WO2015120212A1 - Paint color evaluation system that facilitates examination of color at multiple angles and locations on a vehicle - Google Patents

Paint color evaluation system that facilitates examination of color at multiple angles and locations on a vehicle Download PDF

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Publication number
WO2015120212A1
WO2015120212A1 PCT/US2015/014717 US2015014717W WO2015120212A1 WO 2015120212 A1 WO2015120212 A1 WO 2015120212A1 US 2015014717 W US2015014717 W US 2015014717W WO 2015120212 A1 WO2015120212 A1 WO 2015120212A1
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WO
WIPO (PCT)
Prior art keywords
color
matching
article
major surface
release liner
Prior art date
Application number
PCT/US2015/014717
Other languages
French (fr)
Inventor
Jeffrey R. Janssen
Deborah J. Eilers
Dan M. WITTEK
David A. HUEBL
Original Assignee
3M Innovative Properties Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 3M Innovative Properties Company filed Critical 3M Innovative Properties Company
Publication of WO2015120212A1 publication Critical patent/WO2015120212A1/en

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Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B44DECORATIVE ARTS
    • B44DPAINTING OR ARTISTIC DRAWING, NOT OTHERWISE PROVIDED FOR; PRESERVING PAINTINGS; SURFACE TREATMENT TO OBTAIN SPECIAL ARTISTIC SURFACE EFFECTS OR FINISHES
    • B44D3/00Accessories or implements for use in connection with painting or artistic drawing, not otherwise provided for; Methods or devices for colour determination, selection, or synthesis, e.g. use of colour tables
    • B44D3/003Methods or devices for colour determination, selection or synthesis, e.g. use of colour tables
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00Adhesives in the form of films or foils
    • C09J7/20Adhesives in the form of films or foils characterised by their carriers
    • C09J7/203Adhesives in the form of films or foils characterised by their carriers characterised by the structure of the release feature on the carrier layer
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00Adhesives in the form of films or foils
    • C09J7/20Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22Plastics; Metallised plastics
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00Adhesives in the form of films or foils
    • C09J7/30Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38Pressure-sensitive adhesives [PSA]

Definitions

  • Color-matching paint is an important step in the automobile repair process. It is also one of the most variable steps in the repair process. Typically, automobiles are assigned a paint color code by the manufacturer. This paint color code is often used by the paint formulator to generate an initial or starting point paint formulation. Starting point paint formulations can also be identified using spectrophotometric or paint variance techniques. While such process will approximately match the hue of a painted substrate, they have difficulty accommodating the metallic or pearlescent appearance of some automotive paints. Thus, the starting point paint formulations are typically not adequate matches, and the painter must evaluate paint colors to determine whether they are an adequate match to the vehicle.
  • Evaluation of the paint color is a critical step in the painting process. To make matters more difficult, the automotive paints are becoming thinner, less opaque and even more loaded with pearlescent and fine metallic components.
  • the metallic and pearlescent finishes have color that is highly dependent on the viewing angle and lighting, so a painter will have to evaluate the paint color for adequate match at these different viewing angle and lighting conditions.
  • many newer vehicles are made with body panels that are extremely thin and lightweight compared to body panels used in the past. These lighter panels typically have very sharp feature lines to make them more stable. When a painter paints over these sharp feature lines it is critical that the color matches at a variety of viewing angles.
  • painters use a printed board stock.
  • the paint is applied to the board stock, and the painted board stock is held by the painter in their hand or applied to a holder like a paint stick and held next to the car in an attempt to evaluate for match.
  • This board stock does not conform well to the surface and does not stay in intimate contact with the paint, making it difficult to evaluate the paint from different viewing angles, distances, and lighting conditions.
  • the board stock also has a thick edge, which demonstrates a small edge effect that can disrupt the viewing of the test sample.
  • the present disclosure is generally directed toward articles, systems, and methods that are adapted to accommodate color matching over two-dimensional compound surfaces, including sharp features and the use of metallic paints.
  • the articles and systems described herein are flexible, clean- removal, inexpensive, easy to use articles and systems that allow viewing of paint samples at multiple viewing angles, distances, and lighting conditions, and over sharp features, to guide the painter in a method of color-matching of a paint formulation to a target surface, such as a vehicle under repair.
  • the present disclosure provides a repositionable color-matching article comprising: a flexible substrate having a first major surface and a second major surface disposed opposite the first major surface; and
  • a pressure-sensitive adhesive layer disposed upon the second major surface of the substrate; wherein the adhesive layer comprises a clean removal adhesive.
  • the clean removal adhesive of the color-matching article of can be solvent resistant according to the Solvent Resistance Test and, in some embodiments, can comprise a silicone-free, urea-based adhesive.
  • the present disclosure provides a color-matching system comprising the color-matching articles described herein and a release liner; wherein the release liner comprises a base layer having a first major surface and a second major surface disposed opposite the first major surface; and
  • the adhesive layer of the color-matching article is releasably adhered to the first major surface of the release liner; and wherein the release liner comprises less than 0.5% silicone by weight.
  • the release liner of the color-matching system may optionally further comprise a varnish layer disposed on the first major surface of the base layer.
  • the release liner further comprises a pattern layer.
  • the release liner further comprises a second color layer.
  • the present disclosure provides a color-matching kit comprising the color- matching system and an applicator.
  • the kit further comprises a clear-coat- simulating article, a clear-coat formulation, or a clear-coat-simulating formulation.
  • the present disclosure provides a method of color-matching a paint formulation to a target surface having a color, the method comprising:
  • the method may further comprising any of the steps of:
  • the present disclosure provides a method of color-matching a paint formulation to a target surface having a color, the method comprising:
  • step (a) can further comprises applying the paint formulation over at least a portion of the release liner; and wherein the paint formulation adheres to the release liner.
  • the method can further comprise any of the steps of:
  • the release liner comprises a pattern layer, and the method further comprises:
  • the target surface comprises a surface topography, wherein the color-matching article conforms to the surface topography upon adhering the color- matching articles to a portion of the target surface with the adhesive layer.
  • the surface topography is non-planar.
  • color matching kits and systems according to the present disclosure comprise an air release structure.
  • Fig. 1A is a cross-sectional view of an embodiment of a color-matching article of the present invention.
  • Fig. IB is a cross-sectional view of an embodiment of a color-matching article of the present invention.
  • Fig. 2A is a cross-sectional view of an embodiment of a release liner of the present invention.
  • Fig. 2B is a cross-sectional view of an embodiment of a release liner of the present invention.
  • Fig. 2C is a cross-sectional view of an embodiment of a release liner of the present invention.
  • Fig. 2D is a cross-sectional view of an embodiment of a release liner of the present invention.
  • Fig. 2E is a cross-sectional view of an embodiment of a release liner of the present invention.
  • Fig. 3 is a cross-sectional view of an embodiment of a color-matching system of the present invention.
  • Fig. 4 is a top view of an embodiment of a color-matching system of the present invention.
  • Fig. 5A is a perspective view showing a painter applying a paint formulation to an embodiment of a color-matching article of the present invention.
  • Fig. 5B is a perspective view showing a painter adhering a color-matching article of the present invention to a target surface for color match comparison.
  • Fig. 6A is a perspective view showing a painter applying a paint formulation to an embodiment of a color-matching system of the present invention.
  • Fig. 6B is a perspective view showing a painter removing a color-matching article of the present invention from a release liner of the present invention.
  • Fig. 6C is a perspective view showing a painter adhering a color-matching article of the present invention to a target surface for color match comparison.
  • Fig. 7 is a schematic side view of an exemplary embodiment of a color match system comprising an air release structure according to the present disclosure.
  • Fig. 8 is a schematic side view of an exemplary embodiment of a color match article comprising an air release structure according to the present disclosure.
  • Figs. 9-1 1 are schematic side views of exemplary embodiments of a release liner comprising an air release structure according to the present disclosure.
  • Fig. 12 is a plan view of an exemplary air release structure comprising a random dot pattern according to the present disclosure.
  • Fig. 13 is a plan view of an exemplary air release structure comprising a regular offset row dot pattern according to the present disclosure.
  • Figs. 14-16 are plan views of exemplary air release structures comprising a square cross hatch pattern according to the present disclosure.
  • Fig. 17 is a plan view of an exemplary air release structure comprising a regular offset row dot pattern according to the present disclosure.
  • Fig. 18 is a plan view of an exemplary air release structure comprising abrasions according to the present disclosure.
  • Figs. 1A-1B depict cross sections of a color-matching article 100 of the present invention.
  • the color-matching article 100 comprises a flexible transparent substrate 1 10 having a first major surface 1 1 1 and a second major surface 1 12 disposed opposite the first major surface 1 1 1.
  • a pressure-sensitive adhesive layer 120 is disposed upon the second major surface 1 12 of the substrate 110.
  • an optional first color layer 130 may be disposed upon the first major surface 1 1 1 of the substrate 110.
  • the color-matching articles may be paired with a release liner to comprise a color-matching system.
  • Figs. 2A-2E depict some illustrative embodiments of release liners as described herein.
  • the release liner 200 comprises a base layer 210 having a first major surface 21 1 and a second major surface 212 opposite the first major surface.
  • the first major surface 21 1 of the base layer 210 is non-primed.
  • the second major surface 212 of the base layer 210 is primed.
  • the release liner 200 optionally further comprises a varnish layer 220 disposed on the first major surface 21 1 of the base layer 210.
  • the release liner 200 may further comprise a pattern layer 230, as in Figs. 2B-2E.
  • the pattern layer 230 may be disposed on at least a portion of the first major surface 21 1 of the base layer 210, as in Figs. 2B and 2D. In such embodiments, the pattern layer 230 is therefore disposed between at least a portion of the base layer 210 and at least a portion of the optional varnish layer 220.
  • the pattern layer 230 may be disposed on at least a portion of the second major surface 212 of the base layer 210, as in Figs. 2C and 2E.
  • the release liner 200 may further comprise a second color layer 240 disposed on the second major surface 212 of the base layer 210, as in Figs. 2D and 2E.
  • the pattern layer 230 may be disposed between at least a portion of the second color layer 240 and the second major surface 212 of the base layer 210.
  • a color-matching article of the present invention and a release liner of the present invention are paired to create a color-matching system.
  • Fig. 3 depicts an illustrative embodiment of a color-matching system 300 as described herein, comprising color-matching article 100 and release liner 200.
  • color-matching article 100 comprises substrate layer 1 10 having a first major surface 1 1 1 and a second major surface 1 12 opposite the first major surface 1 1 1, and adhesive layer 120 disposed on the second major surface 1 12 of substrate 1 10.
  • color-matching article 100 further comprises optional first color layer 130 disposed on the first major surface 11 1 of substrate 1 10.
  • release liner 200 comprises base layer 210 having a first major surface 21 1 and a second major surface 212 opposite the first major surface 21 1, and optional varnish layer 220 disposed on the first major surface 211 of base layer 210.
  • release liner 200 further comprises optional pattern layer 230 disposed on the first major surface 21 1 of base layer 210, between optional varnish layer 220 and the first major surface 21 1 of base layer 210.
  • release liner 200 further comprises optional second color layer 240 disposed on the second major surface 212 of base layer 210.
  • the adhesive layer 120 of color- matching article 100 is releasably adhered to optional varnish layer 220 or the first major surface 21 1 of release liner 200.
  • Fig. 4 depicts a top view of an embodiment of a color-matching system 300 of the present invention, comprising color-matching article 100 releasably adhered to release liner 200.
  • release liner 200 may comprise pattern layer 230, which is visible though color- matching article 100.
  • the edges 201 of release liner 200 extend beyond the edges 101 of color-matching article 100.
  • the color-matching articles of Figs. 1A-1B are used in a method of color-matching a paint formulation according to the present invention.
  • a paint formulation to be color-matched to a target surface is first applied over at least a portion of the color-matching article 100.
  • the paint formulation is applied over at least a portion of the first major surface 1 1 1 of the substrate 1 10 of the color-matching article 100.
  • the color-matching article 100 further comprises a first color layer 130 disposed on the first major surface 1 1 1 of the substrate 1 10, as in Fig. IB, the paint formulation is applied over at least a portion of the first color layer 130.
  • the paint formulation may be initially formulated, for example, with reference to paint codes that are provided with an automobile or other target surface, or with reference to color samples that are provided by various paint suppliers.
  • the methods described herein can be used to match metallic and pearlescent paints, as well as non-metallic paints.
  • the paint formulations may be solvent- based or water-based paint formulations.
  • Fig. 5A shows application of paint formulation 42 over the first major surface 1 1 1 of the substrate 1 10 of color-matching article 100 by painter 40 using a pressurized spray gun 41 to form paint layer 42a. It is to be understood that paint formulation 42 may be applied to the color-matching article using any known techniques, including, for example, with a paint roller or paintbrush.
