KR100711037B1 - Discoloration resistant articles for applying color to surfaces and methods for reducing discoloration in articles for applying colors to surfaces - Google Patents

Abstract

A layered article for applying color to a surface is disclosed that includes a sheet for visually recognizable color effects, a binder capable of bonding the sheet to a surface, and a release liner removably attached to the sheet. The article further comprises a material, formulation or barrier that prevents or at least reduces movement from the surface of the foreign formulation to a location in the layered article that affects the visually recognizable color effect delivered by the sheet.

Discoloration, Sheets, Binders, Lamellar Supplies, Foreign Agents, Blocking

Description

Discoloration-resistant articles for applying color to surfaces and methods for reducing discoloration in articles for applying colors to surfaces {DISCOLORATION-RESISTANT ARTICLES FOR APPLYING COLOR ON SURFACE S

FIELD OF THE INVENTION The present invention relates to articles and methods for applying color to a surface, and more particularly, to resistance to discoloration caused by the movement of foreign agents such as foreign dyes and pigments from the surface to which the article is applied. The present invention relates to an article for applying color to a surface, and a method for alleviating or preventing migration of a foreign agent causing such discoloration.

Thin sheets for visually recognizable color effects, such as dry color elements, can be adhesively fixed to a surface by a bonding layer, typically an adhesive, for color application. Heterogeneous materials or agents in or on the surface, such as pigments in the paint coating, can be dissolved (ie melted) into the bonding layer and transferred to a visually perceptible color effect sheet as a permeant. If some foreign agent is present on the surface and migrates to the sheet, it may cause discoloration of the color effect provided by the article. For example, discoloration may be caused by organic pigments found in conventional wall paint that are partially dissolved by the bonding layer and then migrate through the bonding layer into the sheet for visually recognizable color effects. For example, the sheet may be yellowed by the migration of monoazo pigments from the surface. Often, a visually recognizable color effect sheet includes a topcoat that may inhibit volatilization and release of the foreign agent from the article to accelerate accumulation of the foreign agent in the sheet and subsequent discoloration. The concentration of the foreign agent, and thus the degree of discoloration, in the sheet for visually recognizable color effects increases over the life of the article. Low molecular weight components and elevated temperatures in the paint, such as ethylene glycol, flocculent aids and water, accelerate the movement of foreign agents, which will likewise accelerate discoloration.

Summary of the Invention

According to the principles of the present invention, an article is provided for delivering visually recognizable color effects to a surface containing a foreign agent. The article generally includes a sheet for visually recognizable color effects, a binder held by the sheet to bond the sheet to the surface, and a releasable liner removably covering the sheet. In one aspect of the invention, the article may comprise a barrier layer disposed between the sheet and the binder. The barrier layer is effective to reduce the migration of foreign agents from the surface to the sheet. In various specific embodiments, the barrier layer may comprise a glass-coated polymer, a ceramic-coated polymer, a sodium silicate-containing composition, at least one of anionic and cationic layers, or nanocomposites. The barrier layer may optionally comprise a nonwoven material, a metallized material, a cellulose material and / or a polymer layer.

Alternatively, or in addition to the barrier layer, the article, binder, tie layer, and / or barrier layer of the article can absorb the foreign agent to reduce migration of the foreign agent from the surface to the sheet. It may also include a scavenger material. In yet another alternative embodiment, the sheet, binder, tie layer, and / or barrier layer of the article may include neutralizing agents that can modify the foreign agent to reduce the migration of the foreign agent from the surface to the sheet. In another embodiment of the present invention, i.e., an article that delivers a visually recognizable color effect to a surface containing a foreign agent, the binder of the article has a solubility in the foreign agent, substantially different from the solubility of the foreign agent on the surface. . In another embodiment of the invention, the binder controls discoloration.

According to the present invention, a method of preventing and reducing discoloration of a layered article that delivers visually recognizable color effects is provided. The method comprises making the layered article suitable for application to a surface containing a foreign agent and adding a barrier layer, scavenger material, and / or neutralizing agent to one or more layers of the layered article, or one or more layers of the layered article By adjusting the solubility of the foreign agent at the surface to substantially differ from the solubility of the foreign agent at the surface, thereby reducing the migration of the foreign agent from the surface to a portion of the layered article that provides a visually recognizable color effect. Modifying.

BRIEF DESCRIPTION OF THE DRAWINGS The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and, together with the general description of the invention and a detailed description of the embodiments given below, serve to explain the principles of the invention.

1 is a schematic diagram of an article for applying color to a surface, according to one embodiment of the invention.

1A is a schematic diagram similar to FIG. 1, in accordance with an embodiment of the invention.

2 is a schematic diagram of an article for applying color to a surface according to an alternative embodiment of the present invention.

2A is a schematic diagram similar to FIG. 2, in accordance with an embodiment of the invention.

3 is a schematic representation of an article for applying color to a surface according to another alternative embodiment of the present invention.

3A is a schematic diagram similar to FIG. 3, in accordance with an embodiment of the invention.

4 is a graph showing the absorbance of a solution containing a monoazo pigment, with and without various types of activated carbon added.

The present invention provides an article for applying color to a surface that protects a material providing color against discoloration caused by a foreign agent that migrates, diffuses or smears into a portion of the article that supplies the color from the surface to which the article is applied; and It is about a method. As employed herein, the term "color" is used to refer to a color effect, ie, a difference in color recognition. In a specific embodiment, the color effect is in fact a permanent color effect, i.e. a color effect that is not removed or significantly reduced in the case of routine contact or light cleaning or the like. Thus, in effect, permanent color effects are distinguished from temporary color effects that are easily removed or reduced, such as those provided by chalk or crayons. The term "color element" is used herein to refer to an element of the article that provides a color effect. Topcoats or overcoats may also be applied over the color layer. It is understood that the article may also provide other functional effects on the surface when in use. The main function of the article is not limited to providing color or other aesthetic effect.

The term "surface" is used herein to refer to any outer layer or boundary of an object or substrate that can accommodate a color element thereon. Suitable surfaces may be substantially two-dimensional and flat, or substantially three-dimensional and include curved or angled portions, and the like. In one embodiment, the surface to which the color elements are applied using the articles and methods of the present invention include architectural surfaces, ie, surfaces of buildings, fixtures (ie, fixtures) of furniture, furniture, and the like. An architectural building surface may be an interior surface within a building or an exterior surface on the exterior of a building. Substantially three-dimensional architectural surfaces may include, for example, cornering of two-dimensional surfaces such as moldings (eg, moldings around windows or doors), floors, fixtures, furniture, floors, counters, and the like. The building surface may be permanently installed, temporarily installed or movable. In addition, the article of the present invention may be applied to the surface of an article to provide a texture and / or appearance that is the same or different than the building surface. For example, the products of the present invention can be used to apply color layers to fixtures, furniture, and other building supplies. Additional surfaces suitable for application of color using the articles and methods of the present invention will become apparent to those skilled in the art by the description herein.

