein. It is contemplated that one or more members of a group may be included in the group or deleted from the group for convenience and/or patentability reasons. In the event of any such additions or deletions, the specification is considered herein to contain a modified group, thereby satisfying the written description of all markush groups used in the appended claims.

When a group occurs more than once in a formula described herein, each group is "independently" selected, whether or not explicitly stated. For example, when more than one R group is present in the formula, each R group is independently selected.

Reference throughout this specification to "one embodiment," "an embodiment," "certain embodiments," or "some embodiments," etc., means that a particular feature, configuration, composition, or characteristic described in connection with the embodiment is included in at least one embodiment of the present disclosure. Thus, the appearances of such phrases or in various places throughout this specification are not necessarily referring to the same embodiment of the present disclosure. Furthermore, the particular features, configurations, compositions, or characteristics may be combined in any suitable manner in one or more embodiments.

The above summary of the present disclosure is not intended to describe each disclosed embodiment or every implementation of the present disclosure. The following description more particularly exemplifies illustrative embodiments. Throughout this application, guidance is provided through lists of examples, which can be used in various combinations. In each case, the lists cited are intended as representative groups only and are not to be construed as exclusive lists. Thus, the scope of the present disclosure should not be limited to the particular illustrative structures described herein, but rather extends at least to structures described by the language of the claims and the equivalents of those structures. Any elements that are positively recited in the specification as alternatives can be explicitly included in or excluded from the claims in any combination as desired. While various theories and possible mechanisms may have been discussed herein, such discussion should not be used in any way to limit the subject matter which may be claimed.

Drawings

Fig. 1 is a schematic view of an exemplary embodiment of a cleanable article of the present disclosure. The figures are not drawn to scale and are intended to be illustrative only and not limiting.

Detailed Description

Fig. 1 shows an exemplary embodiment of a writable cleanable article 10 including a body member 12 having an outer cover 14 silicone bonded to a front surface 16 thereof. The surface 19 of the outer cover is a hydrophilic, cleanable, writable surface. In the illustrated embodiment, the body member 12 includes a base member 15 having a facing layer 13 on a front surface 17 thereof. The article 10 also includes an optional adhesive layer 18, and an optional removable liner 20 on a back surface 22 of the body member 12. That is, an adhesive layer 18 may be disposed on the back surface 22 of the base member 15, and a removable liner 20 is disposed on the adhesive layer 18.

In certain embodiments, the writable cleanable article 10 comprises: a base member 12 having a front surface 17; a facing layer 13 comprising a cured polymer matrix (organic or inorganic polymer matrix) and a plurality of inorganic nanoparticles dispersed in the cured polymer matrix, wherein the facing layer is disposed on at least a portion of the front surface of the base member; an optional primer layer (not shown) disposed on at least a portion of face layer 13; and a hydrophilic overcoat layer 14 bonded to the topcoat 13 and/or optional primer layer by siloxane bonds; wherein the hydrophilic overcoat layer provides a writable cleanable surface.

Generally, such writable, cleanable articles can be easily and effectively cleaned repeatedly. However, over time, the hydrophilic overcoat 14 can wear away, exposing the underlying optional primer layer and/or topcoat 13. Thus, the advantageous properties of writing, cleaning, rewriting, cleaning, etc., that make such articles writable cleanable may disappear as the hydrophilic surface is at least partially consumed. The compositions used in the methods described herein can improve the performance of writable, cleanable articles, particularly in terms of cleanability. The compositions used in the methods described herein may also complement performance (particularly in terms of cleanability, and in certain embodiments, in terms of writability) to that of (or close to that of) the original, unused, writable, cleanable article.

Illustrative examples of writable cleanable articles include single or filled sheets (e.g., similar to paper), films, adhesive backed labels incorporated into folders, notebook covers, dry erase articles, and the like. For example, in some embodiments, the article is a film having a cured coating (i.e., a topcoat) on a portion of one side of the film and an adhesive on a portion of the other side of the film, wherein the film is laminated to a second substrate that is subsequently framed to make a dry erase board.

In addition, the writable cleanable articles of the present disclosure may also include other optional components, such as a frame, means for storing materials and tools (such as writing implements, erasers, cloths, stationery, etc.), handles for carrying, protective covers, means for hanging from a vertical surface, easels, and the like.

Main body member of product

The body member generally constitutes substantially the majority of the article required for the writable and cleanable surfaces of the present disclosure. For example, it may be a door panel, window, ceiling or other architectural surface, a cabinet or furniture surface, a sign or whiteboard surface, a personal item such as a notebook, tablet surface, etc. The body member may be a film that is capable of adhering to another surface (e.g., a door, window, ceiling or other building surface or vehicle).

In addition to exhibiting other desirable properties, the front surface 16 of the body member 12 exhibits siloxane bonding-capable characteristics. In general, the ability of the body member 12 to be siloxane bondable is achieved by incorporating a siloxane bondable layer 13 (i.e., a top layer) as the front surface 16 of the body member 12, for example, by forming a suitable layer (e.g., a top layer with an optional primer) on the underlying base member 15. In this context, "capable of siloxane bonding" means that the surface has functional groups (e.g., -OH groups) capable of forming siloxane bonds.

Base member of body member

Typically, the base member 15 has a surface comprising a sheet of glass, ceramic, porcelain, paper, metal, organic polymer, or combinations thereof. In certain embodiments, the base member 15 may comprise, consist essentially of, or consist of any of a variety of organic polymeric materials or non-organic or non-polymeric materials. Examples of suitable materials include glass, metal sheets, paper, cardboard, knitted materials, fabrics, and the like.

The base member 15 may be composed of a single layer or multiple layers (e.g., a coextruded multilayer film).

The base member may be opaque, translucent, transparent or clear as desired. In some embodiments, the substrate member is retroreflective. The term "transparent" refers to transmitting at least 85% of incident light in the visible spectrum (wavelengths from 400 nanometers (nm) to 700 nm). The base member (i.e., substrate) may be colored.

The base member 15 may be flexible or inflexible.

In some embodiments, the base member is self-supporting, i.e., dimensionally stable enough to maintain its shape as it is moved, used, or manipulated. In some embodiments, the article is further supported in some manner, such as with a reinforcing frame, adhered to a support surface, and the like.

If desired, the body member can have graphics (e.g., words or symbols as are known in the art) on its surface or embedded therein that are visible through the outer cover. For example, decorative or organizational graphics, logos, etc. may be provided in the article to be visible to an observer, such as by applying legends, decorative emblems, informational logos on the front surface 17 of the base member 15. In addition, the base member may be opaque and/or colored to impart a desired appearance to the resulting article (e.g., a dry erase article).

In many embodiments, the base member is substantially planar, but it should be understood that curved or complex shapes may be constructed.

Accordingly, any of a variety of materials may be suitable for use as the base member 15, including flexible materials such as woven materials, knitted materials, films (e.g., polymeric films), nonwovens, foils, glass films, and the like. In some embodiments, the flexible material comprises a woven material, a nonwoven material, a knitted material, a film (e.g., a polymeric film), and the like.

In some embodiments, the base member is a polymer film. Illustrative examples include polymeric films selected from: polyesters (e.g., polyethylene terephthalate and polybutylene terephthalate), olefins (e.g., polyethylene, polypropylene, and copolymers of propylene, ethylene, and butylene), polyamides, polyimides, phenolic resins, polyvinyl chloride, polycarbonates, allyl diglycol carbonate, polyacrylates (e.g., polymethyl methacrylate), polystyrene, styrene-acrylonitrile copolymers, polysulfones, polyethersulfones, cellulose esters (e.g., acetate and butyrate), biopolymers, polylactic acid, homoepoxy polymers, epoxy addition polymers with a polydiamine or polydithiol, and combinations (e.g., copolymers, mixtures, or blends) of any of the foregoing.

In some embodiments where the article 10 is a film product intended for use in optical applications, such as optical displays, the substrate material will be selected, in part, according to the optical and mechanical properties desired for the intended use. Mechanical properties may include flexibility, dimensional stability, and impact resistance.

In some embodiments, an optically transparent material may be desired. The term "optically transparent" refers to the transparency of a material, typically allowing for a high level of light transmission (e.g., greater than 99% when reflecting losses are corrected) and low haze (e.g., less than 1%). Examples of suitable optically transparent materials include optically transparent polyester films, Triacetate (TAC) films, polyethylene naphthalate, polycarbonate, cellulose acetate, poly (methyl methacrylate), polyolefins such as biaxially oriented polypropylene (BOPP) and simultaneously biaxially oriented polypropylene (S-BOPP).

The thickness of the base member may vary and will generally depend on the intended use of the finished product. In some embodiments, the base member thickness is less than 0.5mm and typically does not exceed 0.2 mm. In some embodiments, the base member is at least 0.02mm thick.

The polymeric material may be formed using conventional film-making techniques, such as extrusion and optional uniaxial or biaxial orientation of the extruded film.