  • the paint layer 42a is then allowed to dry.
  • the painted color-matching article 100a is then adhered to a portion of the target surface with the adhesive layer 120.
  • Fig. 5B shows painter 40 adhering the painted color-matching article 100a to target surface 43.
  • the color-matching article 100/100a conforms to the surface topography of the target surface upon adhering the color-matching article 100/100a to a portion of the target surface 43 with the adhesive layer.
  • the painter or other individual assessing the match of the paint formulation to the target surface assesses the match by comparing the paint formulation on the color-matching article to the target surface and determining whether the paint formulation on the color-matching article closely matches the color of the target surface. Because the color-matching article is adhered to the target surface and can conform to non-planar surface topography, the painter or other individual assessing the match of the paint formulation to the target surface can move around in order to view the paint formulation from multiple distances, viewing angles, and lighting conditions. It may also be desirable to view the painted color-matching article on the target surface under more than one lighting condition such as, for example, artificial light and sunlight.
  • the target surface is an automotive vehicle or vehicle part
  • it may be desirable to simulate a clear coat by adhering a clear-coat-simulating article or applying a clear-coat formulation or clear-coat-simulating formulation over the color-matching article on the target surface prior to assessing the match of the paint formulation to the target surface then assesses the match by comparing the paint formulation on the color-matching article to the target surface and determining whether the paint formulation on the color-matching article closely matches the color of the target surface.
  • Any clear-coat formulation or clear-coat-simulating formulation may be applied, such as, for example, clear-coat spray formulations, solvents that wet the surface and provide a temporary high gloss, clear-coat-simulator sprays, and the like.
  • Any clear- coat-simulating article known in the art may be used, such as, for example, a film/adhesive laminate that simulates a clear coat, or those described in US 6,995,843.
  • some embodiments of the color-matching article described herein can be used as a clear-coat-simulating article. For example, color-matching article 100 shown in Fig.
  • the clear-coat-simulating article may be applied to the painted color-matching article prior to adhering the painted color-matching article to the target surface.
  • the clear-coat-simulating article may be applied to the painted color-matching article after applying the painted color-matching article to the target surface, while the painted color- matching article is adhered to the target surface.
  • Adhesive bonding of the clear-coat-simulating article to the painted color-matching article may be assisted, for example, by used of a hand-held roller, squeegee, or a portable lamination device available under the trade designation "XYRON 510" (Part Number XR 510ATPS) from Xyron, Inc. (Scottsdale, Ariz.).
  • the painted color-matching article After determining whether the paint formulation on the color-matching article closely matches the color of the target surface, the painted color-matching article is removed from the target surface. Upon removal, the paint formulation can be applied directly to the target surface without problems such as low adhesion of the paint formulations, orange-peel texture, color changes, non- wetting, and other surface anomalies, according to the Contamination Test described in the
  • low-surface-energy components such as silicones, fluorochemicals, and polyolefins
  • no low-surface-energy components such as silicones, fluorochemicals, and polyolefins, remain on the target surface after removal of the color-matching article from the target surface. If the paint formulation matched sufficiently, the painter can now paint the target surface with the final formulation.
  • the match was insufficient, or if the painter or other individual assessing the match of the paint formulation wishes to assess another paint formulation for match, it may be desirable to repeat the method described above with the same color-matching article 100/100a, or with a different color-matching article, in order to provide an improved color-matched paint formulation.
  • the color- matching articles described herein can be re -used. For example, the method steps can be repeated, and at least a portion of the painted color-matching article can be repainted. The color-matching article can then be re-adhered to the target surface.
  • the color-matching systems of Figs. 3-4 may be used.
  • a paint formulation to be color-matched to a target surface is first applied over at least a portion of the color-matching article 100 on color-matching system 300.
  • the paint formulation is applied over at least a portion of the first major surface 1 1 1 of the substrate 1 10 of the color-matching article 100.
  • the paint formulation is also applied over at least a portion of the first major surface or the optional varnish layer of the base layer of the release liner, for example, where the edges 201 of release liner 200 extend beyond the edges 101 of release liner 100 (Fig. 4).
  • the color- matching article 100 further comprises a first color layer 130 disposed on the first major surface 1 1 1 of the substrate 1 10, as in Fig.
  • the paint formulation is applied over at least a portion of the first color layer 130.
  • Fig. 6A shows application of paint formulation 42 over the first color layer 130 disposed on the first major surface 1 11 of the substrate 110 of color-matching article 100 releasably adhered to optional varnish layer 220 of release liner 200 by painter 40 using a pressurized spray gun 41 to form paint layer 42a.
  • the paint formulation 42 is also applied over at least a portion of the first major surface 21 1 or the optional varnish layer 220 of the base layer 210 of the release liner 200. It is to be understood that paint formulation 42 may be applied to the color-matching article using any known techniques, including, for example, with a paint roller or paintbrush.
  • the paint layer 42a is then allowed to dry.
  • the painted color-matching article 100a is then removed from release liner 200 and adhered to a portion of the target surface with the adhesive layer 120.
  • Fig. 6B shows painter 40 removing painted color-matching article 100a is then removed from release liner 200.
  • Fig. 6C shows painter 40 adhering the painted color-matching article 100a to target surface 43.
  • the color-matching article 100/ 100a conforms to the surface topography of the target surface upon adhering the color-matching article 100/100a to a portion of the target surface 43 with the adhesive layer.
  • the painter or other individual assessing the match of the paint formulation to the target surface assesses the match by comparing the paint formulation on the color-matching article to the target surface and determining whether the paint formulation on the color-matching article closely matches the color of the target surface.
  • painters need to assess coverage of the paint formulations in addition to color match. Sufficient coverage means the paint formulation has been applied in a fashion where influence from the color of the target surface is minimized.
  • the pigments in the paint formulations are not opaque but are relatively transparent.
  • application of enough paint to provide complete coverage is cost prohibitive, so instead the color of the target surface (e.g. with a primer), is used to influence the final color appearance of the paint formulation applied on the target surface.
  • the color of the primer is controlled and is critical in achieving the color of such translucent coatings. To assist in this the painter can apply the specific primer as the first layer in the paint combination.
  • the color-matching articles described herein can, in some embodiments, be supplied pre-colored with one or more of the common primer colors for the desired use.
  • the method includes the step of assessing visibility of the pattern layer 230 through the paint layer to assess paint coverage.
  • the painter or other individual assessing the match of the paint formulation can also assess coverage of the paint formulation by viewing release liner 200 after removing the painted color-matching article 100a from release liner 200.
  • release liner 200 includes pattern layer 230, and may or may not include second color layer 240.
  • the edges 201 of release liner 200 extend beyond the edges 101 of color-matching article 100 in the color-matching system 300.
  • painter 40 applies paint formulation to the color- matching system, the paint formulation is applied both to at least a portion of the color-matching article 100 and the release liner 200.
  • the unpainted portion of release liner 200 including the portion of pattern layer 230 that is not concealed by the paint formulation, will be visible.
  • the painter or other individual assessing the match and coverage of the paint formulation can compare the painted portion of the release liner to the unpainted portion of the release liner to determine whether the formulation provides adequate coverage over pattern layer 230.
  • the painter or other individual assessing the match of the paint formulation would then assesses the match by comparing the paint formulation on the color-matching article to the target surface and determining whether the paint formulation on the color-matching article closely matches the color of the target surface.
  • Any clear-coat formulation or clear-coat-simulating formulation may be applied, such as, for example, clear-coat spray formulations, solvents that wet the surface and provide a temporary high gloss, clear-coat-simulator sprays, and the like.
  • Any clear-coat-simulating article known in the art may be used, such as, for example, a film/adhesive laminate that simulates a clear coat, or those described in U.S. Pat. No. 6,995,843.
  • some embodiments of the color-matching article described herein can be used as a clear-coat-simulating article, for example, color-matching article 100 shown in Fig. 1A, without the optional first color layer, can be used as a clear-coat-simulating article.
  • color-matching article 100 may be placed over painted color-matching article 100a in order to simulate the appearance of a clear coat.
  • the painted color-matching article is removed from the target surface.
  • the paint formulation can be applied directly to the target surface without problems such as low adhesion of the paint formulations, orange-peel texture, color changes, non- wetting, and other surface anomalies, according to the Contamination Test described in the Examples below.
  • only trace amounts of low-surface-energy components such as silicones, fluorochemicals, and polyolefins, remain on the target surface after removal of the color-matching article from the target surface.
  • no low-surface-energy components such as silicones, fluorochemicals, and polyolefins, remain on the target surface after removal of the color-matching article from the target surface. If the paint formulation matched sufficiently, the painter can now paint the target surface with the final formulation. If the match was insufficient, or if the painter or other individual assessing the match of the paint formulation wishes to assess another paint formulation for match, it may be desirable to repeat the method described above with the same color-matching article 100/100a, or with a different color-matching article, in order to provide an improved color-matched paint formulation. In addition, repetition of the method may optionally include re-assessing paint coverage based on pattern layer 230, as described above.
  • the color-matching articles and systems described herein can be supplied as part of a color- matching kit.
  • the color-matching kit includes one or more color-matching articles as described herein and an applicator.
  • the color-matching kit includes one or more color-matching systems as described herein and an applicator.
  • the color-matching kit may also contain a clear-coat-simulating article, a clear-coat formulation, or a clear-coat-simulating formulation, as described above.
  • the applicator may be used to ensure smooth coverage of the color-matching article to the substrate, of the color-matching article to the release liner for re-use or cataloguing, of the clear-coat-simulating-article to the painted color-matching article, or combinations thereof.
  • the applicator may assist in removing bubbles that form under the color-matching article on the target surface, between the clear-coat-simulating article and the painted color-matching article, or between the color-matching article and the release liner when the color-matching article is placed back on the release liner for re -use or cataloguing.
  • Any applicator known in the art and capable of smoothing the color-matching articles and clear-coat- simulating articles described herein may be used.
  • the applicator is a squeegee or a roller.
  • the color-matching articles and systems of the present invention may be catalogued for later reference or reuse.
  • the color-matching articles have a first major surface and a second major surface and typically comprise a transparent substrate, though non-transparent substrates may be used, in some embodiments, the substrate comprises a polymer film.
  • the polymer film comprises polyester, polycarbonate, acrylic, polyurethane, polyolefin, ethylene vinyl acetate, biaxially-oriented polypropylene, polyvinyl chloride, polystyrene, urethane acrylate, epoxy, epoxy acrylate, and blends thereof.
  • the adhesive comprises a silicone-free urea- based adhesive prepared by the polymerization of reactive oligomers with the general formula X-B- X wherein X is an ethylenically unsaturated group and B is a unit free of silicone and containing urea groups.
  • the reactive oligomers can be prepared from polyamines through chain extension reactions using diaryl carbonates followed by capping reactions with acrylates.
  • the substrate is transparent and achromic (i.e. colorless).
  • the color-matching articles further comprise a pressure-sensitive adhesive layer disposed upon the second major surface of the substrate.
  • the adhesive layer can consist of many different types of pressure-sensitive adhesive materials including acrylic based adhesives which are prepared via a thermally cured process, a UV initiated process or an e-beam curing process.
  • the acrylic can be solvent-based, water-based or 100% solids.
  • the acrylic adhesive could be in the form of a continuous film or it could be in the form of a film with separate phases where the adhesive contains discrete phases such as a microsphere of adhesive within the adhesive film.
  • the resultant adhesive can optionally be crosslinked after coating using common crosslinking techniques such as UV- initiated crosslinking of the polymer, crosslinking via an interpenetrating network around the base polymer, and thermally crosslinking the acrylic polymer using azirdine or isocyanate containing compounds.
  • Crosslinking can also be generated via ionic methods using compounds of zinc, lithium or sodium to associate with ionic portions of the adhesive.
  • the adhesive layer can comprise a rubber material including thermoplastic rubbers, block copolymers or natural rubbers.
  • the rubbers can include polyolefins which can include polymers of ethylene vinyl acetate, poly-alpha olefins (C3-C10), copolymers or blends of poly-alpha olefins with ethylene or propylene based polymers.
  • Poly isobutylene adhesives are common in this category.
  • the rubber adhesives can be solvent-based, water-based or 100 % solids.
  • the rubber-based adhesives can optionally be crosslinked for enhanced properties.
  • the adhesive layer may be a urethane or urea-based adhesive, such as, for example, those described in WO2010132176 Al .
  • the pressure sensitive adhesive layer may be blended with oils, plasticizers, non-pressure sensitive adhesive polymers, tackifiers, stabilizers, pigments, or fillers.
  • stablizers include thermal stabilizers such as antioxidants or hindered amine stabilizers.