Referring to FIG. 1 and in accordance with the principles of the present invention, the article 10 for applying color to the surface 16 comprises a sheet 12 for visually recognizable color effects, such as dry color elements, a binder 14, such as an adhesive. ), A release liner 18 covering the sheet 12, and a barrier layer 20 positioned between the binder 14. The sheet is formed of any suitable material, including but not limited to polymers such as polyurethanes, polyvinyl chlorides, polyvinylidene fluorides, polyacrylates, cellulosic materials and the like and blends and copolymers thereof It may also include a top coat 15. The binder is any material capable of attaching the sheet 12 to the surface 16 at ambient temperature of the environment of the article 10. In some embodiments of the present invention, the sheet 12 may have a thickness of about 0.084 mm (0.0033 inch or 3.3 mil) or less.

The release liner 18 is removable and is intended and suitable for removal at the same time as or after application of the sheet 12 to the surface 16. Typically, the release liner 18 is removed by peeling the liner 18 from the sheet 12. The release liner 18 provides structural support and / or strength to the sheet 12 when the release liner is in film form, for example, and / or facilitates handling of the article during manufacture, storage and use, and optionally the sheet 12 May be used to deliver the finishing material. Exemplary article 10 is described in commonly assigned US application Ser. No. 10 / 324,237, entitled "Articles and Methods for Applying Color to Surface," the disclosure of which is incorporated herein by reference in its entirety. Is disclosed.

In this specification, reference to terms such as "vertical", "horizontal", "below", "above", and the like is made by way of example and not by way of limitation, to establish a reference frame. It is understood that various other frameworks of reference may be used without departing from the spirit and scope of the invention.

With continued reference to FIG. 1, the barrier layer 20 may be a prophylactic barrier layer 20, including, but not limited to, foreign (eg, heterogeneous) substances or agents by mechanisms including diffusion and migration. It acts to eliminate or at least substantially delay the movement of the sheets (originating from the surface 16 to be colored and schematically shown in FIG. 1 and designated by reference numeral 21). Exogenous formulation 21 is understood to be exotic by being present at a finite concentration in sheet 12 or to be considered exogenous by increasing the existing concentration of the formulation normally present in sheet 12. One such foreign agent 21 is present on or covers the surface 16 before the article 10 is applied and mechanically the binder 14 is mechanically bonded for bonding to the surface 16 of the article 10. Organic pigments or dyes present in existing layers such as existing paint layers to be combined.

The barrier layer 20 moves by forming an impermeable or impermeable barrier to the passage or penetration of the foreign agent 21 to prevent or reduce degradation of the properties of the article 12, such as to prevent the occurrence of discoloration. Act as a physical barrier to block, prohibit or otherwise prevent. Alternatively, the barrier layer 20 slows down or delays the rate of movement of the foreign agent 21, such that the sheet 12, such as color, over at least the life of the article 10 for providing color to the surface 16. ) Can be recognizably unaffected. The thickness and properties of the barrier layer 20 are adjusted to provide the desired barrier or delay. The barrier layer 20 has a thickness of about 0.064 mm (2.5 mil or 0.0025 inch) or less, and in some embodiments of the invention, the barrier layer 20 may be 0.025 mm (0.1 mil or 0.001 inch) or thinner. .

The barrier layer 20 is shown in FIG. 1 as being included as a layer, strata, or lamina identifiable in the layered structure of the article 10. In an alternative embodiment of the invention, a barrier layer 20a which is characterized by the same properties as the barrier layer 20 may be included as an element of the binder 14. In another alternative embodiment, a barrier layer 20b, which is characterized by the same properties as the barrier layer 20, may be included as an element of the sheet 12. The barrier layers 20a, 20b are each separated into layers, strata or lamina located within the thickness of the binder 14 or sheet 12, or over the thickness of the corresponding one of the binder 14 or sheet 12. It may be evenly distributed. The barrier layers 20, 20a, 20b may be employed individually or included in the article 10 in any permutation or combination. Each of the barrier layers 20, 20a, 20b may combine two or more of the candidate materials disclosed herein. It is understood that the properties of the barrier layer 20 disclosed herein apply equally to the barrier layers 20a, 20b.

In general, the features and characteristics required for the barrier layer 20 will depend, among other things, on the identity of the foreign agent 21 and its transport mechanism in the barrier layer 20. Several factors are known to affect the transport properties of formulations such as foreign formulations 21 in materials such as barrier layer 20. The chemical properties of the polymers forming the barrier layer 20 affect transport because foreign agent transport is believed to decrease with increasing strength of the force holding the polymer chains together. Polymer backbones are recognized as important factors in determining chain-to-chain forces. The polymer chain should move sideways or open to allow formulation movement or penetration. Polymers having hydroxyl, cyano, halogen, ester and amide bonds are exemplary candidate materials for the barrier layer 20, but the present invention is not so limited. In general, any polymer having a glass transition temperature that exceeds the ambient temperature conditions of the environment of the surface 16 to which the article 10 is applied will have an appropriate chain-to-chain force strength.

Another factor influencing the transport of the foreign agent 21 in the barrier layer 20 is the sensitivity to moisture of the polymer forming the barrier layer 20.

The blocking properties of polar materials that depend on hydrogen bonding for their blocking properties will decrease in the presence of water. Water swells the polymer, which reduces chain-to-chain force and allows penetration. Polymers characterized by such polar bonds include, but are not limited to, esters and cyanos.

Another factor influencing the transport of the foreign agent 21 in the barrier layer 20 is the degree of orientation, crystallinity and packing of the polymers constituting the barrier layer 20. Increasing the crystallinity of the barrier layer 20 reduces the free volume and thus improves barrier properties. Increasing the orientation also improves blocking properties as the route for agent migration becomes a more meandering route. However, the stiffness of the material also increases with increasing crystallinity and orientation, which reduces the flexibility of the article 10.

Another factor influencing the transport of the foreign agent 21 in the barrier layer 20 is the property of the polymer surface in contact with the sheet 12 or the binder 14. The hydrophilic or hydrophobic surface and / or the polar or nonpolar surface may prevent, at least reduce or delay the movement of the foreign agent 21 from the surface 16.

Another factor influencing the transport of the foreign agent 21 in the barrier layer 20 is the presence of additives and modifiers. Additives typically act to reduce chain-to-chain forces to make the polymer flexible, thereby increasing penetration. Blending polymers with weak barrier properties with polymers with acceptable barrier properties will increase the barrier of the weak barrier material.

In one specific embodiment of the invention, the barrier layer 20 comprises from about 3% to about 40% by weight of water-glass or sodium silicate (Na ₂ Si ₄ O ₂ ), from about 3% to about 40% by weight. And a composition of about 20% to about 24% by weight of water. The use of sodium silicate as a barrier layer is disclosed in US Pat. Nos. 1,365,715 and 5,460,855, the disclosures of which are incorporated herein by reference in their entirety. The polymer in the composition imparts flexibility to such barrier layer 20 and the presence of water dilutes the composition to facilitate the coating application process. Sodium silicate is prepared by blending or fusing various ratios of sand and soda ash (ie sodium carbonate) at high temperatures.