In certain embodiments, the base member 15 may be treated to improve adhesion to the facing layer 13. Examples of such treatments include chemical treatments, corona treatments (such as air or nitrogen corona), plasma treatments, flame treatments, or actinic radiation treatments. An optional tie layer may be used to improve interlayer adhesion. Combinations of treatments and/or bonding layers may be used if desired. Thus, the facing layer 13 may be disposed directly on the front surface 15 of the base member 15 or through a bonding layer.

Where the final article is intended for use in a display panel, the base member 15 and other components of the article 10 are typically light transmissive, meaning that light is transmitted such that the display can be viewed. Suitable light transmissive optical films include, but are not limited to, multilayer optical films, microstructured films such as retroreflective sheeting and brightness enhancing films (e.g., reflective or absorptive), polarizing films, diffusing films, and retarder and compensator films such as those described in U.S. patent 7,099,083(Johnson et al).

The finished product may be used in multilayer optical films such as described, for example, in U.S. patent 6,991,695(Tait et al). Exemplary materials that can be used to make polymeric multilayer optical films can be found in PCT publication WO 99/36248(Neavin et al). Further details regarding suitable multilayer optical films and their related constructions can be found in U.S. Pat. No. 5,882,774(Jonza et al) and PCT publications WO 95/17303(Ouderkirk et al) and WO 99/39224(Ouderkirk et al). Polymeric multilayer optical films may include additional layers and coatings selected for their optical, mechanical, and/or chemical properties. The polymer film may also include an inorganic layer, such as a metal or metal oxide coating or layer. Other substrate members for use in the body member of the article 10 of the present disclosure are disclosed in U.S. patent 9,527,336(Mahli et al).

Front surface of main body member (facing)

At least a portion of the front surface 16 of the body member 12 (i.e., the front surface 16 of the cover 13), and preferably substantially the entire front surface thereof, can be siloxane-bonded, i.e., can form a siloxane bond with a suitably formulated outer cover 14. This characteristic is typically provided herein by entrained exposed silicone-bondable particles in the cured polymer matrix in the face layer 13 and/or by an optional silicone-bondable primer layer such as diamond-like glass (described further below).

Depending on the desired application, the front surface 16 of the body member 12 may have a matte or glossy surface. The term "matte surface" refers to a rough or grainy surface or texture lacking high gloss or luster. A matte surface may be smooth to the touch but substantially free of significant light and shine.

Typically, although not necessarily, the front surface 16 of the face layer 13 is also a writable surface (i.e., a writing surface), which is a surface on which, for example, a dry-erase marker can be written.

In certain embodiments, the facing layer is no greater than 10 microns thick, and often no greater than 1 micron thick. In certain embodiments, the top layer is at least 100 nanometers (nm) thick.

In typical embodiments, the facing layer 13 is a non-tacky crosslinked polymer coating or a layer formed from a curable coating composition. The non-tacky crosslinked polymer coating or layer includes an organic polymer matrix (e.g., (meth) acrylate polymer matrix) or an inorganic polymer matrix (e.g., silicone polymer matrix).

Curable coating compositions generally include organic monomers, oligomers, and/or polymerizable polymers that can be monofunctional and/or multifunctional. The polymerizable organic material may be, for example, free-radically polymerizable, cationically polymerizable, and/or polycondensable. In some embodiments, the curable coating composition may further include a curing agent.

Curable coating compositions suitable for use herein (i.e., coatable materials or coatable compositions that are non-solid (e.g., liquid or gel-like) and capable of being applied to a surface) can include any of a variety of film-forming materials. In some embodiments, the coatable material is a polymeric material composed of one or more polymers and/or oligomers in a solvent. In some embodiments, the coatable material is a mixture of one or more monomers, oligomers, and/or polymers in one or more solvents.

Useful polymerizable materials (i.e., one or more monomers, oligomers, and/or polymerizable polymers) include, for example, (meth) acrylates (i.e., acrylates and methacrylates), epoxies, isocyanates, vinyl chloride, vinyl acetate, isoprene, butadiene, styrene, trialkoxysilane-terminated oligomers and polymers, and combinations thereof.

In certain embodiments, the polymerizable material comprises a free-radically polymerizable material. Useful free radically polymerizable materials include, for example, free radically polymerizable monomers and/or oligomers, either or both of which may be monofunctional or polyfunctional. Exemplary free radically polymerizable monomers include styrene and substituted styrenes (e.g., alpha-methylstyrene); vinyl esters (e.g., vinyl acetate); vinyl ethers (e.g., butyl vinyl ether); n-vinyl compounds (e.g., N-vinyl-2-pyrrolidone, N-vinylcaprolactam); acrylamides and substituted acrylamides (e.g., N-dialkyl acrylamides); and acrylates and/or methacrylates (i.e., collectively referred to herein as (meth) acrylates) (e.g., isooctyl (meth) acrylate, nonylphenol ethoxylate (meth) acrylate, isononyl (meth) acrylate, diethylene glycol (meth) acrylate, isobornyl (meth) acrylate, 2- (2-ethoxyethoxy) ethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, butanediol mono (meth) acrylate, β -carboxyethyl (meth) acrylate, isobutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (meth) acrylonitrile, isodecyl (meth) acrylate, dodecyl (meth) acrylate, n-butyl, Methyl (meth) acrylate, hexyl (meth) acrylate, meth (acrylic acid), stearyl (meth) acrylate, hydroxy-functionalized polycaprolactone (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxymethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxyisopropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxyisobutyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, ethylene glycol di (meth) acrylate, hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, 1, 3-propanediol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, 1, 4-cyclohexanediol di (meth) acrylate, 1, 5-pentanediol di (meth) acrylate, propylene glycol, Ethoxylated trimethylolpropane tri (meth) acrylate, glycerol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and neopentyl glycol di (meth) acrylate).

Exemplary free radically polymerizable oligomers include those sold by UCB Chemicals, Smyrna, Georgia, Inc. (e.g., under the trade name EBECRYL) of Schmidia, and those sold by Sartomer Company, Exton, Pennsylvania, of Angstrom, Pa., under the trade name KAYARAD or CN.

In some exemplary embodiments, the facing layer comprises a reaction product layer of a mixture comprising at least one curable component selected from the group consisting of (meth) acrylate monomers, (meth) acrylate oligomers, and combinations thereof. Other curable materials may be selected for other embodiments according to the present disclosure.

Depending on the choice of polymerizable material, the curable coating composition may optionally contain one or more curing agents that aid in polymerizing the polymerizable material. The choice of curing agent for a particular polymerizable material depends on the chemical nature of the copolymerizable material. For example, in the case of epoxy resins, curing agents known for epoxy resins (e.g., dicyandiamide, onium salts, or polythiols) are generally selected. In the case of free-radically polymerizable resins, free-radical thermal initiators and/or photoinitiators are useful curing agents.

Typically, the optional curing agent is used in an amount effective to promote polymerization of the polymerizable material, which will vary depending on, for example, the type of curing agent, the molecular weight of the curing agent, and the method of polymerization. The optional curing agent is typically included in the curable coating composition in an amount of about 0.01 wt% to about 10 wt%, based on the total weight of the curable coating composition, although higher and lower amounts may also be used. If the optional curing agent is a free radical initiator, the amount of curing agent is preferably in the range of 1 to 5 weight percent of the total weight of the curable coating composition, although higher and lower amounts may also be used.

Exemplary free radical photoinitiators include, for example, benzoin ethers (such as benzoin methyl ether and benzoin isopropyl ether), substituted benzoin ethers (such as anisoin methyl ether), substituted acetophenones (such as 2, 2-dimethoxy-2-phenylacetophenone), substituted alpha-ketols (such as 2-methyl-2-hydroxypropiophenone), benzophenone derivatives (such as benzophenone), and acylphosphine oxides. Exemplary commercially available photoinitiators include those available under the trade names IRGACURE (e.g., IRGACURE651, IRGACURE 184, and IRGACURE 819) or DAROCUR (e.g., DAROCUR1173, DAROCUR 4265) from the steam parkerization company of talidun, New York (Ciba Specialty Chemicals, Tarrytown, New York) and LUCIRIN (e.g., LUCIRIN TPO) from BASF, Parsippany, New jersey. Exemplary free radical thermal initiators include: peroxides such as benzoyl peroxide, dibenzoyl peroxide, dilauroyl peroxide, cyclohexane peroxide, methyl ethyl ketone peroxide, hydroperoxides (e.g., t-butyl hydroperoxide) and cumene hydroperoxide, dicyclohexyl peroxydicarbonate, t-butyl perbenzoate, and azo compounds (e.g., 2-azo-bis (isobutyronitrile)).

The curable coating composition can be cured, for example, by exposure to a heat source (e.g., heat, infrared radiation), electromagnetic radiation (e.g., ultraviolet and/or visible radiation), and/or particulate radiation (e.g., an electron beam of gamma radiation).