  • the stabilizer can also include materials that help resist the effects of UV light.
  • the adhesive is typically a clean-removal adhesive.
  • clean removal adhesive it is meant that when the color-matching articles described herein are removed from the target surface, paint formulation can be applied directly to the target surface without problems such as low adhesion of the paint formulations, orange-peel texture, color changes, non- wetting, and other surface anomalies. Clean removal adhesives can be determined according to the Contamination Test described in the examples below.
  • the color matching articles, systems, or any component thereof contain no more than 0.5% by weight of silicones, fluorochemical, and polyolefins.
  • the color matching articles, systems, or any component thereof contain no deliberately-added low-surface-energy components such as silicones, fluorochemicals, or polyolefins. In some embodiments, the color matching articles, systems, or any component thereof, contain trace or nominal levels of low-surface-energy components such as silicones, fluorochemicals, and polyolefins. In some embodiments, the color matching articles, systems, or any component thereof, are essentially free of or contain no low- surface- energy components such as silicones, fluorochemicals, and polyolefins. In some embodiments, the color matching articles, systems, or any component thereof, contain no deliberately-added low-surface-energy components such as silicones, fluorochemicals, or polyolefins. In some embodiments, the color matching articles, systems, or any component thereof, contain trace or nominal levels of low-surface-energy components such as silicones, fluorochemicals, and polyolefins. In some embodiments, the color matching articles, systems, or any component thereof, are
  • fluorochemicals, and polyolefins remain on the target surface after removal of the color-matching article from the target surface.
  • no low-surface-energy components such as silicones, fluorochemicals, and polyolefins, remain on the target surface after removal of the color- matching article from the target surface.
  • plasticizers may be present in the color-matching articles and can transfer to the target surface without interfering with the adhesion or appearance of the intended application of the paint formulation.
  • the adhesive is solvent resistant according to the Solvent Resistance Test described in the examples below. It has been found that certain pressure sensitive adhesives cannot withstand the wax and grease remover solvents used to prep target surfaces, particularly target surfaces in the automotive industry, and will therefore be unable to adhere to the target surface. It has also been found that certain pressure sensitive adhesives cannot withstand the solvents used in clear-coat simulation as described above. Solvent resistance may be achieved by choosing the correct input polymer or crosslinking the polymer to enhance or effectively increase the molecular weight. Alternatively a solvent resistant base polymer can be used. The base polymer can be encompassed by an interpenetrating network of a pressure-sensitive adhesive that is crosslinked to itself and to the base polymer.
  • the adhesive is self-wetting.
  • self wetting refers to an adhesive which is very soft and conformable and is able to be applied with very low lamination pressure.
  • Such adhesives exhibit spontaneous wet out to surfaces.
  • the adhesives exhibit great conformability permitting them to spontaneously wet out substrates.
  • the surface characteristics also permit the adhesives to be bonded and removed from the substrate repeatedly for repositioning or reworking.
  • the color matching article and/or the release liner may comprise an air release structure 320.
  • the topography of the air release structure 320 may comprise any structure suited to provide sufficient air egress.
  • the air release structure may be formed by abrasion to create a roughened surface sufficient to allow the desired air egress.
  • the air release structure may comprise a plurality of discrete protrusions 330 extending normally from the surface upon which it is disposed, with the plurality of protrusions 330 being separated by one or more discrete air passages 340.
  • the air release structure comprises discrete protrusions 330
  • they may take any suitable form or shape, so long as they are separated by one or more air passages 340 in a manner sufficient to effectively release air from the interface between the color matching article and the underlying surface.
  • the protrusions 330 may comprise raised dots, raised polygons, raised irregular shapes, microrep Heated patterns, or combinations thereof.
  • the protrusions 330 may be distributed uniformly, in a repeating pattern, randomly, or combinations thereof.
  • discrete protrusions 330 can extend a feature height "D" from the surface from which they protrude.
  • discrete protrusions may comprise a feature size "A,” a center-to-center feature spacing "B,” and a feature-to-feature spacing "C.”
  • the feature size "A" is determined as an effective diameter (shown as a dotted line).
  • effective diameter means the diameter of a theoretical circle having the same area as the actual shape. For example, for a square having a side length of 1 cm and an area of 1 cm 2 , the effective diameter of that square would be 1.128 cm. An effective diameter can be calculated for any shape and is not limited to squares. In some embodiments, such as the random or regular offset row dot patterns shown in Figures 12 and 13, spacing between adjacent features - whether center-to-center ("B") or feature -to- feature ("C”) may not be uniform, and thus an average of these dimensions can be used.
  • the protrusions 330 of the air release layer may be created by any suitable method.
  • a smooth surface may be modified (such as by compression or material removal) to create one or more air passages 340 recessed therein, thereby effectively resulting in protrusions 330 between the recessed air passages 340.
  • discrete protrusions 330 may be formed on a smooth surface by methods such as screen printing, electrographic printing, offset printing, flexographic printing, gravure printing, inkjet printing, or thermal mass transfer printing.
  • a formable material may be coated onto a smooth surface and subsequently embossed with a tool to create protrusions 330 in the formable material.
  • protrusions 330 are formed from a different or independent material from the underlying major surface (i.e., where material is added to create the protrusions 330), the protrusions 330 may be formed from, for example, a resin or an ink.
  • the adhesive may comprise an air release structure. Adhesive topography or structure can be controlled using microreplication techniques such as in U.S. Pat. No. 6,91 1,243.
  • the relative size and height of the protrusions 330, as well as the pattern and spacing (i.e., by air passages 340) may be chosen such that effective air removal is achieved.
  • a color matching article can inherit the pattern of the protrusions 330.
  • a more deformable color matching article e.g., formed from a thinner, more flexible material may increase the severity of this phenomenon, and thereby tolerate lesser protrusion spacing and height.
  • the following exemplary air release structure dimension ranges - selected in appropriate combinations - may be desirable: Feature Size "A” (300 ⁇ to 1800 ⁇ ); Center-to-Center Feature Spacing "B” (500 ⁇ to 1900 ⁇ ); Feature -to-Feature Spacing "C” (20 ⁇ to 1200 ⁇ ); Feature Height “D” (1 ⁇ to 60 ⁇ ).
  • the following exemplary air release structure dimension ranges - selected in appropriate combinations - may be desirable: Feature Size "A” (300 ⁇ to 1800 ⁇ ); Center-to- Center Feature Spacing "B” (500 ⁇ to 1 100 ⁇ ); Feature-to-Feature Spacing "C” (30 ⁇ to 300 ⁇ ); Feature Height “D” (1.5 ⁇ m to 30 ⁇ ). Choice of dimensions will depend on, for example, the degree of pattern transfer - if any - that is allowable.
  • the air release structure comprises the following exemplary air release structure dimension ranges: Feature Size "A” (300 ⁇ to 800 ⁇ ); Center-to-Center Feature Spacing "B” (500 ⁇ to 800 ⁇ ); Feature-to-Feature Spacing "C” (30 ⁇ to 100 ⁇ ); Feature Height “D” (1.5 ⁇ m to 10 ⁇ ).
  • the air release structure comprises the following exemplary air release structure dimension ranges: Feature Size "A” (500 ⁇ to 700 ⁇ ); Center-to- Center Feature Spacing "B” (500 ⁇ to 800 ⁇ ); Feature-to-Feature Spacing "C” (40 ⁇ to 80 ⁇ ); Feature Height “D” (2 ⁇ m to 8 ⁇ ).
  • Feature Size "A” 500 ⁇ to 700 ⁇
  • Center-to- Center Feature Spacing "B” 500 ⁇ to 800 ⁇
  • Feature-to-Feature Spacing "C” 40 ⁇ to 80 ⁇
  • Feature Height "D” (2 ⁇ m to 8 ⁇ .
  • Examples A-F release liners made according to Release Surface RS-3 herein were utilized, except that the film thickness was 6.9 mil (175.3 ⁇ ). A structure was created on the back side (the second major surface) of the release liners. The "back” is defined as the rear of the film having reverse printing.
  • the color-matching articles used in Examples A-F comprised a film made according to CFA- 1 herein.
  • Dot patterns were printed on the back of the sample articles via hand spreads.
  • 3M Scotch MagicTM Tape (Cat. 810) loops were made and placed on the face side of the article.
  • the articles were placed face side down and secured to the coated side of a 12 inch (30 cm) by 20 inch (51 cm) piece of C-weight olive brown paper with the tape loops, obtained from Wausau Paper Company, Wausau, WI, subsequently saturated with a styrene -butadiene rubber, in order to make it waterproof.
  • a framed stencil or mesh was placed over the article.
  • the article was cured by passing the panel once through a UV processor, available from American Ultraviolet Company, Murray Hill, New Jersey, using two V-bulbs in sequence operating at 400 W/inch (157.5 W/cm) and a web speed of 58ft/min (17.68 m/min), corresponding to a total dose of approximately 510 mJ/cm 2 .
  • a UV processor available from American Ultraviolet Company, Murray Hill, New Jersey
  • Example A was created utilizing a 3 mil (76.2 ⁇ ) thick polyester stencil having a regular pattern of offset rows of 0.015 inch (0.038 cm) diameter holes spaced apart on 0.305 inch (0.775 cm) centers.
  • exemplary regular patterns of offset rows of dots spaced apart on known centers are depicted in Figures 13 and 17.
  • Example B was created utilizing a 1 mil (25.4 ⁇ ) thick stainless steel stencil with 0.030 inch (.076 cm) diameter holes randomly spaced. For reference, a exemplary randomly spaced dot distribution is depicted in Figure 12.
  • Example C was created utilizing a 305 mesh having a regular pattern of offset rows of 0.012 inch (0.031 cm) diameter holes spaced apart on 0.0265 inch (0.0673 cm) centers.
  • Example D was created via abrading the back of the article, by hand, with a maroon 3M ScotchbriteTM pad, back and forth five times with sufficient pressure to create a unidirectional pattern of abrasions.
  • a schematic representation of a unidirectional pattern of abrasions is depicted in Figure 18.
  • Rz is determined by calculating the arithmetic average of the magnitude of the departure (or distance) of the five tallest peaks of the profile from the meanline and by calculating the average of the magnitude of the departure (or distance) of the five lowest valleys of the profile from its meanline. These two averages are then added together to determine Rz.
  • Ra is the arithmetic mean of the magnitude of the departure (or distance) of the profile from its meanline. Both Rz and Ra were measured in three places on each of two replicates using a profilometer, available under the trade designation "SURTRONIC 3+ PROFILOMETER” from Taylor Hobson, Inc., Sheffield, England. The length of scan was 0.03 inches (0.0762 centimeters). For puroposes of the examples herein, Rz was used for Feature Height "D.”
  • Example E was created using 3M Super 77TM Multi Purpose Spray Adhesive to attach an embossed liner, which has a cross hatch pattern, to the back of the article.
  • the dimensions of the cross hatch pattern of Example E are listed in Table I.
  • Exemplary cross hatch patterns (in this case squares) are schematically depicted in Figures 14-16. The liner was applied, starting at the leading edge, using a hand roller to ensure smooth attachment.
  • Example F was created using 3M Super 77TM Multi Purpose Spray Adhesive to attach a film, which has a cross hatch pattern, to the back of the article.
  • the film was applied, starting at the leading edge, using a hand roller to ensure smooth attachment.
  • Examples G-D' a 6.9 mil (175.3 ⁇ ) polyester film, primed on one surface with an ink-receptive layer was utilized.
  • a structure was created on the back side (the second major surface) of the film by using a flexographic printing process.
  • a flexographic printing plate with a four up pattern was utilized to create four patterns simultaneously. The four patterns are listed in Table II below.
  • the printed films were sheeted into 7.5 inch by 10 inch sheets each containing two of the four patterns. These sheets were then subjected to the six different coating conditions ("Trials") according to Table III below.
  • the feature height was subsequently measured in the laboratory using an automated micrometer (Precision Micrometer Model #49-60 manufactured by TESTING MACHINES, INC., Amityville, NY).
  • BCM refer characteristics of an Anilox roll used to transfer ink from an ink reservoir to a flexographic printing plate, as would be known to those skilled in the art of flexographic printing.
  • Anilox Screen Count refers to the number of cells per linear inch (“LPI”). Screen count is measured at the angle of engraving, and can be provided in a range from, for example, 50 LPI to 1200 LPI.
  • Anilox Cell Volume refers to the volume of one cell in units of billionth cubic microns (“BCM").
  • the white ink used in Trials 1 -3 was NUVAFLEW 34 SERIES OPAQUE PRIME WHITE, Product Code 3405, available from ZELLER GMELIN RPrNTING INKS of Richmond, Virginia.
  • any coating material could be used to provide sufficient air egress and lack of pattern transfer.