In another specific embodiment of the present invention, the barrier layer 20 comprises at least one of an anionic layer and a cationic layer capable of capturing or trapping the foreign agent 21. One technique suitable for incorporating such anionic and cationic layers into article 10 is to coat sheet 12 with an aqueous dispersion. Suitable cationic and anionic aqueous dispersions are disclosed in US Pat. No. 6,576,327, the disclosure of which is incorporated herein by reference in its entirety. Specific cation and anionic aqueous dispersions are available, for example, under the trade names ACRONAL®, BUTONAL®, STYROFAN®, and PROPIOFAN® BASF Aktiengesellschaft, Ludwigshafen, Germany. Can be purchased from. The anionic layer is effective for capturing the positively charged foreign agent 21 and the cationic layer is effective for capturing the negatively charged foreign agent 21. Frequently, the barrier layer 20 is constituted by a two-layered or multilayered structure consisting of spatially separated anionic and cationic layers, so that all charged foreign agent particles are captured, regardless of the charge state of the foreign agent 21. It may also be fixed against migration into the seat 12. For example, the upstream anion layer will trap positively charged foreign agent particles and permeate negatively charged heterogeneous particles to be captured by the downstream cation layer further away from the surface 16. Alternatively, the two-layer or multi-layered cation layer may be disposed upstream of the anion layer. Alternatively, the anionic layer or cationic layer may be provided to the binder 14 or mixed as a component of the binder, and the other of the anionic layer or the cationic layer is provided as a separate layer.

In another specific embodiment of the present invention, the barrier layer 20 is a glass-coated polymer. Suitable glass-coated polymers include aluminum oxide-coated polyethylene terephthalate polymers and copolymers, aluminum oxide-coated polypropylene polymers and copolymers, aluminum oxide-coated nylon polymers and copolymers, and combinations of these materials However, it is not limited to this. Such glass coatings are typically transparent inorganic materials. Such glass coating may be applied, for example, by a plasma based deposition process.

In another specific embodiment of the present invention, the barrier layer 20 is a ceramic-coated polymer. One suitable coating material is silicon oxide (SiO _x ), which may be either stoichiometric or non-stoichiometric, which may be deposited by a chemical vapor deposition process using silane as a precursor source. Suitable ceramic-coated materials include silicon oxide-coated oriented polypropylene, silicon oxide-coated polyethylene terephthalate, silicon oxide-coated oriented polyvinyl alcohol, silicon oxide-coated polypropylene, silicon oxide-coated Polyethylene, and combinations thereof, including but not limited to.

In another specific embodiment of the present invention, the barrier layer 20 is a nanoclay-based composite material or plastic nano that creates a tortuous path that the foreign agent 21 must successfully traverse in order to reach the sheet 12. It is a complex. Nanoclay-based composite materials are formed by dispersing nanoclay platelet particles, tactoids of individual platelet particles, aggregates of tactoids, or mixtures thereof in a polymer host matrix. Nanoclay platelet-shaped particles are arranged in a sheetlike structure having the form of a plurality of neighboring bonded layers, where the planar dimension is significantly larger than the thickness of the structure. In some embodiments of the invention, the nanoclay addition in the host polymer resin may exceed about 0.5% by weight. In other embodiments of the invention, the nanoclay addition in the host polymer resin may range from about 0.5% to about 25% by weight. In any case, nanoclay addition is sufficient to form a serpentine route through the host polymer resin. Individual platelet particles may have a thickness of less than about 2 nm and a diameter in the range from about 10 nm to about 5000 nm.

Nanoclay platelet-shaped particles may be composed of any suitable organic or inorganic material, in particular may be composed of phyllosilicates. Natural phyllosilicates suitable for use in the present invention include smectite, such as montmorillonite, saponite, hectorite, mica, vermiculite, bentonite, nontronite, baydelite, volconscote, margotite, and kenyanite. Includes but is not limited to clay. Synthetic phyllosilicates suitable for use in the present invention include, but are not limited to, synthetic mica, synthetic saponite, and synthetic hectorite. Synthetic or natural phyllosilicates may be modified by fluorination or by the addition of organic cations. Phyllosilicates suitable for use in the present invention may be purchased from a variety of sources including Nanocor, Inc. (Arlington Heights, Ill.). Suitable host polymer resins for the matrix include, but are not limited to, polyamide polymers and copolymers, polyethylene terephthalate polymers and copolymers, polypropylene polymers and copolymers, and combinations thereof. Nanoclay platelet-shaped particles may be derived from natural, synthetic and modified phyllosilicates and may be treated to contain organic cations.

Another nanoclay based polymeric material suitable for use in the present invention is AEGIS nanocomposite blocking resin, available from Honeywell, based on nylon 6.

Other inorganic platelet particles suitable for use in the nanocomposite include aluminum or zinc platelets having a thickness of about 3 μm to 10 μm and a diameter of about 4 μm to 17 μm. These inorganic platelet particles may be provided to any of the polymeric host matrices described above in amounts of about 0.1% to 3.5% by weight. Exemplary aluminum platelets can be purchased from Eckhart America L.P. (Lewisville, KY) as aluminum pigment dispersions under the METALURE® trademark.

In another specific embodiment of the present invention, the barrier layer 20 or sheet 12 is formed by a polymer having a crystallinity forming a serpentine path. The polymer forming the barrier layer 20 has a glass transition temperature that is greater than the temperature of the article 10 while being applied to the surface 16 such that the constituent polymer has a low free volume available for migration of the foreign agent 21. You have to have it.

In another specific embodiment of the present invention, the binder 14 or sheet 12 may have a solubility in the foreign agent 21, which is substantially different from the solubility of the foreign agent 21 in the surface 16. . As a result, the foreign agent 21 does not move easily from the surface 16 to the bonding agent 14. If the foreign agent does not enter the binder 14, subsequent migration from the binder 14 to the sheet 12 may not occur subsequently. In this case, the bonding agent 14 functions as the blocking layer 20. The solubility of the foreign agent 21 in the binder 14 may be altered by changing the chemical properties of the adhesive to modify the bond strength between the constituent molecules of the binder 14.

In order to improve the adhesion between the sheet 12 and the barrier layer 20 and / or between the binder 14 and the barrier layer 20, suitable surfaces are corona treated, roughening the target surface to increase the surface area, Swelling of the target surface area, intermolecular mixing or interdiffusion, direct coating of the binder, application of heat or pressure during lamination, inclusion of functionalized polymers to provide covalent or intermolecular bonds, by embossing, brushing or other mechanical methods It may be surface treated by increasing the surface area of one or more layers, or by particle addition or by solvent etching and by a combination thereof. For example, corona treatment involves exposing the sheet 12 to high voltage corona discharge while passing the sheet 12 between the spaced pair of electrodes.

The present invention contemplates that any of the various types of barrier layers 20 disclosed herein may be used alone or in a compatible combination. For example, the barrier layer 20 may be constituted by a two layer structure comprising lamina of nanoclay-based composite material and lamina containing sodium silicate.