The curable coating composition forming the top layer is preferably fully cured. In particular, at least that part of the composition which forms the writing surface should be fully cured. Those skilled in the art are familiar with a variety of curing strategies and can readily select an appropriate strategy, depending in part on the characteristics of the curable coating composition, other components of the article, and the manufacturing facility. Exemplary techniques to maximize curing of UV-curable coating compositions include curing under nitrogen, using a new UV bulb, cleaning the UV bulb prior to use, matching the output spectrum of the UV bulb to the absorption of the initiator, and processing at low speed and/or for longer periods of time. In some embodiments, as the article ages at room temperature, some amount of post-exposure curing may occur over time. In certain embodiments, a second curing process may be required in addition to the first curing described above. The second curing may use the same radiation source as the first curing or it may use a different radiation source. Preferred second curing methods include thermal, electron beam and gamma ray treatments.

The facing layer also includes a plurality of inorganic nanoparticles dispersed in the cured polymer matrix. Such nanoparticles provide exposed-OH groups to the facing layer prior to bonding to the hydrophilic overcoat layer, thereby creating siloxane bonds.

Illustrative examples of inorganic nanoparticles useful in the facing layer of the body member of the present disclosure include alumina, antimony tin oxide, bismuth subsalicylate, boehmite, calcium carbonate, calcium phosphate, ceria, graphene, halloysite, lanthanum boride, lithium carbonate, silver, amorphous silica, colloidal silica, titania, zinc oxide, zirconia, or zirconia.

Suitable nanoparticles can be in a variety of shapes, including regular and irregular shapes, nanotubes, nanoplates, cylinders, and the like.

Suitable nanoparticles can have a wide range of particle sizes (e.g., particle diameters). In some embodiments, the average primary particle size may range from 1 nanometer (nm) to about 100 nm. The particle size and particle size distribution can be determined in known manner, including, for example, by Transmission Electron Microscopy (TEM). In some embodiments, the nanoparticles may have a primary particle size ranging from 5nm to 75 nm. In some embodiments, the nanoparticles may have a primary particle size ranging from 10nm to 30 nm. The term "primary particle size" refers to the average particle size of individual particles that are not agglomerated.

The nanoparticles may be present in an amount effective to enhance the durability of the finished product. In certain embodiments, the cured polymer matrix of the facing layer comprises nanoparticles in an amount of at least 15 wt% based on the total weight of the cured matrix of the facing layer and the nanoparticles. In certain embodiments, the cured polymer matrix of the facing layer includes nanoparticles in an amount up to 85 weight percent based on the total weight of the cured matrix of the facing layer and the nanoparticles.

Typically, the nanoparticles may be present in the coatable composition used to prepare the top coat in an amount of 10 wt% to 95 wt%, based on the total weight of the coatable composition. In some embodiments, the nanoparticles may be present in the coatable composition used to prepare the top layer in an amount of 25 wt% to 80 wt%, based on the total weight of the coatable composition. In other embodiments, the nanoparticles may be present in the coatable composition used to prepare the top coat in an amount of 30 wt% to 70 wt%, based on the total weight of the coatable composition.

Silica nanoparticles (such as fumed silica) are particularly desirable. Silica nanoparticles suitable for use in the articles of the present disclosure are commercially available under the product name NALCO colloidal silica from NALCO Chemical co. Suitable silica products include NALCO products 1040, 1042, 1050, 1060, 2327 and 2329. Suitable fumed silica products include those sold under the trade names AEROSIL series OX-50, OX-130, OX-150, and OX-200 by Degussa AG, Hanau, Germany, of Haagate, Germany, and CAB-O-SPERSE 2095, CAB-O-SPERSE A105, CAB-O-SIL MS by Cabot Corp, Tuscola, IL, Taskora, Ill.

The nanoparticles may be surface modified, which refers to the fact that the nanoparticles have a modified surface such that the nanoparticles provide a stable dispersion. By "stable dispersion" is meant a dispersion that: in this dispersion, the colloidal nanoparticles do not agglomerate after standing for a period of time, such as 24 hours, under ambient conditions, e.g., at room temperature and atmospheric pressure, without terminal electromagnetic forces. Preferably, the surface treatment stabilizes the nanoparticles so that the particles are well dispersed in the coatable composition and result in a substantially homogeneous composition. In addition, at least a portion of the surface of the nanoparticles may be modified with a surface treatment agent so that the stabilized particles may copolymerize or react with the coatable composition during the curing process.

In certain embodiments of the present disclosure, at least a portion of the nanoparticles may be surface modified. In other embodiments, all nanoparticles are surface modified. In other embodiments, none of the nanoparticles are surface modified.

The surface-modified colloidal nanoparticles described herein can have a variety of desirable attributes including, for example: compatibility of the nanoparticles with the coatable composition such that the nanoparticles form a stable dispersion within the coatable composition; the reactivity of the nanoparticles with the coatable composition, thereby making the article more durable; and the viscosity of the low impact or uncured composition. A combination of surface modifications can be used to control the uncured and cured properties of the composition. The surface-modified nanoparticles can improve the optical and physical properties of the coatable composition, for example, increase the mechanical strength of the resin, minimize viscosity changes while increasing the solids volume loading in the coatable composition, and maintain optical clarity while increasing the solids volume loading in the coatable composition.

The metal oxide nanoparticles may be treated with a surface treatment agent to "surface modify" them. Generally, the surface treatment agent has a first end that will attach to the particle surface (covalently, ionically, or by strong physisorption) and a second end that renders the particle compatible with the coatable composition and/or reactive with the coatable composition during curing. Examples of surface treatment agents include alcohols, amines, carboxylic acids, sulfonic acids, phosphonic acids, silanes, and titanates. The type of treating agent may depend on the nature of the metal oxide surface. For example, silanes are generally preferred for silicon dioxide.

Surface treatments suitable for use in the nanoparticles useful herein include compounds such as, for example, isooctyltrimethoxysilane, methoxyethoxyethoxyethoxyethoxyethyl N- (3-triethoxysilylpropyl) carbamate (PEG3TES), SILQUEST A1230, methoxyethoxyethoxyethyl N- (3-triethoxysilylpropyl) carbamate (PEG2TES), 3- (methacryloyloxy) propyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3- (methacryloyloxy) propyltriethoxysilane, 3- (methacryloyloxy) propylmethyldimethoxysilane, 3- (acryloxypropyl) methyldimethoxysilane, 3- (methacryloyloxy) propyldimethylethoxysilane, vinyldimethylethoxysilane, phenyltrimethoxysilane, n-octyltrimethoxysilane, dodecyltrimethoxysilane, octadecyltrimethoxysilane, propyltrimethoxysilane, hexyltrimethoxysilane, vinylmethyldiacetoxysilane, vinylmethyldiethoxysilane, vinyltriacetoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, vinyltrimethoxysilane, vinyltriphenoxysilane, vinyltri-t-butoxysilane, vinyltriisobutoxysilane, vinyltriisopropenoxysilane, vinyltris (2-methoxyethoxy) silane, styrylethyltrimethoxysilane, mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, acrylic acid, methacrylic acid, oleic acid, and mixtures thereof, Stearic acid, dodecanoic acid, 2- [2- (2-methoxyethoxy) ethoxy ] acetic acid (MEEAA), beta-carboxyethyl acrylate, 2- (2-methoxyethoxy) acetic acid, methoxyphenylacetic acid, and mixtures of two or more of the foregoing.

The surface modification may be achieved prior to mixing into the coatable composition, or after mixing. In the case of silanes, it may be preferred to react the silane with the surface of the nanoparticles before the nanoparticles are incorporated into the coatable composition. The amount of surface treatment agent may depend on several factors such as particle size, particle type, modifier molecular weight, and modifier type. Generally, a monolayer of the modifying agent is attached to the surface of the particle. The attachment procedure or the desired reaction conditions also depend on the surface treatment agent used.

Surface modification of particles in colloidal dispersions can be achieved in a variety of ways. The process involves a mixture of the inorganic dispersion with a surface treatment agent and optionally a co-solvent such as, for example, 1-methoxy-2-propanol, ethanol, isopropanol, ethylene glycol, N-dimethylacetamide and 1-methyl-2-pyrrolidone. A co-solvent may be added to enhance the solubility of the surface treatment agent as well as the surface modified particles. The mixture comprising the inorganic sol and the surface treatment agent is then reacted at room temperature or elevated temperature, with or without mixing. For silanes, the surface treatment may be carried out under acid or base conditions at elevated temperatures for a period of time ranging from 1 hour up to 24 hours. In one method, the mixture may be reacted at 85 ℃ for 24 hours to obtain a surface modified sol. In one method of surface modification of metal oxides, surface treatment of the metal oxide may involve adsorption of acidic molecules to the particle surface. The surface modification of the heavy metal oxide is preferably carried out at room temperature.

In some embodiments, the body member 12 is formed by applying a suitable curable coating composition to at least a portion of the front surface 17 of the base member 15 and curing the composition. In some embodiments, the body member may be preformed as part of a preformed writable cleanable article 10 and then bonded to at least a portion of the front surface of a substrate (furniture, door, window, vehicle, etc.), such as laminated or adhered to the substrate using, for example, an adhesive or other tie layer.

As will be appreciated, the coating compositions used to prepare the facings of the articles of the present disclosure may contain optional additives to enhance or control properties as desired, for example, rheology modifiers such as JAYLINK rheology modifiers, colorants (e.g., dyes and/or pigments), flame retardants, antioxidants, stabilizers, antiozonants, plasticizers, UV absorbers, Hindered Amine Light Stabilizers (HALS), and the like.