  • Different coating materials may be selected to provide or avoid other characteristics.
  • the tactile varnish used in Trials 4-6 imparted a tactile stickiness or friction to the air release structure such that the samples, when stacked upon one another (as they might be for packaging purposes), did not readily slide relative to one another. This characteristic may be beneficial in some applications, or may not be desired in others. It is anticipated that a user could choose the coating material according to their particular need. Table II.
  • Example D did not exhibit sufficient air egress, other abraded examples were created and exhibited sufficient air egress without causing pattern transfer.
  • samples of the same film as used for Example D were abraded, measured to have an Rz (Feature Height "D") in a range from 1 1.4 ⁇ to 32.2 ⁇ , and were found to exhibit sufficient air egress and lack of pattern transfer when testing with a CFA-1 color match article.
  • the color-matching article can optionally comprise a first color layer disposed on the first major surface of the substrate.
  • the first color layer can comprise one or more layers of ink or primer coatings.
  • the first color layer comprises a white or gray ink printed onto the first major surface of the substrate.
  • the inks and primers can be solvent-based, water-based or 100 % solids.
  • the inks and primers are free of contaminants or flow control additives that can influence the wet-out of paint on the surface of the first color layer or adhesion of paint onto the surface of the first color layer, e.g.
  • the inks may comprise minor amounts, for example, less than 0.5% by weight, of these contaminants.
  • the inks and primers contain no deliberately- added low-surface-energy components such as silicones, fluorochemicals, or polyolefins.
  • the inks or primers contain trace or nominal levels of low-surface-energy components such as silicones, fluorochemicals, and polyolefins.
  • the color-matching articles can be supplied as pre-colored films that are colored with typical primer colors for the desired end use.
  • colors for the ink or primer layers include white, light gray (Pantone PMS 421), medium gray (Pantone PMS 423), and dark gray (Pantone PMS 425).
  • Exemplary printing inks can be obtained from Zeller-Gmelin Printing Inks (Germany) and Flint Group (USA).
  • the color-matching article has a total average edge thickness (i.e. the combined thickness of the substrate, the adhesive layer, and any optional layers, including the first color layer) ranging from 1.0 to 12.0 mils (25.4 ⁇ to 304.8 ⁇ ). In some embodiments, the color- matching article has a total an average edge thickness of 10 mil or less, such as 9 mil or less, 8 mil of less, 7 mil or less, 6 mil or less. This edge thickness allows better assessment of the paint formulation by avoiding edge effects caused by thicker articles. The edge thickness may be measured by any suitable method such as, for example, using thickness gauges.
  • the color-matching articles of the present invention are flexible such that they are capable of conforming to two dimensional compound surfaces (e.g., surfaces with non-planar surface topography). In some embodiments, the color-matching articles are flexible enough to conform to contours of the target surface. Color-matching articles having sufficient flexibility to conform to two-dimensional compound surfaces and the contours of the target surface include color-matching articles having a drape of 3 inches (7.62 cm) or less according to the Flexibility Test described in the Examples below.
  • the color-matching articles of the present invention can be releasably adhered to a release liner as part of a color-matching system.
  • the release liners described herein comprise a base layer.
  • the base layer can comprise a paper, a film, or a composite of a paper and a film.
  • the base layer provides the rigidity needed for the method of application. For example when a spray technique is used to apply the paint formulation to the color-matching article, the rigidity of the base layer may resist the force of the sprayed paint. In some embodiments, for example for a spray application, a 10 to 20 point board is may be used.
  • the base layer is calendared so at least on one side of the base layer is smooth.
  • the base layer may be a film.
  • a variety of film compositions may be used.
  • the film chemistry of the base layer is compatible with the curing and the painting process.
  • Exemplary films can include films of polyester, polybutyl phthalate, polycarbonate, polystyrene, polypropylenes, polyethylenes, polyvinyl chloride, polyvinyl acetate, acrylic, polyurethanes, copolymers thereof, or multilayer composites thereof.
  • paper and film may be laminated together or a film can be coated on the paper to provide the balance of properties required for the desired application.
  • the base layer is transparent.
  • the base layer is achromic, while in some embodiments, the base layer is colored. In some embodiments, the base layer comprises less than 0.5% by weight of silicones, fluorochemicals, or polyolefins. In some embodiments, the base layer contains no deliberately-added low-surface-energy components such as silicones, fluorochemicals, or polyolefins. In some embodiments, the base layer contains trace or nominal levels of low-surface- energy components such as silicones, fluorochemicals, and polyolefins. In some embodiments, the base layer is essentially free of or contain no low-surface-energy components such as silicones, fluorochemicals, and polyolefins.
  • the release liners can optionally further comprise a varnish layer.
  • the optional varnish layer can comprise a low-adhesion backsize layer.
  • Suitable materials for forming low adhesion backsize layer are known in the art and may be selected, for example, with reference to the type of pressure sensitive adhesive chosen for adhesive layer.
  • Low-adhesion backsize materials include, for example, long chain branched polymers (e.g., copolymers of alkyl acrylate and acrylic acid, stearyl methacrylate-acrylonitrile copolymer), polyvinyl carbamates (e.g., polyvinyl N-octadecyl carbamate), fiuorocarbon polymers, and amines.
  • the release layer is achromic so that it does not impart color to the color-matching article.
  • the components in the low adhesion backsize layer do not migrate or contaminate the paint preparation area.
  • the paint formulation can adhere to the optional varnish layer after the varnish layer has been applied to the base layer and cured.
  • the optional varnish layer contains no deliberately-added low- surface- energy components such as silicones, fluorochemicals, or polyolefms.
  • the varnish layer contains trace or nominal levels of low-surface-energy components such as silicones, fluorochemicals, and polyolefms. In some embodiments, the varnish layer is essentially free of or contains no low-surface-energy components such as silicones, fluorochemicals, and polyolefms. In some embodiments, the optional varnish layer comprises less than 0.5% by weight of silicones, fluorochemicals, or polyolefms.
  • the base layer and optional varnish layer of the release liner comprise less than
  • silicones, fluorochemicals, or polyolefms 0.5% by weight of silicones, fluorochemicals, or polyolefms; contain trace or nominal levels of silicones, fluorochemicals, or polyolefms; or are essentially free of silicones, fluorochemicals, or polyolefms, or the paint formulations can adhere to the release liner, for example in embodiments of the method where the paint formulation is applied to at least a portion of the release liner.
  • the paint adheres strongly, e.g., the paint formulation will not be removed from the release liner by the adhesive of the color-matching article if the color-matching article is placed back on the release liner over the painted portion of the release liner and subsequently removed.
  • the release liner optionally comprises a pattern layer disposed on at least a portion of the release liner.
  • the pattern layer may be disposed between at least a portion of the first major surface of the base layer and the optional varnish layer.
  • the pattern layer may be disposed on at least a portion of the second major surface of the base layer.
  • the pattern layer may be disposed between at least a portion of the second major surface of the base layer and the optional second color layer.
  • the pattern layer may comprise ink and may be applied to the base layer or pattern layer by any known method for forming an image on a base film, including, for example, screen printing, electrographic printing, offset printing, flexographic printing, gravure printing, inkjet printing, or thermal mass transfer printing.
  • the release liner further comprises an optional second color layer.
  • the second color layer may be disposed on at least a portion of the second major surface of the base layer.
  • the second color layer may comprise ink and may be applied to the base layer or pattern layer by any known method for forming an image on a base film, including, for example, screen printing, electrographic printing, offset printing, flexographic printing, gravure printing, inkjet printing, or thermal mass transfer printing.
  • the pattern layer and the second color layer together provide a contrast ratio of 0.6 to 1.0.
  • the contrast ratio is calculated by measuring the CIE Lab color values over a white substrate and over a black substrate in the reflectance mode. The ratio of the L* value over the black substrate to L* value over the white substrate is calculated to produce a contrast ratio. This is a common measure of opacity.
  • the release liner is typically more rigid than the color-matching article. In some embodiments, the release liner is sufficiently rigid to withstand the pressure of a paint spray gun. In some embodiments, the release liner is rigid enough such that it exhibits a drape of greater than 5 inches (12.7 cm) according to the Flexibility Test described in the Examples below.
  • HVLP high volume low pressure
  • room temperature is defined as approximately 70 - 75°F (21.1 - 23.9°C).
  • ATT-9415 A double-sided adhesive transfer tape, having opposing low- and high- tack adhesive layers, part number "09415", obtained from 3M Company, St. Paul, Minnesota.
  • ATT-9457 An adhesive transfer tape, having a high-tack adhesive coated on a double-sided release liner, part number "09457", obtained from 3M Company.
  • RNK-2600 A 2 mil (50.8 ⁇ ) clear polyester film, having a single-sided primed surface, obtained under the trade designation "HOSTAPHAN RNK-2600” from Mitsubishi Films, Greer, South Carolina.
  • WCS A double-sided smooth calendared 10-point board white cardstock, obtained from
  • 7717SW A single, silicone-free, adhesive layer sandwiched between optically clear and white pigmented 2-mil (50.8 ⁇ ) polyester films, obtained under the trade designation "7717SW” from 3M Company.
  • SC160-10 A 4 mil (101.6 ⁇ ), white polyvinyl chloride film having, on one surface, a removable acrylic adhesive covered by a silicone treated paper release liner, obtained under the trade designation "SCOTCHCAL 160-10" from 3M Company.
  • CT 180-31 A light grey 2 mil (50.8 ⁇ ) cast polyvinyl chloride film having, on one surface, a removable acrylic adhesive covered by a silicone release liner, obtained under the trade designation "CONTROLTAC GRAPHIC MARKING SYSTEM 180-31" from 3M Company.
  • IJ180CV3- 10 A white 2 mil (50.8 ⁇ ) cast polyvinyl chloride film having, on one surface, a microstructured adhesive layer, obtained under the trade designation "CONTROLTAC GRAPHIC MARKING SYSTEM IJ180CV3-10" from 3M Company.
  • ODA octadecylacylate
  • MA methyl acrylate
  • AN acrylonitrile
  • AA acrylic acid
  • AIBN 2,2'- azobisisobutyronitrile
  • 182 grams of ethyl acetate were added to a 1 -quart (946.4 mL) amber colored glass bottle at room temperature.
  • the mixture was purged with nitrogen at 1 L/min for 3 minutes, the bottle sealed and then tumbled in a constant temperature water bath at 65°C for 48 hours.
  • the resulting acrylic polymer was cooled to 21°C and diluted to 2.5% by weight solids with toluene.
  • the polymer solution was then coated onto a paper sprayout card, type "ARMC463 2/1 1" obtained from PPG Industries, Pittsburgh, Pennsylvania, using an "RDS04" type Meyer rod from RD Specialties, Webster, New York, and dried for 60 minutes at room temperature.
  • the liner was removed from one side of the ATT-9457 transfer tape and the exposed adhesive face of the tape manually laminated to printed side of the WCS cardstock at room temperature by means of a laminator, model "LS950", from 3M Company.
  • the release liner was removed from the opposing surface of the transfer tape and the film assembly then manually laminated to the non- primed surface of the RNK-2600N film. Feed tension during lamination was balanced to prevent curl and trapping bubbles of the laminated assembly.
  • a 7 mil (177.8 ⁇ ) polyester film primed on one surface with an ink-receptive layer.
  • a horizontal line pattern was produced on one surface of the film using a black fine point permanent marker pen, trade designation "SHARPIE” from Newell Rubbermaid Products, Oak Park, Illinois. The pattern was then spray coated with two successive coats of a white primer, type "RUST-OLEUM
  • PAINTPLUS, PART No. 249058 from Rust-Oleum Corporation, Vernon Hills, Illinois, drying for 5 minutes at room temperature between each application, then allowed to dry for an additional 2 hours.
  • a commercial flexographic printer applied two layers of a UV curable white ink to the optically clear polyester film of 7717SW, cured the ink, then applied one layer of a translucent UV curable gray ink that matched PANTONE PMS 421 LIGHT GRAY, and again cured the ink.
  • a 24 by 24 inch (60.96 by 60.96 cm) sheet of SC160-1 was sprayed with a gray primer, type "RUST-OLEUM PAINTER'S TOUCH ULTRACOVER FLAT GRAY, PART No. 249088" at room temperature, allowed to partially dry for 5 minutes, after which a second coat was applied and the sheet dried for an additional 2 hours. The sheet was then converted into 4 by 6 inch (10.16 by 15.24 cm) segments.
  • CFA-3 Colored Film Assembly 3
  • the release liner was removed from a 4 by 6 inch (10.16 by 15.24 cm) sheet of the CT180-31 film and laminated to the non-adhesive surface of an equally sized sheet of IJ180CV3- 10 film, by means of the LS950 laminator at room temperature. The laminated assembly was then converted into a 3.5 by 6 inch (8.89 by 15.24 cm) sheet.