In another specific embodiment of the invention, the barrier layer 20 is a sheet of polymer that interacts with the barrier layer 20 to reduce the migration of the foreign agent 21 from the surface 16 to the sheet 12 or It may further comprise a film. The polymer film may also be provided as a lamina in the layered structure of the article 10 separate from the barrier layer 20, or alternatively as a lamina disposed in the sheet 12 or the binder 14. May be In various embodiments, the polymer sheet or film may be polyvinylidene chloride polymers and copolymers, polyvinyl alcohol polymers and copolymers, ethylene vinyl alcohol polymers and copolymers, polychlorotrifluoroethylene polymers and copolymers, acrylonitrile meta Acrylate polymers and copolymers, polyacrylonitrile polymers and copolymers, aromatic polyamide polymers and copolymers, amorphous polyamide polymers and copolymers, polyethylene terephthalate polymers and copolymers, polyvinyl chloride polymers and copolymers, poly Vinylidene fluoride polymers, liquid crystalline polymers and copolymers, polystyrenes, polyethylenes, acrylics, styrene-acrylic copolymers, alkyds, polyurethanes, polypropylene polymers and copolymers, oriented polypropylene polymers and copolymers, cellulose polymers, ball Polymers and coatings, aliphatic polyesters, polyhydroxy alcohols, polycaprolactones, polylactic acid, and combinations thereof. The polymer film resists penetration by the foreign agent 21, helping the barrier layer 20 in blocking or restricting the migration of the foreign agent 21 to the sheet 12. The present invention contemplates that the sheet 12 or binder 14 may comprise one of the polymers listed as components, such that no separate polymer layer is required in the layered structure of the article 10.

Exemplary polyvinylidene (PVDC) polymers suitable for use as the polymer film in the barrier layer 20 can be purchased under the SARAN brand name from Dow Chemical Company (Midland, MI). Commercial sources of exemplary polyvinyl alcohol (PVA) are available from Clariant GmbH (Frankfurt, Germany) and E. children. Du Pont De Nemours & Co. (Wilmington, Delaware). Exemplary ethylene vinyl alcohol copolymers are SOARNOLO from Kuraray Co., Ltd. (Kurashiki, Japan) under the EVAL trademark and from Nippon Gohsei (Osaka, Japan). It can be purchased under the trademark. One suitable polychlorotrifluoroethylene (PCTFE) can be purchased from Honeywell International Inc. (Morris Township, NJ) under the ACLAR® trademark. Suitable acrylonitrile methacrylate copolymers can be purchased under the BAREX® trademark from BP, p.l.c. (London, UK). Exemplary aromatic polyamides can be purchased from Mitsubishi Gas Chemical America Inc. (New York, NY) under the MDX6 trade name, and also from Honeywell International Inc. (Morris Township, New Jersey) and BASF AG. It can be purchased from suppliers such as Tiengelshaft (Ludwigshafen, Germany). Suitable amorphous polyamides for use in the present invention are E.I. DuPont de Nemoa & Company (Wilmington, Delaware) can be purchased under the SELAR PA brand name. Exemplary liquid crystalline polymers may be purchased from Ticona (Summit, NJ) under the VECTRAN® trademark.

The polymer (s), copolymer (s), or (co) polymer blend (s) of the polymer film may be optionally crosslinked by connecting adjacent chains to each other during synthesis or by irreversible chemical reactions. Crosslinking may also be accomplished by additional atoms or molecules covalently bonded to the crosslinked chain. Crosslinking may also be accomplished by weaker chemical interactions, some of the crystals, and even physical entanglements. Crosslinking may act to improve the resistance of the barrier layer 20 to the migration of the foreign agent 21 from the surface 16 to which the article 23 is bonded to the sheet 12. The polymer film may be formed from a thermoplastic resin that softens when exposed to heat and returns to its original state when cooled to room temperature or a thermosetting resin that is irreversibly fixed when heated. Thermosetting polymer resins are known to crosslink in contrast to thermoplastic resins.

In another specific embodiment of the present invention, the barrier layer 20 further comprises a nonwoven web composed of a web having an entangled structure of staple length polymeric fibers composed of individual synthetic fibers, filaments, yarns, or one or more thermoplastic polymers. You may. The nonwoven web may also be provided as a lamina in the layered structure of the article 10 separate from the barrier layer 20, or alternatively as a lamina or distribution component of the sheet 12 or the binder 14. have. Nonwoven webs may be formed from many processes, such as, for example, meltblowing processes, spunbonding processes, and bonded carded web processes. Generally, spunbond nonwoven webs are typically formed from a sheet or coalescing structure of entangled filaments having an average diameter of about 10 to 20 microns, and meltblown nonwoven webs generally have sheets or fibers of average diameter less than 10 microns. It is formed from the merged structure. The nonwoven web may be composed of a multilayer laminate characterized by a combination of spunbond and meltblown layers. Typical thermoplastic polymers used to form nonwoven webs include polyethylene, polypropylene, polyolefins such as polybutylene, polyamides such as nile 6, nylon 6/6, nylon 10 and nylon 12, polyethylene terephthalate and polybutylene Polyesters such as terephthalate, polycarbonates, polystyrenes, thermoplastic elastomers, fluoropolymers, vinyl polymers, and blends and copolymers thereof.

In another specific embodiment of the present invention, the barrier layer 20 is made of wood pulp fibers, cotton (cellulose) fibers, rayon (regenerated cellulose) fibers, acetate (cellulose acetate) fibers and triacetate (cellulose triacetate) fibers. It may further comprise a cellulose nonwoven material formed from an entangled mat or assembly of cellulosic fibers. The cellulosic nonwoven material may also be provided as a lamina in the layered structure of the article 10 separate from the barrier layer 20, or alternatively as a lamina or distribution component of the sheet 12 or the binder 14. It may be. The nonwoven material may also be characterized by a composite blend of cellulose fibers and thermoplastic or synthetic fibers or filaments formed by, for example, hydroentangling. The nonwoven material may also be constructed from one or more webs of cellulose fibers and one or more webs of thermoplastic fibers and filaments laminated together.

In another specific embodiment of the present invention, the barrier layer 20 may further comprise a metallized film formed from a metallized coating or foil, and optionally a layer of polymer film on which the metallized coating or foil is laminated. The metallized film may also be provided as a lamina in the layered structure of the article 10 separate from the barrier layer 20, or alternatively as a lamina disposed in the sheet 12 or the binder 14. have. Suitable metallized films are those materials in the form of metallized polyethylene terephthalate polymers and copolymers, metallized polypropylene polymers and copolymers, metallized polyamide polymers and copolymers, metal foils, and layers laminated for example with laminates. Combinations of but are not limited to. The metallized film may be formed by processes such as vapor phase metallization or chemical vapor deposition of metals such as aluminum, or other metals such as gold, silver, and copper on at least one planar surface of the polymer film. The metallized film may be introduced into the manufacturing process to form the article 10 as a lamination.