The coating composition used to prepare the top coat may be applied from one or more solvents. Exemplary solvents include ketones and alcohols such as methyl ethyl ketone, methoxypropanol, methoxyethanol, and the like.

The coating composition used to prepare the top layer is preferably coated on the base member using conventional techniques, such as bar coating, roll coating, curtain coating, gravure coating, spray coating, or dip coating techniques. Preferred methods include bar coating and roll coating, or air knife coating to adjust thickness. Once coated, a variety of curing strategies well known to those skilled in the art can be used.

As noted above, at least a portion of the front surface 16 of the body member 12, and in some cases substantially the entire front surface thereof, can be siloxane bonded, i.e., can form a siloxane bond with a suitably formulated outer cover. In some embodiments, the ability of the body member to be siloxane-bonded is achieved by exposing siloxane-bonded nanoparticles in the cured polymer matrix of the facing layer 13. An illustrative example of a method of achieving this is to treat the front surface 16 of the face layer 13 (i.e., the front surface 16 of the body member 12) with a plasma etch, corona treatment, flame treatment, or otherwise surface treating the face layer prior to applying the overcoat layer. Alternatively or additionally, a primer layer capable of bonding with silicone is disposed on the facing surface.

Optional primer layer on top of the topcoat

In some embodiments, a primer layer is disposed between the face layer 13 and the outer cover layer 14. Such a primer layer may be, for example, disposed on a surface of the topcoatA "diamond-like glass" layer or a sintered silica layer. Such primer layers are typically capable of bonding with siloxanes because they provide-OH groups. Other primer compositions may be used to provide-OH groups. Examples of such compositions include tetraalkoxysilanes, oligomers thereof, lithium silicate, sodium silicate, potassium silicate, silica (e.g., silica particles), or combinations thereof. In certain embodiments, surface 16 of facing layer 13 can be surface modified by conventional vapor coating or vapor deposition processes to form SiO or SiO as described in U.S. Pat. No. 4,338,377(Beck et al)₂And (3) thin-layer primer. The surface modification of the substrate may also include vapor coating or vapor deposition of alkoxysilanes.

Typically, although not necessarily, the primer layer may be a writable surface (i.e., writing surface), which is a surface on which, for example, a dry-erase marker may be written.

In certain embodiments, the primer layer is diamond-like glass. U.S. Pat. No. 6,696,157(David et al) discloses diamond-like glass (sometimes referred to as "DLG") films and methods for their preparation, which can be used to prepare primer layers of the present disclosure. One advantage of such materials is that they provide a front surface on the body member that is capable of siloxane bonding, such materials provide a strong bond to the outer cover, and such layers can also provide rigidity and dimensional stability that act to support the outer cover, making the resulting writable cleanable article durable and resistant to breakage. This is particularly beneficial when the components underlying the base member are relatively soft.

Exemplary diamond-like glass materials suitable for use in the present invention comprise a carbon-rich diamond-like amorphous covalent system comprising carbon, silicon, hydrogen, and oxygen. DLG is produced by depositing a dense random covalent system comprising carbon, silicon, hydrogen and oxygen under ion bombardment conditions by placing the substrate on an energized electrode in a radio frequency ("RF") chemical reactor. In a particular implementation, DLG is deposited under intense ion bombardment conditions of a tetramethylsilane and oxygen mixture. Generally, DLG exhibits negligible optical absorption in the visible and ultraviolet regions (i.e., 250 to 800 nm). Additionally, DLG generally exhibits improved resistance to flex cracking and excellent adhesion to many substrates including ceramics, glass, metals, and polymers compared to other types of carbon-containing films.

DLG comprises at least 30 at% carbon, at least 25 at% silicon, and less than or equal to 45 at% oxygen. DLG typically contains 30 to 50 atomic% carbon. In particular implementations, the DLG may include 25 atomic% to 35 atomic% silicon. Additionally, in certain implementations, DLG includes 20 atomic% to 40 atomic% oxygen. In a particularly advantageous implementation, DLG comprises 30 to 36 at% carbon, 26 to 32 at% silicon, and 35 to 41 at% oxygen, on a hydrogen free basis. "not counting hydrogen" refers to the atomic composition of a substance determined by a method such as chemical analysis Electron Spectroscopy (ESCA) that does not detect hydrogen even if a large amount of hydrogen is present in the thin film.

In certain embodiments, the optional primer layer (e.g., DLG primer layer) disposed on the body member is 0.1 to 2 microns thick, although other thicknesses can be used as desired.

In certain embodiments, facing layer 13 of body member 12 may be treated to improve the adhesion of DLG. Typically, such treatment includes plasma treatment.

Outer coating

The outer cover 14 is generally formed by applying a curable liquid outer cover composition comprising a silicone-bondable component to at least a portion of the front surface 16 of the body member 12. The coating composition is then cured such that a solid overcoat layer 14 is formed that is siloxane bonded to the face layer 13 of the body member 12 and/or is a siloxane-bondable primer layer disposed on the face layer.

The resulting construction (i.e., the encased body member, or the base member having a facing disposed on the body member and an overcoat disposed on the facing) has a cleanable (e.g., cleaned with a dry-erase marker) and rewritable (e.g., rewritten with a dry-erase marker) writing surface (i.e., a writable surface) 19.

The outer cover has a hydrophilic surface, preferably a highly hydrophilic surface. As used herein, "hydrophilic" is used to refer to a surface that is wetted by an aqueous solution and does not exhibit whether or not the layer absorbs aqueous solution. A surface on which a drop of water or aqueous solution exhibits a static water contact angle of less than 50 ° is said to be "hydrophilic" according to ASTM D7334-08. In contrast, hydrophobic surfaces have a water contact angle of 50 ° or greater.

In certain embodiments, the hydrophilic overcoat comprises sulfonate functional groups, phosphate functional groups, phosphonate functional groups, carboxylate functional groups, or a combination thereof. In certain embodiments, the hydrophilic overcoat comprises sulfonate functional groups.

In exemplary embodiments, the resulting overcoat layer is applied at least a monolayer thick. As used herein, "at least a monolayer thick" includes a monolayer or thicker layer of molecules covalently bonded (through siloxane bonds) to the underlying topcoat surface and/or the primer on the topcoat surface.

In certain embodiments, the overcoat layer is at least 0.3 microns thick. Typically, the overcoat layer is no greater than 10 microns thick, and preferably no greater than 1 micron thick. Such thicknesses may be measured using an ellipsometer, such as model L115C from gantner science corporation (Gaertner scientific corp.). It should be understood that articles of the present disclosure may be prepared using outer covers of other thicknesses.

In certain embodiments, the hydrophilic overcoat layer is formed from one or more zwitterionic compounds, such as a zwitterionic silane. The zwitterionic compound is a neutral compound having charges of different signs in the molecule.

In some embodiments, the overcoat layer is formed from at least one zwitterionic silane selected from the group consisting of phosphate functional silanes, phosphonate functional silanes, phosphonic acid functional silanes, carboxylate functional silanes, and sulfonate functional silanes. Such silanes include groups (e.g., sulfonate groups (SO) for imparting a desired high hydrophilicity to a surface to provide suitable cleanability₃ ^-)). Herein, silane refers to a silicon-containing compound having a group capable of forming a siloxane bond with a surface layer. Typically, such groups are alkoxysilane or silanol groups.

Illustrative examples of zwitterionic compounds include those disclosed in U.S. publication 2017/0275495(Riddle et al).

In certain embodiments, the zwitterionic compound is a sulfonate-functional zwitterionic compound, such as a zwitterionic sulfonate-functional silane compound. In certain embodiments, the zwitterionic hydrophilic overcoating is derived from a zwitterionic compound comprising a sulfonate functional group and an alkoxysilane group and/or a silanol functional group.

In certain embodiments, the zwitterionic sulfonate-functional silane compounds used to prepare the overcoats of the present disclosure have the following formula (I), wherein:

(R¹O)_p-Si(R²)_q-W-N⁺(R³)(R⁴)-(CH₂)_m-SO₃ ^-(I)

wherein:

each R¹Independently hydrogen, a methyl group or an ethyl group;

each R²Independently a hydroxyl group, (C1 to C4) an alkyl group, and (C1 to C4) an alkoxy group (preferably, a methyl group or an ethyl group);

each R³And R⁴Independently saturated or unsaturated, linear, branched or cyclic organic groups (preferably having 20 carbon atoms or less) which may be linked together, optionally together with atoms of the group W, to form a ring;

w is an organic linking group;

p is an integer of 1 to 3;

m is an integer of 1 to 10 (preferably 1 to 4);

q is 0 or 1; and is

p+q＝3。

The organic linking group W of formula (I) is preferably selected from saturated or unsaturated linear, 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, hydroxyl-substituted alkylene groups, hydroxyl-substituted monooxaalkylene groups, divalent hydrocarbon groups with an oxa-backbone substitution, divalent hydrocarbon groups with a mono-thia-backbone substitution, divalent hydrocarbon groups with an oxa-thia-backbone substitution, divalent hydrocarbon groups with a dioxo-thia-backbone substitution, arylene groups, arylalkylene groups, alkylarylene groups, and substituted alkylarylene groups.