  • the liner was removed from one side of a 6 by 30 inch (15.24 by 76.20 cm) sheet of the ATT-9415 and the non-primed surface of a 6 by 30 inch (17.78 by 76.20 cm) sheet of RNK-2600N polyester film manually laminated to the transfer tape of by means of the LS950 laminator at room temperature. The non-primed face of the RNK-2600N film was then sprayed with the Part No.
  • a sheet of CFA-2 was trimmed to 3.75 by 6 inches (9.53 by 15.24 cm), the liner removed, and the sheet centrally positioned over a 4.25 by 6.5 inch (10.80 by 16.51 cm) sheet of RS-1, thereby providing an exposed 0.25 inch (10.16 mm) border of the release surface.
  • the assembly was then laminated at room temperature by means of the LS950 laminator.
  • Example 2 The procedure generally described in Example 1 was repeated, wherein both the CFA-2 and RS- 1 were trimmed to 3.5 by 5.5 inches (8.89 by 13.97 cm), thereby eliminating the exposed border of the release surface.
  • Example 1 The procedure generally described in Example 1 was repeated, wherein the CFA-2 was replaced by CFA-3.
  • Example 2 The procedure generally described in Example 2 was repeated, wherein the CFA-2 was replaced with CFA-3.
  • Example 6 The procedure generally described in Example 1 was repeated, wherein the CFA-2 was replaced with CFA-4.
  • Example 6 The procedure generally described in Example 1 was repeated, wherein the CFA-2 was replaced with CFA-4.
  • Example 1 The procedure generally described in Example 1 was repeated, wherein the CFA-2 was replaced with CFA-5.
  • Example 2 The procedure generally described in Example 1 was repeated, wherein the CFA-2 was replaced with CFA-1 and the RS-1 was replaced with RS-2.
  • Example 9 The procedure generally described in Example 2 was repeated, wherein the CFA-2 was replaced with CFA- 1 and the RS- 1 was replaced with RS-2.
  • Example 10 The procedure generally described in Example 7 was repeated, wherein the RS-2 was replaced with RS-3.
  • Example 10 The procedure generally described in Example 7 was repeated, wherein the RS-2 was replaced with RS-3.
  • Example 7 The procedure generally described in Example 7 was repeated, wherein the RS-2 was replaced with RS-3.
  • the paint was then sprayed onto the example using a model "SATA JET 4000 NR" HVLP paint gun from Sata GmbH, Komwestheim, Germany, employing a 1.3 mm tip at 30 psi (206.8 kPa) gauge pressure and 8 - 10 psi (55.2 - 69.0 kPa) air cap pressure, at room temperature. After 5 minutes a second coat was applied and the example dried for 60 minutes.
  • a black painted steel test panel having a "DUPONT RK 8148" clearcoat finish was obtained from ACT Laboratories, Inc., Hillsdale, Michigan.
  • the adhesive side of a 1 by 4 inch (2.54 by 10.16 cm) example was positioned over the test panel such that approximately 3 inches (7.62 cm) of the adhesive coated example contacted the clearcoat surface and the remaining 2.54 cm extended beyond the edge of the panel.
  • the example was then manually laminated to the test panel using a rubber roller at an approximate force of between 3-5 Kg, after which it was conditioned at room temperature and 50% RH for 2 hours.
  • the extended portion of the example was clamped to the sensor of a model "SP- 102C 3090 adhesion test instrument, obtained from IMASS, Inc., Accord, Massachusetts.
  • the resiliency of the colored film assembly (CFA) adhesive to a commercial solvent was evaluated as follows. Ten drops of solvent, obtained under the trade designation "R859 WAX AND GREASE REMOVER” from AkzoNobel N.V., Amsterdam, the Netherlands, formed an approximately one inch (2.54 cm) diameter pool on the backside of the CFA sample. The solvent was then allowed to reside for 5 minutes at room temperature. Wearing a neoprene glove, the test area was manually rubbed with the index finger until the adhesive was removed. The time taken to remove the adhesive, and the ease with which it was removed, subjectively rated on a scale of 1 - 5, with 5 being the easiest, were recorded. Results are listed in Table 4.
  • a water based silver paint was prepared using "ENVIROBASE” type base components, obtained from PPG Industries, Strongville, Ohio, according to PPG color code 5451.
  • the color matching films were applied to a test panel and removed.
  • the silver paint was then applied to the test areas using a model "NR 4000" spray gun with a 1.3 mm tip, obtained from SATA GmbH & Co., KG, Kornwestheim, Germany.
  • Gauge pressure was set at 30 psi (206.8 kPa). None of the exemplary color matching films caused defects as evidenced by coating defects, including non wetted areas and non uniform appearance.
  • Embodiment 1 is a repositionable color-matching article comprising:
  • a flexible substrate having a first major surface and a second major surface disposed opposite the first major surface
  • Embodiment 2 is a color-matching article according to embodiment 1 , further comprising a first color layer disposed upon the first major surface of the substrate.
  • Embodiment 3 is a color-matching article according to any one of embodiments 1 or 2, wherein the clean removal adhesive is solvent resistant according to the Solvent Resistance Test.
  • Embodiment 4 is the color-matching article of any one of embodiments 1 to 3, wherein the adhesive is self-wetting.
  • Embodiment 5 is a color-matching article according to any one of embodiments 1 to 4, wherein the adhesive comprises a silicone-free, urea-based adhesive.
  • Embodiment 6 is a color-matching article according to any one of embodiments 1 to 5, wherein the article has an average edge thickness of 10 mils or less.
  • Embodiment 7 is a color-matching article according to any one of claims 1 to 6, wherein the article exhibits a drape of 3 inches (7.62 cm) or less according to the Flexibility Test.
  • Embodiment 8 is a color-matching system comprising the color-matching article according to any one of embodiments 1 to 7; and a release liner;
  • release liner comprises:
  • a base layer having a first major surface and a second major surface disposed opposite the first major surface
  • release liner comprises less than 0.5% silicone by weight.
  • Embodiment 9 is a color-matching system according to embodiment 8, wherein the release liner further comprises a varnish layer disposed on the first major surface of the base layer.
  • Embodiment 10 is a color-matching system according to any one of embodiments 8 or 9, wherein the release liner further comprises a pattern layer.
  • Embodiment 1 1 is a color-matching system according to embodiment 10, wherein the pattern layer is disposed on at least a portion of the second major surface of the base layer.
  • Embodiment 12 is a color-matching system according to embodiment 10, wherein the pattern layer is disposed on at least a portion of the first major surface of the base layer.
  • Embodiment 13 is a color-matching system according to any one of embodiments 8 to 12, wherein the release liner further comprises a second color layer disposed on the second major surface of the base layer, the pattern layer, or combinations thereof.
  • Embodiment 14 is a color-matching system according to any one of embodiments 8 to 13, wherein one or more edges of the release liner extend beyond one or more edges of the color- matching article.
  • Embodiment 15 is a color-matching kit comprising:
  • Embodiment 16 is a color-matching kit of embodiment 15, wherein the applicator is selected from a squeegee or a roller.
  • Embodiment 17 is a color-matching kit of any one of embodiments 15-16, further comprising a clear-coat-simulating article, a clear-coat formulation, or a clear-coat-simulating formulation.
  • Embodiment 18 is a method of color-matching a paint formulation to a target surface having a color, the method comprising:
  • Embodiment 19 is a method according to embodiment 18, further comprising the step of: (bl) adhering a clear-coat-simulating article or applying a clear-coat formulation or clear- coat-simulating formulation over the color-matching article.
  • Embodiment 20 is a method according to any one of embodiments 18 or 19, further comprising:
  • Embodiment 21 is a method according to embodiment 20, further comprising:
  • Embodiment 22 is a method of color-matching a paint formulation to a target surface having a color, the method comprising:
  • Embodiment 23 is a method according to embodiment 22, wherein step (a) further comprises applying the paint formulation over at least a portion of the release liner; and wherein the paint formulation adheres to the release liner.
  • Embodiment 24 is a method according to any one of embodiments 22 or 23, further comprising the step of:
  • Embodiment 25 is a method according to any one of embodiments 22 to 24, further comprising:
  • Embodiment 26 is a method according to embodiment 25, further comprising:
  • Embodiment 27 is a method according to any one of embodiments 22 to 26, wherein the release liner comprises a pattern layer, further comprising: (al) assessing visibility of the pattern layer through the paint layer.
  • Embodiment 28 is a method according to any one of embodiments 18-27, wherein the target surface comprises a surface topography, wherein the color-matching article conforms to the surface topography upon adhering the color-matching articles to a portion of the target surface with the adhesive layer.
  • Embodiment 29 is a method according to embodiment 28, wherein the surface topography is non-planar.
  • Embodiment 30 is a method according to any one of embodiments 18-29, wherein in step (a) the paint formulation is applied over at least a portion of the first major surface of the substrate to form a paint layer on the color-matching article.
  • Embodiment 31 is a method according to any one of embodiments 18-29, wherein the color- matching article further comprises a first color layer disposed on the first major surface of the substrate and wherein in step (a) the paint formulation is applied over at least a portion of the first color layer to form a paint layer on the color-matching article.
  • Embodiment 32 is a repositionable color-matching article of any of embodiments 1-7 wherein the adhesive layer comprises an air release structure.
  • Embodiment 33 is a color-matching system of any of embodiments 8-14 or 32 wherein the release liner comprises an air release structure.
  • Embodiments 34 is a color matching system of embodiment 33 wherein the air release structure is disposed on at least one of the first major surface or the second major surface.
  • Embodiment 35 is a color-matching kit comprising the color-matching system of embodiment 34 and an applicator.
  • Embodiment 36 is a color matching system component comprising an air release structure on a major surface thereof.
  • Embodiment 37 is a component as in embodiment 36 wherein the air release structure comprises discrete protrusions having an average feature size in a range from 300 micrometers to 1800 micrometers.
  • Embodiment 38 is a component as in any of embodiments 36-37 wherein the air release structure comprises discrete protrusions having an average feature height in a range from 1 micrometer to 60 micrometers.
  • Embodiment 39 is a component as in any of embodiments 36-38 wherein the air release structure comprises discrete protrusions having an average center-to-center spacing in a range from 500 micrometers to 900 micrometers.
  • Embodiment 40 is a component as in any of embodiments 36-39 wherein the air release structure comprises discrete protrusions having an average feature-to-feature spacing in a range from 20 micrometers to 1200 micrometers.
  • Embodiment 41 is a component as in any of embodiments 36-40 wherein the component is one of a color matching article or a release liner.
  • Embodiment 42 is a component as in any of embodiments 37-41 wherein the discrete protrusions are arranged on the major surface in one of a regular pattern of offset rows, a regular pattern of aligned rows, a randomly distributed pattern, or a cross hatch pattern.
  • Embodiment 43 is a component as in any of embodiments 37-42 wherein the discrete protrusions are formed by one of screen printing, electrographic printing, offset printing, flexographic printing, gravure printing, inkjet printing, thermal mass transfer printing, embossing, microreplication, or combinations thereof.
  • Embodiment 44 is a component as in embodiment 36 wherein the air release structure comprises a plurality of abrasions.
  • Embodiment 45 is a component as in embodiment 44 wherein the abrasions result in an average feature height in a range from 10 micrometer to 50 micrometers.
  • Embodiment 46 is a component as in any of embodiments 44-45 wherein the component is one of a color matching article or a release liner.
  • Embodiment 47 is a color matching system comprising
  • Embodiment 48 is a release liner comprising a major surface and an air release structure disposed on the major surface, the air release structure comprising a plurality of discrete features comprising:
  • Embodiment 49 is the release liner as in embodiment 48 wherein the plurality of discrete protrusions comprises a regular pattern of features.
  • Embodiment 50 is a release liner as in any of embodiments 48-49 wherein the discrete protrusions comprises a regular pattern of offset rows of circular dots.

Abstract

Color-matching articles and systems are described. The color-matching articles (100) comprise a flexible substrate (110) having a first major surface (111) and a second major surface (112) disposed opposite the first major surface and a clean-removal pressure-sensitive adhesive layer disposed upon the second major surface of the substrate. The color-matching systems (300) comprise the color-matching articles (100) and a release liner (200) comprising a base layer (210) having a first major surface (211) and a second major surface (212) disposed opposite the first major surface. The adhesive layer of the color-matching article is releasably adhered to the first major surface of the release liner. The color-matching articles and systems may comprise less than 0.5% by weight of silicones, fluorochemicals, and polyolefins. Methods of color-matching a paint formulation to a target surface using the color-matching articles and systems are also described. Air release structures disposed on the color matching article and/or the release liner are also disclosed.