In another specific embodiment of the present invention, the barrier layer 20 may further comprise a flexible cellulose material. The flexible cellulosic material may also be provided as a lamina in the layered structure of the article 10 separate from the barrier layer 20, or alternatively as part of the sheet 12 or the binder 14. Cellulose material is any material having cellulose or a cellulose derivative as a component. Suitable cellulosic materials include paper, paper coated with butyrate lacquer, cotton, typical wood pulp, non-wood cellulose fibers, cellulose acetate, cellulose triacetate, rayon, thermomechanical wood pulp, chemical wood pulp, debonded chemical wood pulp, milk Weeds (milkweed), bacterial cellulose, and combinations thereof, but is not limited thereto. The fibers may also be crosslinked, sulfonated, silked, heat treated, mixed with thermoplastic stabilizer fibers, or treated with wet strength formulations. Mixtures of various fibers can be used, including coforms, and other mixtures of co-precipitated thermoplastic fibers and wood fibers. Cellulose acetate is made from wood pulp treated with acetic anhydride to form acetate pieces. Cellulose acetate is produced in a wide variety of thicknesses ranging from 0.025 mm to 0.13 mm (0.001 inch to 0.005 inch) and is usually transparent. Cellulose acetate butyrate is an optically clear lacquer that can be applied to paper or incorporated wood pulp.

Cellulose materials consist mainly of calcium carbonate, titanium dioxide, silica, satin white, barit, mica, zinc oxide, plastic pigments, or kaolin mainly consisting of kaolinite (hydrated aluminum silicate (Al ₂ Si ₂ O ₅ (OH) ₄ )) It may also be coated with a layer or coating with any conventional pigments containing clay pigments. The pigment containing coating is applied to the sheet 12 as an aqueous suspension or dispersion of pigment material in a binder, including but not limited to starch, protein, styrene butadiene dispersion or lattice, polyvinyl acetate and lattice, and acrylic lattice. . The presence of the pigment-containing coating provides an additional barrier effect to the cellulosic material, to enhance the barrier effect of the cellulosic material, or to block or delay the migration of the foreign agent 21 into the layer 12. It can also be provided to a cellulose material. Generally, such pigment containing coatings have a thickness in the range of about 20 μm to about 80 μm. Pigment containing coatings may be modified, for example, by surface treatment containing soluble metal salts to increase their barrier properties.

In addition to the barrier layer 20, the present invention interacts with the barrier layer 20 to reduce or prevent the migration of the foreign agent 21 from the surface 16 to the sheet 12 in addition to the barrier layer 20. It is contemplated that the scavenger material 32 (FIG. 2) and / or neutralizer 46 (FIG. 3) disclosed herein may be included. The scavenger material 32 and / or neutralizer 46 may be provided in a separate layer or one or more laminates of the layered article 10, including the sheet 12, the binder 14, and the barrier layer 20. May be included in me. The trapping agent material 32 disposed in the article 10 includes zeolites, mesoporous zeolites, high surface area carbon blacks, DGB carbon blacks, polycationic molecules, polyvinylpyrrolidone polymers and copolymers, cyclodextrin compounds, activated carbon, cations Carbon, cationic inert materials, anionic materials, magnesium oxide, activated alumina, mixed metal oxides, nanoparticles of metal oxides, coconut carbon, wood carbon, carbon nanotubes, carbon nanofibers, ion exchange resins, dye transfer inhibitors, And materials selected from combinations, blends or mixtures of these materials.

Referring to FIG. 1A, the article 10 includes one or more tie layers 22 disposed between the sheet 12 and the barrier layer 20, and / or the binder 14, as shown in FIG. 1A. It may further comprise one or more tie layers (not shown but similar to tie layer 22) disposed between the barrier layers 20. The present invention contemplates that one or more tie layers 22 may act as or include the barrier layer 20. Typical materials forming at least a portion of each tie layer 22 include functionalized polyolefins, ethylene acrylates, ethylene vinyl acetates, functionalized acrylics, polyvinyl chlorides, polyolefins, polyethoxylates, and combinations, blends and copolymers thereof. It includes. Each tie layer 22 also captures interactions with the barrier layer 20 to reduce or prevent the migration of the foreign agent 21 from the surface 16 to the sheet 12, as disclosed herein. It may contain an agent material 32 (FIG. 2) and / or a neutralizer 46 (FIG. 3).

Referring to FIG. 2, wherein like reference numerals refer to like features in FIG. 1 and according to another embodiment of the present invention, the article 23 for applying color to the surface 16 is a sheet 24 for visually recognizable color effects. ), A binder 26, and a release liner 30. The sheet 24 is similar to the sheet 12 and may comprise a topcoat 25 as a lamina, the binder 26 is similar to the binder 14, and the release liner 30 is a release liner ( Same as 18).

According to the principles of the present invention, the article 23 is such that the foreign agent 21 cannot affect the properties such as the color of the sheet 24 over the life of the article 23 on the surface 16. 23) further comprises a scavenger material (shown schematically at 32) capable of absorbing or capturing the foreign agent 21 moved from the surface 16 to which it is applied. The scavenger material 32 is applied to the foreign agent by trapping, absorbing, adsorbing or trapping in a manner effective to block or prevent migration, such as by diffusion, migration or smearing of the foreign agent 21 into the sheet 24. 21 is erased, which prevents deterioration of the properties of the article 23. For example, the action of the scavenger material 32 may eliminate the occurrence of discoloration in the sheet 24. Alternatively, the scavenger material 32 merely slows or delays the movement of the foreign agent 21 by trapping or absorption, such that the properties of the sheet 24, such as color, are on the surface 16 It can be made to be not recognizably influenced over at least the lifetime of (23). The scavenger material 32 is present at and / or in a concentration effective to mitigate, reduce or eliminate the effect on the sheet 24 of the foreign agent 21 arising from the surface 16. The scavenger material 32 may be applied by a variety of techniques, including but not limited to printing, extrusion, coextrusion, coating, spraying, and combinations of these techniques.

In various specific embodiments of the present invention, the scavenger material 32 is a polycation molecule, a polyvinylpyrrolidone polymer and copolymer, a cyclodextrin compound, activated carbon, cationic carbon, cationic inert material, anionic material, magnesium oxide, active Materials selected from alumina, mixed metal oxides, nanoparticles of metal oxides, coconut carbon, wood carbon, carbon nanotubes, carbon nanofibers, ion exchange resins, dye transfer inhibitors, and combinations, blends or mixtures of these materials to be. The scavenger material 32 may optionally include at least one additional scavenger component selected from zeolites, mesoporous zeolites, high surface area carbon blacks, and / or DGB carbon blacks.

The scavenger material 32 is shown in FIG. 2 as being constrained or contained as a layer, strata or lamina discernable within the layered structure of the article 23. In alternative embodiments of the present invention, a scavenger material 32a that is characterized by the same properties as the scavenger material 32 may be included as a component of the binder 26. In yet another alternative embodiment, a scavenger material 32b that is characterized by the same properties as the scavenger material 32a may be included as a component of the sheet 24. The scavenger material 32a, 32b is separated as a layer, strata, or lamina, respectively, located within the thickness of the binder 26 or sheet 24, or the thickness of the corresponding one of the binder 26 or sheet 24, respectively. It may be evenly distributed over. The scavenger material 32, 32a, 32b may be employed individually or included in the article 23 in any permutation or combination. Each of the trapping agent materials 32, 32a, 32b may combine two or more of the candidate materials disclosed herein. It is understood that the properties of the trapping agent material 32 disclosed herein are representative of the trapping agent materials 32a and 32b.