Suitable examples of zwitterionic compounds of formula (I) are described in U.S. Pat. No. 5,936,703(Miyazaki et al) and International publications WO 2007/146680(Schlenoff) and WO 2009/119690(Yamazaki et al) and include the following zwitterionic functional groups (-W-N)⁺(R³)(R⁴)-(CH₂)_m-SO₃ ^-)：

In certain embodiments, the sulfonate-functional silane compound used to prepare the overcoats of the present disclosure has the following formula (II), wherein:

(R¹O)_p-Si(R²)_q-CH₂CH₂CH₂-N⁺(CH₃)₂-(CH₂)_m-SO₃ ^-(II)

wherein:

each R¹Independently hydrogen, a methyl group or an ethyl group;

each R²Independently a hydroxyl group, (C1 to C4) an alkyl group, and (C1 to C4) an alkoxy group (preferably, a methyl group or an ethyl group);

p is an integer of 1 to 3;

m is an integer of 1 to 10 (preferably 1 to 4);

q is 0 or 1; and is

p+q＝3。

Suitable examples of zwitterionic compounds of formula (II) are described in us patent 5,936,703(Miyazaki et al), including for example:

(CH₃O)₃Si-CH₂CH₂CH₂-N⁺(CH₃)₂-CH₂CH₂CH₂-SO₃ ^-(ii) a And

(CH₃CH₂O)₂Si(CH₃)-CH₂CH₂CH₂-N⁺(CH₃)₂-CH₂CH₂CH₂-SO₃ ^-。

other examples of suitable zwitterionic compounds that can be prepared using standard techniques known to those skilled in the art include the following:

while the following is directed to sulfonate-functional coating compositions for use in preparing the overcoat layer of a writable cleanable article as described herein, such disclosure is also applicable to other coating compositions using other hydrophilic coating compositions (e.g., other zwitterionic compounds, such as phosphate-functional compounds).

The sulfonate-functional coating composition used to prepare the overcoat layer of the writable cleanable articles of the present disclosure typically comprises a sulfonate-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 sulfonate-functional coating composition used to prepare the overcoat layer of the writable cleanable articles of the present disclosure typically comprises a sulfonate-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 a single layer coating thickness, a relatively dilute coating composition is used. Alternatively, a relatively concentrated coating composition may be used, and subsequently rinsed.

The sulfonate-functional coating composition used to prepare the overcoat layer of the writable cleanable article of the present disclosure preferably comprises an alcohol, water, or hydroalcoholic solution (i.e., alcohol and/or water). Typically, such alcohols are lower alcohols (e.g., (C1 to C8) alcohols, and more typically (C1 to C4) alcohols), such as methanol, ethanol, propanol, 2-propanol, and the like. Preferably, the sulfonate-functional coating composition is an aqueous solution. As used herein, the term "aqueous solution" refers to a solution containing water. Such solutions may use water as the only solvent or they may use a combination of water and organic solvents such as alcohols and acetone. Organic solvents may also be included in the hydrophilic treatment composition in order to improve its freeze-thaw stability. Typically, the solvent is present in an amount up to 50% by weight of the composition and preferably in the range of 5 to 50% by weight of the composition.

The sulfonate-functional coating composition used to prepare the overcoat layer of the writable cleanable article of the present disclosure can be acidic, basic, or neutral. The performance durability of the coating can be affected by pH. For example, coating compositions containing sulfonate-functional zwitterionic compounds are preferably neutral.

The sulfonate-functional coating composition used to prepare the overcoat layer of the writable cleanable article of the present disclosure can be provided at a variety of viscosities. Thus, for example, the viscosity may vary from a low viscosity like water to a high viscosity like a paste. They may also be provided in the form of a gel.

Useful coating compositions comprise greater than 1 wt.%, greater than 2 wt.% solids, or at least 3 wt.% solids, and typically up to 20 wt.% solids. Solids generally refer to components other than water.

In addition, a variety of other ingredients can be incorporated into the composition for use in preparing the outer cover of the writable cleanable article of the present disclosure. Thus, for example, conventional surfactants, cationic surfactants, anionic surfactants or nonionic surfactants can be used. Detergents and wetting agents may also be used. If necessary, at least one of a water-soluble alkali metal silicate, a tetraalkoxysilane monomer, a tetraalkoxysilane oligomer and an inorganic silica sol may be used. In certain embodiments, the hydrophilic overcoat layer further comprises a water soluble alkali metal silicate, particularly lithium silicate. Such additional ingredients for preparing the overcoat layer are described below with respect to cleaning and protective compositions. However, in certain embodiments, the composition used to form the overcoat layer does not comprise a surfactant.

The sulfonate-functional coating composition is preferably applied to the body member using conventional techniques such as bar coating, roll coating, curtain coating, rotogravure coating, spray coating or dip coating techniques. Preferred methods include bar coating and roll coating, or air knife coating to adjust thickness.

Once coated, the sulfonate-functional composition is typically dried in a circulation oven at a temperature of 20 ℃ to 150 ℃. The inert gas may be circulated. The temperature may be further increased to speed up the drying process, but care must be taken to avoid damage to the substrate.

Such hydrophilic outer covers provide a cleanable surface such that the articles described herein can be easily cleaned, such as by wiping with only dry cloth, paper towels, or the like, or in some cases, with water.

For example, in embodiments where the article is a dry erase article, the surface of the outer cover can be easily written on and then easily cleaned. Obviously, even permanent marker writing can be easily removed by wiping, preferably after the first application of water and/or water vapor (e.g., by breathing). Generally, the methods of the present disclosure include removing permanent marker writing from a surface by simply applying water (e.g., tap water at room temperature) and/or water vapor (e.g., human breath) and wiping. As used herein, "wipe" refers to a gentle wipe, typically one or more strokes or scrapes (typically only a few times) with manual use of, for example, tissue, towel, or cloth without significant pressure (e.g., typically no more than 350 grams).

In some instances, cleaning of surfaces, such as wiping dry erase boards, is facilitated by the use of a cleaner composition, preferably a cleaning and protective composition as described below.

Cleaning and protective composition

The cleaning and protective compositions of the present disclosure have multiple functions, i.e., they are multi-functional compositions. The compositions exhibit a variety of functions, they remove unwanted components from the substrate surface, impart hydrophilic properties to the substrate surface, and impart easy-to-clean properties to the substrate surface. That is, they are capable of cleaning and protecting the surface of the substrate to which they are applied. In this context, protection generally refers to the easier removal of one or more contaminants (e.g., dry erase markers) after the composition is applied to the surface of a substrate, such as a writable cleanable article.

The writable cleanable articles described herein can be easily and effectively cleaned repeatedly, however, such advantageous properties that make them writable cleanable can also disappear due to the consumption of the surface layer. Surprisingly, such compositions also return performance (particularly in terms of cleanability, and in some embodiments, in terms of writability) to that of (or close to that of) the original, unused, writable, cleanable article.

This is particularly advantageous for films applied to vehicles. For example, the surfaces of many vehicles (such as buses and railway cars) are often graffiti by vandals using, for example, paint or markers. Certain commercially available surface protective films use low surface energy components that render the film non-writable. It is believed that if the paint of the destroyer does not adhere in the manner they desire, the destroyer will choose a different method (scraping or chiseling) to destroy the surface. Thus, the writable surface allows a destroyer to alter the surface without the destroyer knowing that the indicia are easy to remove. The surface may be easily cleaned by rain, brushing, or automated vehicle washing systems. Thus, the writable, cleanable articles described herein are particularly advantageous for use on vehicles where the surface is easily altered.

Such compositions may be dispersions or solutions. They typically comprise a hydrophilic silane, a surfactant and water.

Such compositions can be applied to clean surfaces, soiled surfaces, surfaces including irregularities and defects, previously cleaned surfaces, and combinations thereof, and can be reused. Typically, such compositions are applied to a surface of a writable cleanable article as described herein, wherein the hydrophilic overcoat layer has a hydrophilic surface that is at least partially consumed. Such consumption adversely affects the cleanability of the surface, and may even adversely affect the writability of the surface. The use of the cleaning and protective composition on a writable surface increases the amount of hydrophilic silane on the surface and increases the hydrophilicity of the surface, thereby replenishing the hydrophilic overcoat layer and restoring the cleanability and even the writability of the surface.

Such compositions also preferably impart sufficient hydrophilic properties to the surface such that when the surface is subsequently marked with a permanent marker, the mark can be substantially removed or even completely removed from the surface (e.g., by spraying the surface and mark with water, then wiping) with at least one of water (e.g., tap water at ambient temperature), water vapor (e.g., the breath of an individual), wiping (e.g., gently wiping with a tissue, paper towel, cloth up to several times), a cleaning composition, and combinations thereof.