Description

PAINT COLOR EVALUATION SYSTEM THAT FACILITATES EXAMINATION OF COLOR AT MULTIPLE ANGLES AND LOCATIONS ON A VEHICLE Background
Color-matching paint is an important step in the automobile repair process. It is also one of the most variable steps in the repair process. Typically, automobiles are assigned a paint color code by the manufacturer. This paint color code is often used by the paint formulator to generate an initial or starting point paint formulation. Starting point paint formulations can also be identified using spectrophotometric or paint variance techniques. While such process will approximately match the hue of a painted substrate, they have difficulty accommodating the metallic or pearlescent appearance of some automotive paints. Thus, the starting point paint formulations are typically not adequate matches, and the painter must evaluate paint colors to determine whether they are an adequate match to the vehicle.
Evaluation of the paint color is a critical step in the painting process. To make matters more difficult, the automotive paints are becoming thinner, less opaque and even more loaded with pearlescent and fine metallic components. The metallic and pearlescent finishes have color that is highly dependent on the viewing angle and lighting, so a painter will have to evaluate the paint color for adequate match at these different viewing angle and lighting conditions. In addition, many newer vehicles are made with body panels that are extremely thin and lightweight compared to body panels used in the past. These lighter panels typically have very sharp feature lines to make them more stable. When a painter paints over these sharp feature lines it is critical that the color matches at a variety of viewing angles.
Several approaches exist for evaluating paint colors for adequate match. Some painters mix the paint and spray it directly on the vehicle; if it does not match, they will re-mix and spray, continuing the process until a sufficient match is achieved. However, because automotive paint is very expensive and this process wastes paint, this method can be very expensive.
Other painters use a printed board stock. The paint is applied to the board stock, and the painted board stock is held by the painter in their hand or applied to a holder like a paint stick and held next to the car in an attempt to evaluate for match. This board stock does not conform well to the surface and does not stay in intimate contact with the paint, making it difficult to evaluate the paint from different viewing angles, distances, and lighting conditions. The board stock also has a thick edge, which demonstrates a small edge effect that can disrupt the viewing of the test sample.
Another approach is apply test paint to a paintable magnetic sheet and apply the magnetic sheet to the vehicle to evaluate match of the paint. This method suffers from edge effects created by the thick edge of the magnetic sheet, which makes it difficult to replicate the sharpness of the feature line when applied. And, while the magnetic sheet does bond to most metal surfaces, current trends in vehicle construction use aluminum, plastic, or other non-magnetic materials for the vehicle body, rendering the magnetic feature useless.
Thus, a need exists for an inexpensive, easy-to-use article that allows viewing of paint samples at multiple viewing angles, distances, and lighting conditions, and over sharp features, to guide the painter in color-matching of a paint formulation to a target surface, for example, a vehicle under repair.
Summary
The present disclosure is generally directed toward articles, systems, and methods that are adapted to accommodate color matching over two-dimensional compound surfaces, including sharp features and the use of metallic paints. The articles and systems described herein are flexible, clean- removal, inexpensive, easy to use articles and systems that allow viewing of paint samples at multiple viewing angles, distances, and lighting conditions, and over sharp features, to guide the painter in a method of color-matching of a paint formulation to a target surface, such as a vehicle under repair.
In one aspect, the present disclosure provides a repositionable color-matching article comprising: a flexible substrate having a first major surface and a second major surface disposed opposite the first major surface; and
a pressure-sensitive adhesive layer disposed upon the second major surface of the substrate; wherein the adhesive layer comprises a clean removal adhesive.
The clean removal adhesive of the color-matching article of can be solvent resistant according to the Solvent Resistance Test and, in some embodiments, can comprise a silicone-free, urea-based adhesive.
In another aspect, the present disclosure provides a color-matching system comprising the color-matching articles described herein and a release liner; wherein the release liner comprises a base layer having a first major surface and a second major surface disposed opposite the first major surface; and
wherein the adhesive layer of the color-matching article is releasably adhered to the first major surface of the release liner; and wherein the release liner comprises less than 0.5% silicone by weight.
The release liner of the color-matching system may optionally further comprise a varnish layer disposed on the first major surface of the base layer. In some embodiments, the release liner further comprises a pattern layer. In some embodiments, the release liner further comprises a second color layer.
In another aspect, the present disclosure provides a color-matching kit comprising the color- matching system and an applicator. In some embodiments, the kit further comprises a clear-coat- simulating article, a clear-coat formulation, or a clear-coat-simulating formulation. In another aspect, the present disclosure provides a method of color-matching a paint formulation to a target surface having a color, the method comprising:
(a) applying the paint formulation over at least a portion of the repositionable color- matching article described herein;
(b) adhering the color-matching article to a portion of the target surface with the adhesive layer;
(c) comparing the paint formulation on the color-matching article to the target surface; and
(d) determining whether the paint formulation on the color-matching article closely matches the color of the target surface.
The method may further comprising any of the steps of:
(bl) adhering a clear-coat-simulating article or applying a clear-coat formulation or clear- coat-simulating formulation over the color-matching article;
(e) removing the color-matching article from the target surface, wherein upon removal, no contaminants remain on the target surface according to the Contamination Test; and
(f) repeating steps (a)-(c) or (a)-(e).
In another aspect, the present disclosure provides a method of color-matching a paint formulation to a target surface having a color, the method comprising:
(a) applying the paint formulation over at least a portion of the color-matching article of the color-matching system;
(b) removing the color-matching article from the release liner;
(c) adhering the color-matching article to a portion of the target surface with the adhesive layer;
(d) comparing the paint formulation on the color-matching article to the target surface; and
(e) determining whether the paint formulation on the color-matching article closely matches the color of the target surface.
In some embodiments, step (a) can further comprises applying the paint formulation over at least a portion of the release liner; and wherein the paint formulation adheres to the release liner.
The method can further comprise any of the steps of:
(cl) adhering a clear-coat-simulating article over the color-matching article;
(f) removing the color-matching article from the target surface; and
(g) repeating steps (a)-(e), or (a)-(f).
In some embodiments, the release liner comprises a pattern layer, and the method further comprises:
(al) assessing visibility of the pattern layer through the paint layer.
In some embodiments of the method, the target surface comprises a surface topography, wherein the color-matching article conforms to the surface topography upon adhering the color- matching articles to a portion of the target surface with the adhesive layer. In some embodiments, the surface topography is non-planar.
In some embodiments, color matching kits and systems according to the present disclosure, including color matching articles and release liners, comprise an air release structure.
Other features and aspects of the present disclosure will become apparent by consideration of the detailed description and accompanying drawings. In no event, however, should the above summaries be construed as limitations on the claimed subject matter.
Brief Description of the Drawings
Fig. 1A is a cross-sectional view of an embodiment of a color-matching article of the present invention.
Fig. IB is a cross-sectional view of an embodiment of a color-matching article of the present invention.
Fig. 2A is a cross-sectional view of an embodiment of a release liner of the present invention.
Fig. 2B is a cross-sectional view of an embodiment of a release liner of the present invention.
Fig. 2C is a cross-sectional view of an embodiment of a release liner of the present invention.
Fig. 2D is a cross-sectional view of an embodiment of a release liner of the present invention.
Fig. 2E is a cross-sectional view of an embodiment of a release liner of the present invention.
Fig. 3 is a cross-sectional view of an embodiment of a color-matching system of the present invention.
Fig. 4 is a top view of an embodiment of a color-matching system of the present invention. Fig. 5A is a perspective view showing a painter applying a paint formulation to an embodiment of a color-matching article of the present invention.
Fig. 5B is a perspective view showing a painter adhering a color-matching article of the present invention to a target surface for color match comparison.
Fig. 6A is a perspective view showing a painter applying a paint formulation to an embodiment of a color-matching system of the present invention.
Fig. 6B is a perspective view showing a painter removing a color-matching article of the present invention from a release liner of the present invention.
Fig. 6C is a perspective view showing a painter adhering a color-matching article of the present invention to a target surface for color match comparison. Fig. 7 is a schematic side view of an exemplary embodiment of a color match system comprising an air release structure according to the present disclosure.
Fig. 8 is a schematic side view of an exemplary embodiment of a color match article comprising an air release structure according to the present disclosure.
Figs. 9-1 1 are schematic side views of exemplary embodiments of a release liner comprising an air release structure according to the present disclosure.
Fig. 12 is a plan view of an exemplary air release structure comprising a random dot pattern according to the present disclosure.
Fig. 13 is a plan view of an exemplary air release structure comprising a regular offset row dot pattern according to the present disclosure.
Figs. 14-16 are plan views of exemplary air release structures comprising a square cross hatch pattern according to the present disclosure.
Fig. 17 is a plan view of an exemplary air release structure comprising a regular offset row dot pattern according to the present disclosure.
Fig. 18 is a plan view of an exemplary air release structure comprising abrasions according to the present disclosure.
While the above-identified drawings and figures set forth embodiments of the invention, other embodiments are also contemplated, as noted in the discussion. In all cases, this disclosure presents the invention by way of representation and not limitation. It should be understood that numerous other modifications and embodiments can be devised by those skilled in the art, which fall within the scope and spirit of this invention.
The figures may not be drawn to scale. Detailed Description
In the following description of illustrative embodiments, reference is made to the accompanying figures of the drawing which form a part hereof, and in which are shown, by way of illustration, specific embodiments. It is to be understood that other embodiments may be utilized and structural changes may be made without departing from the scope of the present invention.
Unless otherwise indicated, all numbers expressing feature sizes, amounts, and physical properties used in the specification and claims are to be understood as being modified in all instances by the term "about." Accordingly, unless indicated to the contrary, the numerical parameters set forth in the foregoing specification and attached claims are approximations that can vary depending upon the desired properties sought to be obtained by those skilled in the art utilizing the teachings disclosed herein. The use of numerical ranges by endpoints includes all numbers within that range (e.g. 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, and 5) and any range within that range. As used herein, "a," "an," "the," "at least one," and "one or more" are used interchangeably. The present invention describes color-matching articles, systems, and methods of using color-matching articles and systems for the color-matching of paint formulations to target surfaces.
Some illustrative embodiments of color-matching articles as described herein are depicted in Figs. 1A-1B. Figs. 1A- 1B depict cross sections of a color-matching article 100 of the present invention. The color-matching article 100 comprises a flexible transparent substrate 1 10 having a first major surface 1 1 1 and a second major surface 1 12 disposed opposite the first major surface 1 1 1. A pressure-sensitive adhesive layer 120 is disposed upon the second major surface 1 12 of the substrate 110. As in Fig. IB, an optional first color layer 130 may be disposed upon the first major surface 1 1 1 of the substrate 110.
In some embodiments, the color-matching articles may be paired with a release liner to comprise a color-matching system. Figs. 2A-2E depict some illustrative embodiments of release liners as described herein. Figs. 2A-2E depict cross sections of a release liner 200 of the present invention. The release liner 200 comprises a base layer 210 having a first major surface 21 1 and a second major surface 212 opposite the first major surface. In some embodiments, the first major surface 21 1 of the base layer 210 is non-primed. In some embodiments, the second major surface 212 of the base layer 210 is primed. The release liner 200 optionally further comprises a varnish layer 220 disposed on the first major surface 21 1 of the base layer 210. In some embodiments, the release liner 200 may further comprise a pattern layer 230, as in Figs. 2B-2E. In some embodiments, the pattern layer 230 may be disposed on at least a portion of the first major surface 21 1 of the base layer 210, as in Figs. 2B and 2D. In such embodiments, the pattern layer 230 is therefore disposed between at least a portion of the base layer 210 and at least a portion of the optional varnish layer 220. In some embodiments, the pattern layer 230 may be disposed on at least a portion of the second major surface 212 of the base layer 210, as in Figs. 2C and 2E. In some embodiments, the release liner 200 may further comprise a second color layer 240 disposed on the second major surface 212 of the base layer 210, as in Figs. 2D and 2E. In some embodiments, the pattern layer 230 may be disposed between at least a portion of the second color layer 240 and the second major surface 212 of the base layer 210.
In some embodiments, a color-matching article of the present invention and a release liner of the present invention are paired to create a color-matching system. Fig. 3 depicts an illustrative embodiment of a color-matching system 300 as described herein, comprising color-matching article 100 and release liner 200. In the illustrated embodiment, color-matching article 100 comprises substrate layer 1 10 having a first major surface 1 1 1 and a second major surface 1 12 opposite the first major surface 1 1 1, and adhesive layer 120 disposed on the second major surface 1 12 of substrate 1 10. In the illustrated embodiment, color-matching article 100 further comprises optional first color layer 130 disposed on the first major surface 11 1 of substrate 1 10. In the illustrated embodiment, release liner 200 comprises base layer 210 having a first major surface 21 1 and a second major surface 212 opposite the first major surface 21 1, and optional varnish layer 220 disposed on the first major surface 211 of base layer 210. In the illustrated embodiment, release liner 200 further comprises optional pattern layer 230 disposed on the first major surface 21 1 of base layer 210, between optional varnish layer 220 and the first major surface 21 1 of base layer 210. In the illustrated embodiment, release liner 200 further comprises optional second color layer 240 disposed on the second major surface 212 of base layer 210. The adhesive layer 120 of color- matching article 100 is releasably adhered to optional varnish layer 220 or the first major surface 21 1 of release liner 200.