In one embodiment of the invention and as described above, the scavenger material 32 may be a dye transfer inhibitor. The dye transfer inhibitor may be present in the sheet 24 or the binder 26 in an amount effective to prevent dye transfer to the sheet or to delay dye transfer to the sheet 24 over the functional life of the article 23. Generally, the dye transfer inhibitor is present in an amount ranging from about 0.01% to about 10% by weight based on the weight of the composition. Suitable dye transfer inhibitors include dye polyvinyl pyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, manganese phthalocyanine, peroxidase, and combinations thereof Including but not limited to. Exemplary dye transfer inhibitors are disclosed in commonly assigned US Pat. No. 5,633,225, the disclosure of which is incorporated herein by reference in its entirety.

In another embodiment of the present invention and as described above, the scavenger material 32 is able to absorb the foreign agent 21 moved from the surface 16 to which the article 23 is applied due to its high porosity level. Activated carbon may be used. Activated carbon may be provided in particle form, fiber form, nanotube form, binder, solvent, ink and ink form containing activated carbon particles, and mixtures of these various forms. In the form of particles, fibers and nanotubes, the average particle size may range from about 3 μm to about 70 μm, and preferably about 12.5 μm or less. The ink form may be applied as a separate layer by any conventional printing technique, or alternatively dispersed in the binder 26 and by techniques such as printing, extrusion, coextrusion, coating, spraying, and combinations of these techniques. May be authorized.

Suitable particle forms of activated carbon include Calgon Carbon Corp. (Pittsburg, PA), Specialty Chemicals Division of MeadWestvaco Corp. (Covington, VA), and Carbochem Inc. (Ardmore, PA) can be purchased from a variety of sources. Specific particle forms of activated carbon that may be useful in practicing the present invention include Calgon carbon ADP coconut based activated carbon, RGC wood based activated carbon (WAC) from Midwest Baco, RGC WAC + PVAm, Nuchar SN-30 (WAC) and Nuchar. SA-1500 (WAC), and Carbochem CA-10 (WAC).

In another embodiment of the present invention and as described above, the scavenger material 32 may comprise a coating applied to the sheet 27, which contains a cyclodextrin compound, which may be substituted or derivatized. In general, cyclodextrins are cyclic oligosaccharides composed of glucopyranose units linked by at least 5, preferably at least 6 a-1,4 bonds. One such cyclodextrin-based barrier layer 20 is an extruded film coating composed of about 0.1% to about 60% by weight of cyclodextrin compound dissolved or dispersed in the thermoplastic diluent constituting the remainder of the composition. An extruded film coating, which may have a thickness in a range from about 0.0075 mm (0.3 mil) to about 0.038 mm (1.5 mil), is included as a lamination in the structure of the article 23 at a location between the sheet 24 and the binder 26. do. Cyclodextrin compounds may also be used as aqueous or other solvent-based solutions of cyclodextrin compounds with inert carriers or film forming agents (eg, binders), such as starches, modified starches, celluloses, modified celluloses, and film-forming polymers, or It may be applied by solution coating the sheet 24 with the dispersion. After the water or solvent is removed, the residual film should contain about 0.1 grams of cyclodextrin per square meter to about 0.6 grams of cyclodextrin per square meter. A scavenger material 32 comprising such a cyclodextrin compound is disclosed in International Application No. PCT / US99 / 08017.

In another embodiment of the present invention and as described above, the trapping agent material 32 may comprise an ion exchange resin. Ion exchange resins are polymeric resins containing fixed ions or electrically charged fragments permanently attached to the polymer backbone.

Referring to FIG. 2A, where the same reference numerals refer to the same features in FIGS. 1A and 2, the article 23 is one or more tie layers 22 disposed between the sheet 24 and the binder 26 and / or The barrier layer 20 may further be included. If identifiable as a separate lamina, the one or more tie layers 22, scavenger material 32 and barrier layer 20 may be arranged in any suitable order within the thickness of the article 23. The tie layer (s) may be trapped in the trapping agent material 32, or other lamina of the layered article 23, to reduce or prevent the migration of the foreign agent 21 from the surface 16 to the sheet 12. It may contain a portion of the scavenger material 32 that interacts with other portions of the agent material 32. The blocking layer 20 may be any of the candidate blocking layers 20 disclosed herein. Alternatively, the barrier layer 20 of the article 23 may be formed from a polymer, cellulosic material, nonwoven material, or metallized film, as disclosed herein.

Referring to FIG. 3 and in accordance with another embodiment of the present invention, the article 36 for applying color to the surface 16 includes a sheet 38 for visually recognizable color effects, one surface 42 of the sheet 38. Binder 40, such as an adhesive on the sheet), and a release liner 44. Sheet 38 is similar to sheets 12 and 24 and may include a topcoat 45 as a separate lamina, binder 40 is similar to binders 14 and 26, and a release liner ( 44 is the same as the release liner 18, 30.

The article 36 further comprises a neutralizing agent (shown schematically at 46) capable of breaking the chemical bonds of the foreign agent 21 moved from the surface 16. The neutralizer 46 is effective to block or prevent diffusion into the sheet 38 to prevent degradation of the properties of the article 36 (eg, discoloration of color), such as to prevent or reduce the occurrence of discoloration. Breaking the chemical bond of the foreign agent 21 in a manner. Alternatively, the neutralizing agent 46 can slow or delay the movement of the foreign agent 21 so that the properties of the sheet 38 are not appreciably affected over at least the functional life of the article 36. . Neutralizing agent 46 is present at a concentration and / or location effective to reduce or eliminate migration of foreign agent 21 from surface 16 to sheet 36.

Neutralizing agent 46 is shown in FIG. 3 as being constrained or included as a layer, strata or lamina discernible in the layered structure of article 36. In an alternative embodiment of the invention, a neutralizing agent 46a, which is characterized by the same properties as the neutralizing agent 46, may be included as a component of the binder 40. In yet another alternative embodiment, a neutralizing agent 46b, which is characterized by the same properties as the neutralizing agent 46a, may be included as a component of the sheet 38. The neutralizing agents 46a, 46b are each separated as a layer, strata or lamina located within the thickness of the binder 40 or sheet 38, or over the thickness of the corresponding one of the binder 40 or sheet 38. It may be evenly distributed. The neutralizing agents 46, 46a, 46b may be employed individually or included into the article 36 in any permutation or combination. Each of the neutralizers 46, 46a, 46b may combine two or more of the candidate materials disclosed herein. It is understood that the properties of the neutralizing agent 46 disclosed herein are representative of the neutralizing agents 46a, 46b.

In one specific embodiment of the present invention, the neutralizing agent 46 is a bleaching compound that neutralizes the color associated with the foreign agent 21 resulting from the surface 16 to which the article 36 is applied. Bleach compounds may also be known oxidants for washing, hard surface cleaning, automatic dish washing or tooth cleaning purposes. Bleaching compounds suitable for use in the present invention include, but are not limited to, halogen bleaches such as hypohalite, such as hypochlorite bleach, oxygen bleach, peroxide bleach, sodium borohydride, peracid, and mixtures thereof. The bleach compound acts to break the chemical bonds of the foreign agent 21 so that the foreign agent 21 no longer reveals or exhibits a recognizable color that may discolor the sheet 38.