In certain embodiments, the cleaning and protection composition preferably comprises an amount of hydrophilic silane and an amount of surfactant such that the ratio of the weight of hydrophilic silane to the weight of surfactant in the composition is at least 1:1, at least 1:2, at least 1:3, at least 1:10, at least 1:40, or at least 1: 400. That is, in such compositions, the amount of surfactant is equal to or greater than the amount of hydrophilic silane. In certain embodiments, the cleaning and protection composition preferably comprises an amount of hydrophilic silane and an amount of surfactant such that the ratio of the weight of hydrophilic silane to the weight of surfactant in the composition is from 1:2 to 1:100 or even from 1:3 to 1: 20. The composition is generally more useful on regularly cleaned surfaces, which are not subject to accumulation of contaminants and therefore protection is not critical, but repeated use can provide protection and make the surface easier to clean.

The cleaning and protective composition may be acidic, basic or neutral. The pH of the composition can be modified to achieve a desired pH using any suitable acid or base known in the art, including, for example, organic and inorganic acids, or carbonates, such as potassium or sodium carbonate. Compositions comprising sulfonate-functional zwitterionic compounds having a pH of 5 to 8 are neutral, or even at their isoelectric point.

The cleansing and protective compositions may be provided in a variety of forms, including, for example, as concentrates that are diluted prior to use (e.g., with water, solvents, or aqueous-based compositions containing organic solvents) or as ready-to-use compositions, liquids, pastes, foams, foaming liquids, gels, and gelling liquids. The multi-functional composition has a viscosity suitable for its intended use or application, including, for example, a viscosity ranging from a low viscosity like water to a high viscosity like a paste at 22 ℃ (72 ° f).

In certain embodiments, useful cleaning and protection compositions comprise no greater than 2 wt.% solids, or even no greater than 1 wt.% solids, and typically at least 0.05 wt.% solids. Solids generally refer to components other than water.

Hydrophilic silanes for cleaning and protecting compositions

Suitable hydrophilic silanes are preferably water soluble, and in some embodiments, suitable hydrophilic silanes are non-polymeric compounds. They are siloxane-bondable, i.e., capable of forming a siloxane bond with the overcoat, topcoat and/or optional primer layer.

Useful hydrophilic silanes include, for example, individual molecules, oligomers (typically less than 100 repeating units, and typically only a few repeating units), such as monodisperse oligomers and polydisperse oligomers, and combinations thereof, and preferably have a number average molecular weight of no greater than (i.e., up to) 5000 grams per mole (g/mol), no greater than 3000g/mol, no greater than 1500g/mol, no greater than 1000g/mol, or even no greater than 500 g/mol. The hydrophilic silane is optionally the reaction product of at least two hydrophilic silane molecules.

These hydrophilic silanes are generally selected to provide protectant properties to the compositions of the present disclosure. The hydrophilic silane can be any of a variety of different classes of hydrophilic silanes, including, for example, zwitterionic silanes, non-zwitterionic silanes (e.g., cationic silanes, anionic silanes, and nonionic silanes), silanes comprising a functional group (e.g., a functional group attached directly to a silicon molecule, a functional group attached to another molecule on a silane compound, and combinations thereof), and combinations thereof. Useful functional groups include, for example, alkoxysilane groups, siloxy groups (e.g., silanols), hydroxyl groups, sulfonate groups, phosphonate groups, carboxylate groups, glucamide groups, sugar groups, polyvinyl alcohol groups, quaternary ammonium groups, halogens (e.g., chlorine and bromine), sulfur groups (e.g., thiols and xanthates), color-imparting agents (e.g., ultraviolet agents (e.g., diazonium groups) and peroxide groups), click-reactive groups, biologically active groups (e.g., biotin), and combinations thereof.

Examples of suitable classes of hydrophilic silanes comprising functional groups include sulfonate-functional zwitterionic silanes, sulfonate-functional non-zwitterionic silanes (e.g., sulfonated anionic silanes, sulfonated nonionic silanes, and sulfonated cationic silanes), hydroxysulfonate silanes, phosphonate silanes (e.g., 3- (trihydroxysilyl) propylmethyl-phosphonate monosodium salt), carboxylate silanes, glucamide silanes, polyhydroxyalkylsilanes, polyhydroxyarylsilanes, hydroxypolyoxirane silanes, polyethyleneoxide silanes, and combinations thereof.

Useful sulfonate-functional zwitterionic silanes are those represented by formulas (I) and (II) described above for the overcoat layer of the writable cleanable article.

One useful class of sulfonate-functional non-zwitterionic silanes has the following formula (III):

[(MO)(Q_n)Si(XCH₂SO₃ ^-)_3-n]Y_2/nr ^+r(III)

wherein:

each Q is independently selected from the group consisting of a hydroxyl group, an alkyl group containing 1 to 4 carbon atoms, and an alkoxy group containing 1 to 4 carbon atoms;

m is selected from hydrogen, an alkali metal and an organic cation of a strong organic base having an average molecular weight of less than 150 and a pKa of greater than 11;

x is an organic linking group;

y is selected from the group consisting of hydrogen, alkaline earth metals, organic cations of a protonated weak base having an average molecular weight of less than 200 and a pKa of less than 11, organic cations of an alkali metal and a strong organic base having an average molecular weight of less than 150 and a pKa of greater than 11, with the proviso that when Y is hydrogen, an alkaline earth metal or an organic cation of a protonated weak base, M is hydrogen;

r is equal to the valence of Y; and is

n is 1 or 2.

Preferred non-zwitterionic compounds of (III) include alkoxysilane compounds in which Q is an alkoxy group containing 1 to 4 carbon atoms.

The silane of formula (III) is preferably at least 30 wt%, at least 40 wt% or even 45 wt% to 55 wt%, and no more than 15 wt%, based on the weight of the compound in anhydrous acid form.

Useful organic linking groups X of formula (III) include, for example, alkylene, cycloalkylene, alkyl-substituted cycloalkylene, hydroxy-substituted alkylene, hydroxy-substituted monooxaalkylene, divalent hydrocarbon with a monooxabackbone substitution, divalent hydrocarbon with a monothiohetero backbone substitution, divalent hydrocarbon with an oxa-thiabackbone substitution, divalent hydrocarbon with a dioxo-thiabackbone substitution, arylene, arylalkylene, alkylarylene, and substituted alkylarylene.

Examples of useful Y groups of formula (III) include 4-aminopyridine, 2-methoxyethylamine, benzylamine, 2, 4-dimethylimidazole, and 3- [ 2-ethoxy (2-ethoxyethoxy)]Propylamine, a,⁺N(CH₃)₄And⁺N(CH₂CH₃)₄。

suitable sulfonate-functional non-zwitterionic silanes of the formula (III) include, for example, (HO)₃Si-CH₂CH₂CH₂-O-CH₂-CH(OH)-CH₂SO₃-H⁺；(HO)₃Si-CH₂CH(OH)-CH₂SO₃-H⁺；(HO)₃Si-CH₂CH₂CH₂SO₃-H⁺；(HO)₃Si-C₆H₄-CH₂CH₂SO₃-H⁺；(HO)₂Si-[CH₂CH₂SO₃H⁺]₂；(HO)-Si(CH₃)₂-CH₂CH₂SO3-H⁺；(NaO)(HO)₂Si-CH₂CH₂CH₂-O-CH₂-CH(OH)-CH₂SO₃-Na⁺(ii) a And (HO)₃Si-CH₂CH₂SO₃-K⁺And those sulfonate-functional non-zwitterionic silanes of formula (III) described in U.S. Pat. Nos. 4,152,165 (Langer et al) and 4,338,377(Beck et al).

The cleaning and protective composition preferably comprises at least 0.0001 wt.%, at least 0.001 wt.%, or in certain embodiments at least 0.005 wt.%, at least 0.01 wt.%, or at least 0.05 wt.% hydrophilic silane. The cleaning and protection composition preferably comprises up to 10 wt.%, or in certain embodiments no more than 3 wt.%, no more than 2 wt.%, no more than 1.5 wt.%, no more than 1 wt.%, no more than 0.75 wt.%, or even no more than 0.5 wt.% of the hydrophilic silane. The hydrophilic silane is optionally provided in a concentrated form, which can be diluted to achieve the above weight percentages of hydrophilic silane.

Surfactants in cleaning and protecting compositions

Suitable surfactants include, for example, anionic, nonionic, cationic, and amphoteric surfactants and combinations thereof. These surfactants can provide cleaning properties, wetting properties, or both to the compositions of the present disclosure.

The cleaning and protection composition may comprise more than one surfactant. One or more surfactants are typically selected for use as a cleaning agent. One or more surfactants are typically selected to act as wetting agents. The cleaning agent may be a detergent, a foaming agent, a dispersing agent, an emulsifier, or a combination thereof. The surfactants in such detergents typically comprise a hydrophilic moiety that is anionic, cationic, amphoteric, quaternary amino, or zwitterionic, and a hydrophobic moiety comprising a hydrocarbon chain, a fluorocarbon chain, a silicone chain, or a combination thereof. The wetting agent can be selected from a variety of materials that reduce the surface tension of the composition. Such wetting agents typically comprise nonionic surfactants, hydrotropes, hydrophilic monomers or polymers, or combinations thereof.

In certain embodiments of the cleaning and protection compositions, one surfactant may be an anionic surfactant and one may be a nonionic surfactant.