Fig. 4 depicts a top view of an embodiment of a color-matching system 300 of the present invention, comprising color-matching article 100 releasably adhered to release liner 200. In some embodiments, release liner 200 may comprise pattern layer 230, which is visible though color- matching article 100. In some embodiments, the edges 201 of release liner 200 extend beyond the edges 101 of color-matching article 100.
The color-matching articles of Figs. 1A-1B are used in a method of color-matching a paint formulation according to the present invention. In some embodiments of the method, a paint formulation to be color-matched to a target surface is first applied over at least a portion of the color-matching article 100. In some embodiments, the paint formulation is applied over at least a portion of the first major surface 1 1 1 of the substrate 1 10 of the color-matching article 100. In some embodiments, where the color-matching article 100 further comprises a first color layer 130 disposed on the first major surface 1 1 1 of the substrate 1 10, as in Fig. IB, the paint formulation is applied over at least a portion of the first color layer 130. In some embodiments, the paint formulation may be initially formulated, for example, with reference to paint codes that are provided with an automobile or other target surface, or with reference to color samples that are provided by various paint suppliers. Notably, the methods described herein can be used to match metallic and pearlescent paints, as well as non-metallic paints. In addition, the paint formulations may be solvent- based or water-based paint formulations. Fig. 5A shows application of paint formulation 42 over the first major surface 1 1 1 of the substrate 1 10 of color-matching article 100 by painter 40 using a pressurized spray gun 41 to form paint layer 42a. It is to be understood that paint formulation 42 may be applied to the color-matching article using any known techniques, including, for example, with a paint roller or paintbrush. In some embodiments of the method, the paint layer 42a is then allowed to dry. The painted color-matching article 100a is then adhered to a portion of the target surface with the adhesive layer 120. Fig. 5B shows painter 40 adhering the painted color-matching article 100a to target surface 43. The color-matching article 100/100a conforms to the surface topography of the target surface upon adhering the color-matching article 100/100a to a portion of the target surface 43 with the adhesive layer. Once the color-matching article 100/ 100a is adhered to the target surface, the painter or other individual assessing the match of the paint formulation to the target surface then assesses the match by comparing the paint formulation on the color-matching article to the target surface and determining whether the paint formulation on the color-matching article closely matches the color of the target surface. Because the color-matching article is adhered to the target surface and can conform to non-planar surface topography, the painter or other individual assessing the match of the paint formulation to the target surface can move around in order to view the paint formulation from multiple distances, viewing angles, and lighting conditions. It may also be desirable to view the painted color-matching article on the target surface under more than one lighting condition such as, for example, artificial light and sunlight.
In some embodiments, for example, where the target surface is an automotive vehicle or vehicle part, it may be desirable to simulate a clear coat by adhering a clear-coat-simulating article or applying a clear-coat formulation or clear-coat-simulating formulation over the color-matching article on the target surface prior to assessing the match of the paint formulation to the target surface then assesses the match by comparing the paint formulation on the color-matching article to the target surface and determining whether the paint formulation on the color-matching article closely matches the color of the target surface. Any clear-coat formulation or clear-coat-simulating formulation may be applied, such as, for example, clear-coat spray formulations, solvents that wet the surface and provide a temporary high gloss, clear-coat-simulator sprays, and the like. Any clear- coat-simulating article known in the art may be used, such as, for example, a film/adhesive laminate that simulates a clear coat, or those described in US 6,995,843. In addition, some embodiments of the color-matching article described herein can be used as a clear-coat-simulating article. For example, color-matching article 100 shown in Fig. 1A, without the optional first color layer, may be placed over painted color-matching article 100a in order to simulate the appearance of a clear coat. Then, when the painter or other individual assessing the match of the paint formulation is comparing the paint formulation on the color-matching article to the target surface and determining whether the paint formulation on the color-matching article closely matches the color of the target surface, the visual effects of the clear coat on the paint formulation that may affect the match can be seen. In some embodiments, the clear-coat-simulating article may be applied to the painted color-matching article prior to adhering the painted color-matching article to the target surface. In some
embodiments, the clear-coat-simulating article may be applied to the painted color-matching article after applying the painted color-matching article to the target surface, while the painted color- matching article is adhered to the target surface. Adhesive bonding of the clear-coat-simulating article to the painted color-matching article may be assisted, for example, by used of a hand-held roller, squeegee, or a portable lamination device available under the trade designation "XYRON 510" (Part Number XR 510ATPS) from Xyron, Inc. (Scottsdale, Ariz.).
After determining whether the paint formulation on the color-matching article closely matches the color of the target surface, the painted color-matching article is removed from the target surface. Upon removal, the paint formulation can be applied directly to the target surface without problems such as low adhesion of the paint formulations, orange-peel texture, color changes, non- wetting, and other surface anomalies, according to the Contamination Test described in the
Examples below. In some embodiments, only trace amounts of low-surface-energy components such as silicones, fluorochemicals, and polyolefins, remain on the target surface after removal of the color-matching article from the target surface. In some embodiments, no low-surface-energy components such as silicones, fluorochemicals, and polyolefins, remain on the target surface after removal of the color-matching article from the target surface. If the paint formulation matched sufficiently, the painter can now paint the target surface with the final formulation. If the match was insufficient, or if the painter or other individual assessing the match of the paint formulation wishes to assess another paint formulation for match, it may be desirable to repeat the method described above with the same color-matching article 100/100a, or with a different color-matching article, in order to provide an improved color-matched paint formulation. In some embodiments, the color- matching articles described herein can be re -used. For example, the method steps can be repeated, and at least a portion of the painted color-matching article can be repainted. The color-matching article can then be re-adhered to the target surface.
In some embodiments of the method, the color-matching systems of Figs. 3-4 may be used.
In some embodiments of the method, a paint formulation to be color-matched to a target surface is first applied over at least a portion of the color-matching article 100 on color-matching system 300. In some embodiments, the paint formulation is applied over at least a portion of the first major surface 1 1 1 of the substrate 1 10 of the color-matching article 100. In some embodiments, the paint formulation is also applied over at least a portion of the first major surface or the optional varnish layer of the base layer of the release liner, for example, where the edges 201 of release liner 200 extend beyond the edges 101 of release liner 100 (Fig. 4). In some embodiments, where the color- matching article 100 further comprises a first color layer 130 disposed on the first major surface 1 1 1 of the substrate 1 10, as in Fig. IB and Fig. 3, the paint formulation is applied over at least a portion of the first color layer 130. Fig. 6A shows application of paint formulation 42 over the first color layer 130 disposed on the first major surface 1 11 of the substrate 110 of color-matching article 100 releasably adhered to optional varnish layer 220 of release liner 200 by painter 40 using a pressurized spray gun 41 to form paint layer 42a. In some embodiments, the paint formulation 42 is also applied over at least a portion of the first major surface 21 1 or the optional varnish layer 220 of the base layer 210 of the release liner 200. It is to be understood that paint formulation 42 may be applied to the color-matching article using any known techniques, including, for example, with a paint roller or paintbrush. In some embodiments of the method, the paint layer 42a is then allowed to dry. The painted color-matching article 100a is then removed from release liner 200 and adhered to a portion of the target surface with the adhesive layer 120. Fig. 6B shows painter 40 removing painted color-matching article 100a is then removed from release liner 200. Fig. 6C shows painter 40 adhering the painted color-matching article 100a to target surface 43. The color-matching article 100/ 100a conforms to the surface topography of the target surface upon adhering the color-matching article 100/100a to a portion of the target surface 43 with the adhesive layer. Once the color- matching article 100/100a is adhered to the target surface, the painter or other individual assessing the match of the paint formulation to the target surface then assesses the match by comparing the paint formulation on the color-matching article to the target surface and determining whether the paint formulation on the color-matching article closely matches the color of the target surface.
In some instances painters need to assess coverage of the paint formulations in addition to color match. Sufficient coverage means the paint formulation has been applied in a fashion where influence from the color of the target surface is minimized. There are occasions where the pigments in the paint formulations are not opaque but are relatively transparent. In such instances, application of enough paint to provide complete coverage is cost prohibitive, so instead the color of the target surface (e.g. with a primer), is used to influence the final color appearance of the paint formulation applied on the target surface. The color of the primer is controlled and is critical in achieving the color of such translucent coatings. To assist in this the painter can apply the specific primer as the first layer in the paint combination. The color-matching articles described herein can, in some embodiments, be supplied pre-colored with one or more of the common primer colors for the desired use. In some embodiments, the method includes the step of assessing visibility of the pattern layer 230 through the paint layer to assess paint coverage. In some embodiments, the painter or other individual assessing the match of the paint formulation can also assess coverage of the paint formulation by viewing release liner 200 after removing the painted color-matching article 100a from release liner 200. In such embodiments, release liner 200 includes pattern layer 230, and may or may not include second color layer 240. Additionally, in some embodiments, as in Fig 4, the edges 201 of release liner 200 extend beyond the edges 101 of color-matching article 100 in the color-matching system 300. When, as in Fig. 6A, painter 40 applies paint formulation to the color- matching system, the paint formulation is applied both to at least a portion of the color-matching article 100 and the release liner 200. When the painted color-matching article 100 is removed from release liner 200, as in Fig. 6B, the unpainted portion of release liner 200, including the portion of pattern layer 230 that is not concealed by the paint formulation, will be visible. Thus, the painter or other individual assessing the match and coverage of the paint formulation can compare the painted portion of the release liner to the unpainted portion of the release liner to determine whether the formulation provides adequate coverage over pattern layer 230.
In some embodiments, as in the methods described above, it may be desirable to simulate a clear coat by applying a clear-coat formulation or clear-coat-simulating formulation, or adhering a clear-coat-simulating article over the color-matching article on the target surface prior to assessing the match of the paint formulation to the target surface. The painter or other individual assessing the match of the paint formulation would then assesses the match by comparing the paint formulation on the color-matching article to the target surface and determining whether the paint formulation on the color-matching article closely matches the color of the target surface. Any clear-coat formulation or clear-coat-simulating formulation may be applied, such as, for example, clear-coat spray formulations, solvents that wet the surface and provide a temporary high gloss, clear-coat-simulator sprays, and the like. Any clear-coat-simulating article known in the art may be used, such as, for example, a film/adhesive laminate that simulates a clear coat, or those described in U.S. Pat. No. 6,995,843. In addition, some embodiments of the color-matching article described herein can be used as a clear-coat-simulating article, for example, color-matching article 100 shown in Fig. 1A, without the optional first color layer, can be used as a clear-coat-simulating article. For example, color-matching article 100 may be placed over painted color-matching article 100a in order to simulate the appearance of a clear coat.
After determining whether the paint formulation on the color-matching article closely matches the color of the target surface, the painted color-matching article is removed from the target surface. Upon removal, the paint formulation can be applied directly to the target surface without problems such as low adhesion of the paint formulations, orange-peel texture, color changes, non- wetting, and other surface anomalies, according to the Contamination Test described in the Examples below. In some embodiments, only trace amounts of low-surface-energy components such as silicones, fluorochemicals, and polyolefins, remain on the target surface after removal of the color-matching article from the target surface. In some embodiments, no low-surface-energy components such as silicones, fluorochemicals, and polyolefins, remain on the target surface after removal of the color-matching article from the target surface. If the paint formulation matched sufficiently, the painter can now paint the target surface with the final formulation. If the match was insufficient, or if the painter or other individual assessing the match of the paint formulation wishes to assess another paint formulation for match, it may be desirable to repeat the method described above with the same color-matching article 100/100a, or with a different color-matching article, in order to provide an improved color-matched paint formulation. In addition, repetition of the method may optionally include re-assessing paint coverage based on pattern layer 230, as described above.