In another specific embodiment, the neutralizing agent 46 is an optical brightener or fluorescent bleach included in the sheet 38 or, if present, in the topcoat 45. As is known to those skilled in the art, optical brighteners are colorless fluorescent dyes commonly used to make white fabrics appear visually brighter. Optical brighteners, when applied to the surface 16, are exposed to ultraviolet light in the wavelength range of about 300 nm to about 430 nm, such as ultraviolet light included in the artificial or natural light irradiation article 36, from about 400 nm to about 500 nm. It functions by emitting visible light in the wavelength range of. Optical brighteners interfere for the active site in the sheet 38, thereby interfering with the dye or pigment such as the foreign agent 21. Optical brighteners act to visually block the color exhibited by the foreign agent 21. Optical brighteners are vinylene, imino, 2-pyrazoling-1,3-diyl, 1,4-phenylene, 2,5-furandiyl, 2,5-thiophendiyl, phenyl, fur- 2-yl, pyrazol-4-yl, pyrazol-1-yl, 1,2,3-triazol-2-yl, 1,2,4-triazol-1-yl, 1,3,5- Triazin-2-yl, 1,2,4-oxadiazol-5-yl, 1,4-naphthylene, benzofuran-2-yl, benzoxazol-2-yl, benzimidazol-2-yl Molecularly as a chromophore consisting of constituent blocks selected from, 4,7-coumarinindayl, naphtha [1,2-d] triazol-2-yl, naphthalimido, pyren-1-yl, and combinations thereof linked together It consists of. Suitable optical brighteners are described in Ullmann's Encyclopedia of Industrial Chemistry, Vol. 18A, pp. 153-176.

In another specific embodiment of the present invention, the neutralizing agent 46 is added to the sheet 38 or the binder 40 to discolor the foreign agent 21 moved from the surface 16 to which the article 36 is applied. It acts as a pH regulator. The pH adjuster breaks the chemical bond of the foreign agent 21 to prevent the foreign agent 21 from displaying or otherwise revealing a visually recognizable color, or at least the foreign agent 21 has a unique visually recognizable color. The ability to reveal is significantly reduced. The pH adjuster is chemically compatible with the material (s) constituting the sheet 38 if added to the sheet 38 and / or chemically compatible with the material characterizing the binder 40 if added to the binder 40. It may also be an adult any acidic or alkaline substance.

Referring to FIG. 3A, where the same reference numerals refer to the same features of FIGS. 1A and 3, the article 36 may include one or more tie layers 22 and / or a barrier disposed between the sheet 38 and the binder 40. It may further comprise layer 20. The barrier layer 20 and / or tie layer (s) 22 may also optionally contain a scavenger material 32 (FIG. 2) disclosed herein that acts in combination with the neutralizer 46. The optional optical capture agent material 32 may also be provided as a separate lamina in the layered structure of the article 36, or alternatively as part of the sheet 38 or the binder 40. Alternatively, the scavenger material 32 is included as a separate lamina in the layered structure of the article 23 and / or the component or lamination in the sheet 24 and / or the binder 26 of the article 23. May be included as me. The barrier layer 20 of the article 36 may be any of the barrier layers 20 disclosed herein, or alternatively be formed from a material selected from polymers, cellulosic materials, nonwoven materials, or metallized films. It may be. The scavenger material 32 in the article 36 includes zeolites, mesoporous zeolites, high surface area carbon blacks, DGB carbon blacks, polycationic molecules, polyvinylpyrrolidone polymers and copolymers, cyclodextrin compounds, activated carbon, cationic carbons, Cationic inert materials, anionic materials, magnesium oxide, activated alumina, mixed metal oxides, nanoparticles of metal oxides, coconut carbon, wood carbon, carbon nanotubes, carbon nanofibers, ion exchange resins, dye transfer inhibitors, and these A material selected from blends, blends or mixtures of materials.

The present invention indicates that the article 36 may include the barrier layer 20 (FIG. 1), the trapping agent material 32 (FIG. 2), and the neutralizer 46 (FIG. 3) in any possible permutation or combination. Consider. Thus, the barrier layer 20, the scavenger material 32 and / or the neutralizing agent 46 are individually acting collectively to reduce or prevent migration of the foreign agent 21 from the surface 16 to the sheet 38. You can also contribute. In some embodiments of the present invention, the individual contributions are not sufficient to independently achieve the desired prevention or reduction of the migration of the foreign agent 21, but in total the individual contributions may produce the desired effect. The present invention also provides more than one type of barrier layer 20, more than one type of scavenger material 32 and / or more than one to provide the desired desired prevention or reduction of the migration of the foreign agent 21. It is contemplated that tangible neutralizers 46 may be provided in combination.

The barrier layer 20 (FIG. 1), the scavenger material 32 (FIG. 2), or the neutralizer 46 (FIG. 3) is homogeneously or uniformly on the plane of the corresponding article 10, 23 or 36. It may be distributed. Alternatively, the barrier layer 20, scavenger material 32 or neutralizer 46 may have an amount or density of barrier layer 20, scavenger material 32 or neutralizer 46 across the horizontal plane of the article. It may be distributed in a heterogeneous pattern to have spatial dependence. For example, barrier layer 20, scavenger material 32, or neutralizer 46 may not be present in any article region, have a concentration or thickness gradient across the article's horizontal plane, or otherwise located within the article's horizontal plane. In other concentrations or thicknesses (ie, greater concentrations or thicknesses near the peripheral edges of the article), and the like. The concentration or thickness in the pattern may be adjusted systematically or randomly, and all areas of the horizontal plane of the article may not have a concentration or thickness of zero of the barrier layer 20, the scavenger material 32, or the neutralizer 46. It may be.

Color change / stability is measured according to the following procedure. Square samples with one side of 7.62 cm are provided. The sample is adhesively mounted on a rigid backing board while carefully removing air bubbles and wrinkles. Any top carrier layer or release liner is removed from the sample to expose the color layer.

Prepare a solid support plate as follows. A board made of drywall is provided. The plate was prepared by Behr Premium Plus PVA Drywall Primer & Sealer No. 73 is painted with commercially available primers such as those available from Behr Corporation as white latexes. Upon drying the plate is painted with a paint having a color of 49.3 grams / liter. Suitable paints include Behr, Premium Plus Interior Semi-Gloss Enamel Pastel Base no. It can be purchased from Versa as 3500. Painting may consist of synthetic wool rollers having a fluff of about 6.35 mm. The plate is placed on a horizontal surface and primed / painted until the surface has a uniform and homogeneous primer / paint coating. Allow 24 hours between coatings at 50% RH and 20 degrees Celsius. ASTM test method E1164 and color measurements for determination of rich color are determined in L.a.b. A baseline L * A * B colorimeter measurement of the sample is performed according to E308 for conversion to scale. The Minolta CM508d colorimeter with pulsed xenon arc lamp was found to be suitable by the following settings: 2 ° / C; SCE; 8 mm sample area. After baseline measurements are made, the samples are placed in a 60 degree Celsius test oven. Samples are removed every hour and tested again for L * A * B * as described above. The hourly test takes place until the recorded change in B * (called ΔB *) is less than 10% between successive measurements.