Useful anionic surfactants include surfactants having the following molecular structures, including: (1) at least one hydrophobic moiety (e.g., alkyl groups having from 6 to 20 carbon atoms in the chain, alkylaryl groups, alkenyl groups, and combinations thereof), (2) at least one anionic group (e.g., sulfate, sulfonate, phosphate, polyoxyethylene sulfate, polyoxyethylene sulfonate, polyoxyethylene phosphate, and combinations thereof), (3) salts of such anionic groups (e.g., alkali metal salts, ammonium salts, tertiary amine salts, and combinations thereof), and combinations thereof.

Useful anionic surfactants include, for example, fatty acid salts (e.g., sodium stearate and sodium laurate), carboxylic acid salts (e.g., alkyl carboxylates (carboxylates) and polyalkoxy carboxylates, alcohol ethoxylated carboxylates, and nonylphenol ethoxylated carboxylates); sulfonates (e.g., alkylsulfonates (alpha-olefin sulfonates), alkylbenzene sulfonates (e.g., sodium dodecylbenzenesulfonate), alkylaryl sulfonates (e.g., sodium alkylaryl sulfonates), and sulfonated fatty acid esters); sulfates (e.g., sulfated alcohols (e.g., fatty alcohol sulfates such as sodium lauryl sulfate), salts of sulfated alcohol ethoxylates, salts of sulfated alkyl phenols, alkyl sulfates (e.g., sodium lauryl sulfate), sulfosuccinates, and alkyl ether sulfates), aliphatic soaps, fluorosurfactants, anionic silicone surfactants, and combinations thereof.

Suitable commercially available anionic surfactants include: sodium lauryl sulfate surfactant available under the tradename TEXAPON L-100 from Hangao, Wilmington, Delaware, Wilkinson, and Stepan Chemical Co., Northfield, Ill.A. from Stepan Chemical Co., Nustrife, Ill.; sodium lauryl ether sulfate surfactant available from steviopan chemical under the tradename POLYSTEP B-12; ammonium lauryl sulfate surfactant available from hangao under the trade name STANDAPOL a; sodium dodecylbenzene sulfonate surfactant available from Rhone-Poulenc, Inc., Cranberry, N.J., under the tradename SIPHOTE Ds-10; decyl (sulfophenoxy) benzenesulfonic acid disodium salt available under The trade designation DOWFAX C10L from Dow Chemical Company, Midland, Michigan, Midland.

Useful amphoteric surfactants include, for example, amphoteric betaines (e.g., cocamidopropyl betaine), amphoteric sulfobetaines (cocamidopropyl hydroxysulfobetaine and cocamidopropyl dimethyl sulfobetaine), amphoteric imidazolines, and combinations thereof. Useful cocamidopropyl dimethyl sulfobetaines are commercially available from Longsha Group, Inc. of Basel, Switzerland, under the trade name LONZAINECS. Useful coco alkanolamide surfactants are commercially available from mona chemistry (MonaChemicals) under the trade name MONAMID 150-ADD. Other commercially available amphoteric surfactants that may be used include, for example, caprylic glycinate (an example of which is available under the trade name REWOTERIC AMV from Witco Corp.) and caprylyl amphoteric dipropionate (an example of which is available under the trade name AMPHOTERGE KJ-2 from Longsha Group, Inc. (Lonza Group Ltd)).

Examples of useful nonionic surfactants include polyoxyethylene glycol ethers (e.g., octaethylene glycol monolauryl ether, pentaethylene glycol monolauryl ether, polyoxyethylene lauryl ether, polyoxyethylene cetyl ether), polyoxyethylene glycol alkylphenol ethers (e.g., polyoxyethylene glycol octylphenol ether and polyoxyethylene glycol nonylphenol ether), polyoxyethylene sorbitan monooleate ether, polyoxyethylene lauryl ether, polyoxypropylene glycol alkyl ether, glucoside alkyl ethers (e.g., decyl glucoside, lauryl glucoside, and octyl glucoside), glycerol alkyl esters, polyoxyethylene glycol sorbitan alkyl esters, monodecanoyl sucrose, cocamide, dodecyl dimethyl amine oxide, alkoxylated alcohol nonionic surfactants (e.g., ethoxylated alcohols, propoxylated alcohols, and ethoxylated propoxylated alcohols). Useful nonionic surfactants include: alkoxylated alcohols commercially available from Shell Chemical LP, Houston, Tex under the trade designations NEODOL 23-3 and NEODOL 23-5 and from Ronaplug corporation under the trade designation IGEPAL CO-630; laurylamine oxide commercially available from Longsha group, Inc. under the trade name BARLOX LF; and alkylphenol ethoxylates and ethoxylated vegetable oils commercially available under the trade designation Emulphor EL-719 from GAF corporation (GAF corp., Frankfort, Germany), Frankfort, Germany.

Examples of useful cationic surfactants include dodecyl ammonium chloride, dodecyl ammonium bromide, dodecyl trimethyl ammonium bromide, dodecyl pyridinium chloride, dodecyl pyridinium bromide, hexadecyl trimethyl ammonium bromide, cationic quaternary ammonium, and combinations thereof.

Other useful surfactants are described in U.S. Pat. No. 6,040,053(Scholz et al).

The surfactant is preferably present in the cleaning and protecting composition in an amount sufficient to lower the surface tension of the composition and to clean the surface relative to a composition not containing the surfactant. The cleaning and protective composition preferably comprises at least 0.02 wt.%, or at least 0.03 wt.%, or at least 0.05 wt.%, or at least 10 wt.% of a surfactant. The cleaning and protective composition preferably comprises no more than 0.4 wt.% or no more than 0.25 wt.% surfactant. In certain embodiments, the cleaning and protection composition preferably comprises from 0.05 wt.% to 0.2 wt.% or from 0.07 wt.% to 0.15 wt.% of a surfactant.

Water (W)

The amount of water present in the cleaning and protective composition varies depending on the purpose and form of the composition. The cleaning and protective compositions can be provided in a variety of forms, including, for example, as concentrates that can be used as is, concentrates that are diluted prior to use, and as ready-to-use compositions. Useful concentrate compositions comprise at least 60 wt.%, at least 65 wt.%, or at least 70 wt.% water. Useful concentrate compositions include no greater than 97 wt.%, no greater than 95 wt.%, or no greater than 90 wt.% water. In certain embodiments, useful concentrate compositions comprise from 75% to 97% or even from 75% to 95% by weight water.

Useful ready-to-use compositions comprise at least 70 wt.%, at least 80 wt.%, at least 90 wt.%, at least 95 wt.%, 80 wt.% to 99.75 wt.%, or even 80 wt.% to 97 wt.% water.

Optional Components in cleaning and protective compositions

The cleaning and protective composition optionally comprises one or more silicates, polyalkoxysilanes, or combinations thereof. These components may provide cleaning capabilities (e.g., due to an increase in the pH of the composition). They may also provide protection (e.g., due to cross-linking).

Typically, the silicate is water soluble, and preferably is a water soluble alkali metal silicate. Examples of suitable water-soluble alkali metal silicates include lithium silicate, sodium silicate, potassium silicate, alkyl polysilicates, and combinations thereof.

When present in the composition, the water-soluble alkali metal silicate is preferably present in an amount of at least 0.0001 wt.%, at least 0.001 wt.%, at least 0.01 wt.%, at least 0.02 wt.%, at least 0.05 wt.%, at least 0.1 wt.%, or at least 0.2 wt.%. When present in the composition, the water-soluble alkali metal silicate is preferably present in an amount of no greater than 10 wt.% or no greater than 5 wt.%. In certain embodiments, the water-soluble alkali metal silicate is present in an amount of from 0.02 wt.% to 1 wt.%, or even from 0.1 wt.% to 0.5 wt.%.

Generally, polyalkoxysilanes are less hydrophilic than the hydrophilic silanes described herein. They may be water soluble, alcohol soluble or both. Examples of suitable polyalkoxysilanes include poly (diethoxysiloxane), tetraalkoxysilanes (e.g., oligomers of Tetraethylorthosilicate (TEOS) and tetraalkoxysilane), and combinations thereof.

When present in the composition, the polyalkoxysilane is preferably present in an amount of at least 0.0001%, at least 0.001%, at least 0.01%, at least 0.02%, at least 0.05%, at least 0.1%, or at least 0.2% by weight. When present in the composition, the polyalkoxysilane is preferably present in an amount of no greater than 10% by weight or no greater than 5% by weight. In certain embodiments, when present in the composition, the polyalkoxysilane is preferably present in an amount of from 0.02% to 1% by weight, at or even from 0.1% to 0.5% by weight.

The cleaning and protection composition may also optionally include an inorganic sol, such as a silica sol, an alumina sol, a zirconium sol, and combinations thereof. Examples of useful silica sols include aqueous inorganic silica sols and non-aqueous silica sols. A variety of inorganic silica sols in aqueous media are suitable, including, for example, silica sols in water and silica sols in water-alcohol solutions. Useful inorganic sols are commercially available under the trade name LUDOX from dupont DE Nemours and co, inc, Wilmington, DE, located in Wilmington, dalton, delavay, NYACOL, located in NYACOL, located in Ashland, Maine, and Ondea NALCO Chemical company, okd Brook, Illinois, located in okburke, Illinois. One useful silica sol is a NALCO 2326 silica sol having an average particle size of 5 nanometers, a pH of 10.5, and a solids content of 15 wt.%. Other commercially available silica sols that may be used are available from Nalco 1115 and NALCO 1130 from Nalco Chemical company of Neppervell, Illinois, under the trade name REMASOLSP30 from Lemei corporation (Remet Corp.), under the trade name LUDOX SM from DuPont corporation (E.I. DuPont de Nemours Co., Inc.), and from Nissan Chemical Co., under the trade names SNOWTEX ST-OUP, SNTEX ST-UP, and SNOWTEXST-PS-S.

Useful non-aqueous silica sols (also referred to as silica organosols) include sol dispersions in which the liquid phase is an organic solvent or an aqueous organic solvent. The particles of the sol are preferably nanoscale particles. The sodium stabilized silica nanoparticles are preferably acidified prior to dilution with an organic solvent such as ethanol. Dilution prior to acidification can produce poor or uneven coatings. The ammonium stabilized silica nanoparticles can generally be diluted and acidified in any order.

When present, the cleaning and protection composition preferably comprises at least 0.005 wt.%, at least 0.01 wt.%, or at least 0.05 wt.% of an inorganic sol (e.g., an inorganic silica sol). When present, the cleaning and protection composition preferably comprises no greater than 3 wt.%, no greater than 2 wt.%, no greater than 1.5 wt.%, or even no greater than 1 wt.% of an inorganic sol (e.g., an inorganic silica sol).

The cleaning and protective composition also optionally comprises water insoluble abrasive particles, organic solvents (e.g., water soluble solvents), detergents, chelating agents (e.g., EDTA (ethylenediaminetetraacetate salts), sodium citrate, and zeolite compounds), fillers, abrasives, thickeners, builders (e.g., sodium tripolyphosphate, sodium carbonate, sodium silicate, and combinations thereof), sequestering agents, bleaching agents (e.g., chlorine, oxygen (i.e., chlorine-free bleaching agents), and combinations thereof), pH adjusters, antioxidants, preservatives, fragrances, colorants (e.g., dyes), and combinations thereof.

Examples of suitable water-insoluble abrasive particles include silica (e.g., silica particles, such as silica nanoparticles), perlite, calcium carbonate, calcium oxide, calcium hydroxide, pumice, and combinations thereof.

When present in the composition, the water insoluble particles are preferably present in an amount of from 0.1 to 40 wt%, from 0.1 to 10 wt% or even from 1 to 5 wt%.

The cleaning and protective composition may also optionally comprise an organic solvent. When the cleaning and protection composition is a concentrate, the composition is optionally diluted with an organic solvent or a mixture of an organic solvent and water. Useful organic solvents include, for example, alcohols (e.g., methanol, ethanol, isopropanol, 2-propanol, 1-methoxy-2-propanol, 2-butoxyethanol, and combinations thereof), d-limonene, monoethanolamine, diethylene glycol ethyl ether, tripropylene glycol monomethyl ether, dipropylene glycol n-propyl ether, acetone, and combinations thereof.

When present, the cleaning and protection composition comprises no more than 50 wt.%, from 0.1 wt.% to 30 wt.%, from 0.2 wt.% to 10 wt.%, or even from 0.5 wt.% to 5 wt.% of organic solvent.

Thickeners can help thicken the composition and can also be useful in situations where it is desirable to increase the time a consumer can wipe the composition before it runs down a vertical surface. Examples of useful thickeners include polyacrylic acid polymers and copolymers, examples of which are available under the trade designation CARBOPOL ETD 2623 from goodrich Corporation of Charlotte, North Carolina (b.f. goodrich Corporation, Charlotte, North Carolina) and ACCUSOL 821 from Rohm and Haas Company of Philadelphia, Pennsylvania, hydroxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, and combinations thereof.

Reagent kit

The present disclosure also provides kits comprising the writable cleanable article and the cleaning and protecting composition in any suitable package. For example, the cleaning and protective composition may be packaged in a container equipped with a dispenser (e.g., a plastic bottle equipped with a sprayer or spray pump in a ready-to-use form), or in a container from which the composition may be transferred to another container or in which the composition may be diluted (e.g., when the composition is in a concentrate form).

A writable cleanable article as described herein is included in a kit of the present disclosure. In certain embodiments, the writable cleanable article 10 comprises: a base member 12 having a front surface 17; a facing layer 13 comprising a cured polymer matrix (organic or inorganic polymer matrix) and a plurality of inorganic nanoparticles dispersed in the cured polymer matrix, wherein the facing layer is disposed on at least a portion of the front surface of the base member; an optional primer layer (not shown) disposed on at least a portion of face layer 13; and a hydrophilic overcoat layer 14 bonded to the topcoat 13 and/or optional primer layer by siloxane bonds; wherein the hydrophilic overcoat layer provides a writable cleanable surface. In certain embodiments, the article 10 further includes an adhesive layer 18, and a removable liner 20 on a back surface 22 of the body member 12.

Examples of suitable adhesives include any of a variety of adhesives. The adhesive is typically selected based on the type of substrate to which it is to be adhered. The binder may be a polymer dispersed in a solvent or water and coated on the release liner and dried, and optionally crosslinked. If solvent-based or aqueous pressure sensitive adhesive compositions are employed, the adhesive typically undergoes a drying step to remove all or most of the liquid carrier. Additional coating steps may be necessary to achieve a smooth surface. The adhesive may also be hot melt coated onto the liner or microstructured backing. Alternatively, the pre-adhesive composition of monomers may be coated on the liner and polymerized with an energy source, such as heat, UV radiation, or electron beam radiation.

The thickness of the adhesive depends on several factors including, for example, the adhesive composition, the type of structure used to form the microstructured surface, the type of substrate, and the thickness of the film. The thickness can be adjusted by one skilled in the art to meet the particular application factors.

Preferred adhesives are pressure sensitive adhesives. Classes of pressure sensitive adhesives include acrylics, tackified rubbers (natural or synthetic), ethylene vinyl acetates, silicones, and the like. Suitable acrylic adhesives are disclosed, for example, in U.S. Pat. No. 3,239,478(Harlan), 3,935,338(Robertson), 4,952,650(Young et al), 4,181,752(Martens et al), 5,169,727(Boardman), U.S. Pat. No. RE 24,906 (Uhlrich). Preferred classes of pressure sensitive adhesives are the reaction products of at least an alkyl acrylate and at least one reinforcing comonomer. Suitable alkyl acrylates are those having a homopolymer glass transition temperature of less than-10 ℃ and include, for example, n-butyl acrylate, 2-ethylhexyl acrylate, isooctyl acrylate, isononyl acrylate, octadecyl acrylate, and the like. Suitable reinforcing monomers are those having a homopolymer glass transition temperature at or above-10 ℃ and include, for example, acrylic acid, itaconic acid, isobornyl acrylate, N-dimethylacrylamide, N-vinyl caprolactam, N-vinyl pyrrolidone, and the like.

The pressure sensitive adhesive may optionally include one or more additives. Additives selected from the group consisting of initiators, fillers, plasticizers, tackifiers, chain transfer agents, fiber reinforcements, foaming agents, antioxidants, stabilizers, flame retardants, viscosity enhancers, colorants, and mixtures thereof may be used depending on the polymerization process, coating process, end use, and the like.

Examples of suitable release liners include any of a wide variety of materials. Exemplary materials include organic polymers such as polyethylene, polypropylene, polyester, cellulose acetate, polyvinyl chloride, and polyvinylidene fluoride, as well as paper or other substrates coated or laminated with such organic polymers. These embossable coated papers or thermoplastic films are typically siliconized or otherwise treated to improve release characteristics. The thickness of the release liner can vary widely depending on the desired effect. Further, the release liner may be provided with structure by using various techniques, such as those disclosed in U.S. patent 5,650,215 (Mazurek).

Wiping article

The present disclosure also provides a wipe (i.e., towelette) comprising an absorbent substrate (typically a sheet) impregnated with the cleaning and protection composition as described herein. Such compositions are impregnated at a desired weight into an absorbent substrate, which may be formed from a variety of woven or nonwoven fibers, fiber blends, and/or foams having sufficient wet strength and absorbency to maintain an effective amount of the composition. From the viewpoint of cleaning and protective effects, it is preferable to use an absorbent substrate having a high absorption capacity (for example, 5 g/g to 20 g/g, preferably 9 g/g to 20 g/g). The absorbent capacity of an absorbent substrate is the ability of such a substrate to hold liquid when supported horizontally. The substrate used herein is typically a coherent fiber or filamentary product having a web or carded fibrous structure (when the fiber strength is suitable to allow carding), or a fibrous mat in which the fibers or filaments are randomly distributed in a random array (i.e., an array of fibers in a carded web in which partial orientation of the fibers is often present and completely random distributed orientation is also often present) or are substantially aligned. The fibers or filaments may be natural or synthetic.