The article 10 according to the invention may have an opacity of at least 99, preferably at least 99.3 and more preferably at least 99.5 as measured according to ASTM standard D2805. Furthermore, such articles have less than 0.084 mm, preferably less than 0.076 mm, more preferably less than 0.064 mm, more preferably 0.05 when measured under a restraining load of 8.74 grams by a presser foot of 5 mm diameter. It may have a thickness of less than mm and more preferably less than 0.04 mm. The article 10 thus made will have an opacity to thickness ratio of at least 40, preferably at least 50 and more preferably at least 55 per mm.

Example  One

A solution of 10 grams of Hansa Yellow (monoazo) pigment and 2-propanol (IPA) was prepared. The peak was found on the absorbance curve of the 10 ppm solution using a spectrophotometer. The main absorption peak was observed at a wavelength of about 404 nm. All subsequent absorbance readings were made at 404 nm. The absorbance at 404 nm of 2, 4, 6, 8, and 10 ppm solutions was determined for the calibration curve. Various types of activated carbon (approximately 45-63 microns in diameter) were added to the 10 ppm solution and stirred continuously in a stir plate. Carbon free solution was used as a control. Aliquots were removed as samples after 30, 60 and 120 minutes. The sample was centrifuged to remove carbon and the absorbance was sampled using a spectrophotometer. The results are shown in FIG.

The top curve shows the absorption of the control and the bottom four curves show the absorption after the addition of various types of activated carbon. It is evident from FIG. 4 that the absorbance characterizing the 404 nm peak of the Hansa Yellow pigment is significantly reduced due to the presence of activated carbon in the solution. Specifically, the absorbance is reduced by the action of activated carbon by a coefficient of at least 5 and by one or more orders. In order from the lowest decrease in absorbance to the highest decrease in absorbance, the specific activated carbons in the solution are Midwestbacco SA-1500 wood-based activated carbon, wood-based activated carbon, coconut-based activated carbon, and Midwest-Barco RGC wood-based activated carbon, respectively.

Because of the high porosity levels, activated carbon is effective in absorbing Hansa yellow (monoazo) pigments. Although not shown in FIG. 4, it was observed that increasing the amount of carbon added to the solution increased the amount of yellow pigment removed from the solution. If the foreign agent is located between the color sheet and the surface to which the article is applied, the foreign agent must be effective in preventing migration of the foreign agent by acting as a trapping agent material. As a result, the color sheet will not discolor as activated carbon captures the migrating foreign agent before the foreign agent enters the color sheet.

36 additional samples were made and tested according to the procedure described above. The results are shown in Table 1 below.

All documents cited in the Detailed Description of the Invention are incorporated herein by reference in their entirety, and citation of any document should not be construed as an admission that this document is a prior art relating to the present invention.

While specific embodiments of the invention have been illustrated and described, it will be apparent to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the invention. Accordingly, all such changes and modifications that fall within the scope of the invention are intended to be included in the appended claims.

Claims (19)

An article for delivering visually recognizable color effects to surfaces Sheet for visually recognizable color effects, A binder held by the sheet to bond the sheet to the surface; And Polycationic molecules, polyvinylpyrrolidone polymers and copolymers, cyclodextrin compounds, activated carbon, cationic carbon, cationic inert materials, anionic materials, magnesium oxide, activated alumina, mixed metal oxides, nanoparticles of metal oxides, coconut carbon , Selected from wood-based carbon, carbon nanotubes, carbon nanofibers, ion exchange resins, dye transfer inhibitors, and combinations thereof, and acts to eliminate foreign agents, effective to reduce migration of foreign agents from the surface to the sheet. An article comprising a capture agent material. The article of claim 1, further comprising at least one of a barrier layer and a tie layer, wherein the trapping agent material is present in at least one of the sheet, the binder, the barrier layer, and the tie layer. 3. The method of claim 2, wherein at least one of the binder, the trapping agent material, and the sheet is zeolite, mesoporous zeolite, which interacts with the trapping agent material to reduce migration of foreign agent from the surface to the sheet, An article further comprising at least one of high surface area carbon black, and DGB carbon black. The article of claim 2, wherein at least one of the sheet and the binder comprises the scavenger material. The article of claim 1, wherein the trapping agent material is positioned as a layer between the sheet and the binder. 6. The article of claim 5, wherein said trapping agent material is activated carbon provided in a form selected from the group consisting of particles, fibers, nanotubes, inks, and combinations thereof. An article for delivering visually recognizable color effects to surfaces Sheets for visually recognizable color effects; And Neutralizer that acts to modify the foreign agent, effective to reduce migration of the foreign agent from the surface to the sheet Supplies comprising. 8. The article of claim 7, further comprising at least one of a barrier layer and a tie layer, wherein the neutralizer is present in at least one of the sheet, the bonding agent, the barrier layer, and the tie layer. The article of claim 8, wherein at least one of the sheet and the binder comprises the neutralizing agent. 8. The article of claim 7, wherein the neutralizing agent is positioned as a layer between the sheet and the binder. 8. The article of claim 7, wherein said neutralizer is selected from the group consisting of bleach compounds, optical brighteners, pH adjusters, and combinations thereof. 8. The article of claim 7, further comprising a trapping agent material that interacts with the neutralizing agent to reduce the migration of foreign agents from the surface to the sheet. The article of claim 7, further comprising a barrier layer that interacts with the neutralizer to reduce migration of foreign agents from the surface to the sheet. The article of claim 13, further comprising a trapping agent material that interacts with the neutralizing agent and the barrier layer to reduce the migration of foreign agents from the surface to the sheet. An article for delivering visually recognizable color effects, Includes sheets for visually recognizable color effects, Wherein the binder has a solubility in the foreign agent that is substantially different from the solubility of the foreign agent at the surface, wherein the difference in solubility is effective to reduce migration of the foreign agent from the surface to the sheet. A method of preventing and reducing discoloration of a layered article for delivering visually recognizable color effects to a surface, comprising the following steps: Providing a layered article for application to a surface; And Deforming the layered article by at least one of the following to reduce migration of the foreign agent from the surface to a portion of the layered article that provides a visually recognizable color effect: Adding a neutralizer to one or more layers of the layered article, Polycationic molecules, polyvinylpyrrolidone polymers and copolymers, cyclodextrin compounds, activated carbon, cationic carbon, cationic inert materials, anionic materials, magnesium oxide, activated alumina, mixed metal oxides, nanoparticles of metal oxides, coconut carbon Adding a scavenger material selected from the group consisting of wood-based carbon, carbon nanotubes, carbon nanofibers, ion exchange resins, dye transfer inhibitors, and combinations thereof to one or more layers of the layered article, and A barrier layer selected from the group consisting of glass-coated polymers, ceramic-coated polymers, sodium silicate-containing compositions, at least one of anionic and cationic layers, nanocomposites, and combinations thereof may provide visually recognizable color effects. Added to be placed between the surface and a portion of the layered article to provide. An article for applying an aesthetic effect to a surface, the article comprising a binder and a color element for bonding the article to the surface, wherein the opacity to thickness ratio exceeds 45. 18. The article of claim 17, wherein the opacity to thickness ratio is greater than 50. 19. The article of claim 18, wherein the opacity to thickness ratio is greater than 55.

Images