The color-matching articles and systems described herein can be supplied as part of a color- matching kit. In some embodiments, the color-matching kit includes one or more color-matching articles as described herein and an applicator. In some embodiments, the color-matching kit includes one or more color-matching systems as described herein and an applicator. In some embodiments, the color-matching kit may also contain a clear-coat-simulating article, a clear-coat formulation, or a clear-coat-simulating formulation, as described above. The applicator may be used to ensure smooth coverage of the color-matching article to the substrate, of the color-matching article to the release liner for re-use or cataloguing, of the clear-coat-simulating-article to the painted color-matching article, or combinations thereof. For example, the applicator may assist in removing bubbles that form under the color-matching article on the target surface, between the clear-coat-simulating article and the painted color-matching article, or between the color-matching article and the release liner when the color-matching article is placed back on the release liner for re -use or cataloguing. Any applicator known in the art and capable of smoothing the color-matching articles and clear-coat- simulating articles described herein may be used. In some embodiments, the applicator is a squeegee or a roller.
The color-matching articles and systems of the present invention may be catalogued for later reference or reuse.
Components making up the color-matching articles, release liners, and color-matching systems are further described below.
The color-matching articles have a first major surface and a second major surface and typically comprise a transparent substrate, though non-transparent substrates may be used, in some embodiments, the substrate comprises a polymer film. In some embodiments, the polymer film comprises polyester, polycarbonate, acrylic, polyurethane, polyolefin, ethylene vinyl acetate, biaxially-oriented polypropylene, polyvinyl chloride, polystyrene, urethane acrylate, epoxy, epoxy acrylate, and blends thereof. In some embodiments, the adhesive comprises a silicone-free urea- based adhesive prepared by the polymerization of reactive oligomers with the general formula X-B- X wherein X is an ethylenically unsaturated group and B is a unit free of silicone and containing urea groups. The reactive oligomers can be prepared from polyamines through chain extension reactions using diaryl carbonates followed by capping reactions with acrylates. In some
embodiments, the substrate is transparent and achromic (i.e. colorless).
The color-matching articles further comprise a pressure-sensitive adhesive layer disposed upon the second major surface of the substrate. The adhesive layer can consist of many different types of pressure-sensitive adhesive materials including acrylic based adhesives which are prepared via a thermally cured process, a UV initiated process or an e-beam curing process. The acrylic can be solvent-based, water-based or 100% solids. The acrylic adhesive could be in the form of a continuous film or it could be in the form of a film with separate phases where the adhesive contains discrete phases such as a microsphere of adhesive within the adhesive film. The resultant adhesive can optionally be crosslinked after coating using common crosslinking techniques such as UV- initiated crosslinking of the polymer, crosslinking via an interpenetrating network around the base polymer, and thermally crosslinking the acrylic polymer using azirdine or isocyanate containing compounds. Crosslinking can also be generated via ionic methods using compounds of zinc, lithium or sodium to associate with ionic portions of the adhesive.
In some embodiments, the adhesive layer can comprise a rubber material including thermoplastic rubbers, block copolymers or natural rubbers. The rubbers can include polyolefins which can include polymers of ethylene vinyl acetate, poly-alpha olefins (C3-C10), copolymers or blends of poly-alpha olefins with ethylene or propylene based polymers. Poly isobutylene adhesives are common in this category. The rubber adhesives can be solvent-based, water-based or 100 % solids. The rubber-based adhesives can optionally be crosslinked for enhanced properties. In some embodiments, the adhesive layer may be a urethane or urea-based adhesive, such as, for example, those described in WO2010132176 Al .
The pressure sensitive adhesive layer may be blended with oils, plasticizers, non-pressure sensitive adhesive polymers, tackifiers, stabilizers, pigments, or fillers. In some embodiments, stablizers include thermal stabilizers such as antioxidants or hindered amine stabilizers. The stabilizer can also include materials that help resist the effects of UV light.
The adhesive is typically a clean-removal adhesive. By clean removal adhesive, it is meant that when the color-matching articles described herein are removed from the target surface, paint formulation can be applied directly to the target surface without problems such as low adhesion of the paint formulations, orange-peel texture, color changes, non- wetting, and other surface anomalies. Clean removal adhesives can be determined according to the Contamination Test described in the examples below. It has been discovered that when non-trace amounts of low-surface-energy components such as silicones, fluorochemical, polyolefins, and the like remain on the target surface after removal of the color-matching article, the low-surface-energy components interfere with adhesion and appearance of the intended application of the paint formulation, resulting, for example, in orange-peel texture, color changes, non- wetting, and other surface anomalies after application of the final paint formulation to the target surface (e.g., vehicle). In some embodiments the color matching articles, systems, or any component thereof, contain no more than 0.5% by weight of silicones, fluorochemical, and polyolefins. In some embodiments, the color matching articles, systems, or any component thereof, contain no deliberately-added low-surface-energy components such as silicones, fluorochemicals, or polyolefins. In some embodiments, the color matching articles, systems, or any component thereof, contain trace or nominal levels of low-surface-energy components such as silicones, fluorochemicals, and polyolefins. In some embodiments, the color matching articles, systems, or any component thereof, are essentially free of or contain no low- surface- energy components such as silicones, fluorochemicals, and polyolefins. In some
embodiments, only trace amounts of low-surface-energy components such as silicones,
fluorochemicals, and polyolefins, remain on the target surface after removal of the color-matching article from the target surface. In some embodiments, no low-surface-energy components such as silicones, fluorochemicals, and polyolefins, remain on the target surface after removal of the color- matching article from the target surface.. In addition, it has been found that plasticizers may be present in the color-matching articles and can transfer to the target surface without interfering with the adhesion or appearance of the intended application of the paint formulation.
In some embodiments, the adhesive is solvent resistant according to the Solvent Resistance Test described in the examples below. It has been found that certain pressure sensitive adhesives cannot withstand the wax and grease remover solvents used to prep target surfaces, particularly target surfaces in the automotive industry, and will therefore be unable to adhere to the target surface. It has also been found that certain pressure sensitive adhesives cannot withstand the solvents used in clear-coat simulation as described above. Solvent resistance may be achieved by choosing the correct input polymer or crosslinking the polymer to enhance or effectively increase the molecular weight. Alternatively a solvent resistant base polymer can be used. The base polymer can be encompassed by an interpenetrating network of a pressure-sensitive adhesive that is crosslinked to itself and to the base polymer.
In some embodiments, the adhesive is self-wetting. Unless otherwise indicated, "self wetting" refers to an adhesive which is very soft and conformable and is able to be applied with very low lamination pressure. Such adhesives exhibit spontaneous wet out to surfaces. The adhesives exhibit great conformability permitting them to spontaneously wet out substrates. The surface characteristics also permit the adhesives to be bonded and removed from the substrate repeatedly for repositioning or reworking.
It has been observed that unwanted deformations in the color matching article can cause changes in its surface appearance and result in difficulty in assessing a proper color match. These deformations can be caused by non-uniform adherence of the color matching article either to the release liner or the target surface. One example of unwanted deformation is bubbles forming between the color matching article and the surface to which it is applied. Bubbles can occur when air becomes trapped between the color matching article and the underlying surface. To address this issue, the color matching article and/or the release liner may comprise an air release structure 320.
The topography of the air release structure 320 may comprise any structure suited to provide sufficient air egress. For example, the air release structure may be formed by abrasion to create a roughened surface sufficient to allow the desired air egress. Alternatively, or in combination with a roughened surface, the air release structure may comprise a plurality of discrete protrusions 330 extending normally from the surface upon which it is disposed, with the plurality of protrusions 330 being separated by one or more discrete air passages 340. When a color matching article according to the present disclosure is placed upon a surface comprising an air release structure 320 (or when the color matching article itself comprises an air release structure), air that could otherwise become trapped and form bubbles between the color matching article and the surface is permitted to egress. Formation of bubbles under the color matching article is thereby mitigated or prevented.
Where the air release structure comprises discrete protrusions 330, they may take any suitable form or shape, so long as they are separated by one or more air passages 340 in a manner sufficient to effectively release air from the interface between the color matching article and the underlying surface. For example, the protrusions 330 may comprise raised dots, raised polygons, raised irregular shapes, microrep Heated patterns, or combinations thereof. The protrusions 330 may be distributed uniformly, in a repeating pattern, randomly, or combinations thereof.
As shown in the appended figures, the features of an air release structure may be dimensioned in various ways, so long as sufficient air egress can be achieved. For example, as shown in Figure 7, discrete protrusions 330 can extend a feature height "D" from the surface from which they protrude. As shown in Figures 12-17, discrete protrusions may comprise a feature size "A," a center-to-center feature spacing "B," and a feature-to-feature spacing "C." As can be seen in Figures 14-16, wherein the discrete protrusions are in the shape of squares, the feature size "A" is determined as an effective diameter (shown as a dotted line). As used herein, "effective diameter" means the diameter of a theoretical circle having the same area as the actual shape. For example, for a square having a side length of 1 cm and an area of 1 cm2, the effective diameter of that square would be 1.128 cm. An effective diameter can be calculated for any shape and is not limited to squares. In some embodiments, such as the random or regular offset row dot patterns shown in Figures 12 and 13, spacing between adjacent features - whether center-to-center ("B") or feature -to- feature ("C") may not be uniform, and thus an average of these dimensions can be used.
The protrusions 330 of the air release layer may be created by any suitable method. For example, a smooth surface may be modified (such as by compression or material removal) to create one or more air passages 340 recessed therein, thereby effectively resulting in protrusions 330 between the recessed air passages 340. Alternatively, discrete protrusions 330 may be formed on a smooth surface by methods such as screen printing, electrographic printing, offset printing, flexographic printing, gravure printing, inkjet printing, or thermal mass transfer printing. In still other embodiments, a formable material may be coated onto a smooth surface and subsequently embossed with a tool to create protrusions 330 in the formable material. Where protrusions 330 are formed from a different or independent material from the underlying major surface (i.e., where material is added to create the protrusions 330), the protrusions 330 may be formed from, for example, a resin or an ink. In some embodiments, the adhesive may comprise an air release structure. Adhesive topography or structure can be controlled using microreplication techniques such as in U.S. Pat. No. 6,91 1,243.
The relative size and height of the protrusions 330, as well as the pattern and spacing (i.e., by air passages 340) may be chosen such that effective air removal is achieved. However, it has been observed in some circumstances that providing too much space between protrusions 330 - and/or protrusions 330 that are too tall relative to their spacing from one another - can result in unwanted deformation of the color match article. For example, in some circumstances, a color matching article can inherit the pattern of the protrusions 330. Moreover, a more deformable color matching article (e.g., formed from a thinner, more flexible material) may increase the severity of this phenomenon, and thereby tolerate lesser protrusion spacing and height. In the examples described below, a 2 mil (50.8 micrometer) thick polyester film was used. It is expected that the performance for air release and pattern transfer would change depending on the material and thickness of the color match article, and therefore that different air release structure may be suitable for different film types. Therefore, one skilled in the art, guided by the teachings herein, could choose a combination of color match article and air release structure to achieve suitable air egress and lack of pattern transfer as desired for a particular application. Depending on the color match film chosen, the following exemplary air release structure dimension ranges - selected in appropriate combinations - may be desirable: Feature Size "A" (300 μηι to 1800 μηι); Center-to-Center Feature Spacing "B" (500 μηι to 1900 μηι); Feature -to-Feature Spacing "C" (20 μηι to 1200 μτη); Feature Height "D" (1 μηι to 60 μτη).
For the CFA- 1 color match article used herein - and for films of comparable thickness and material characteristics - , the following exemplary air release structure dimension ranges - selected in appropriate combinations - may be desirable: Feature Size "A" (300 μηι to 1800 μτη); Center-to- Center Feature Spacing "B" (500 μηι to 1 100 μτη); Feature-to-Feature Spacing "C" (30 μηι to 300 μτη); Feature Height "D" (1.5 μm to 30 μτη). Choice of dimensions will depend on, for example, the degree of pattern transfer - if any - that is allowable.
In a preferred embodiment, the air release structure comprises the following exemplary air release structure dimension ranges: Feature Size "A" (300 μηι to 800 μτη); Center-to-Center Feature Spacing "B" (500 μηι to 800 μτη); Feature-to-Feature Spacing "C" (30 μηι to 100 μτη); Feature Height "D" (1.5 μm to 10 μιη).
In another preferred embodiment, the air release structure comprises the following exemplary air release structure dimension ranges: Feature Size "A" (500 μηι to 700 μτη); Center-to- Center Feature Spacing "B" (500 μηι to 800 μτη); Feature-to-Feature Spacing "C" (40 μηι to 80 μτη); Feature Height "D" (2 μm to 8 μτη). Example Preparation for Air Release Structure - Examples A-F
To create Examples A-F, release liners made according to Release Surface RS-3 herein were utilized, except that the film thickness was 6.9 mil (175.3 μηι). A structure was created on the back side (the second major surface) of the release liners. The "back" is defined as the rear of the film having reverse printing. The color-matching articles used in Examples A-F comprised a film made according to CFA- 1 herein.
Screen Printing Procedure - Examples A-C
Dot patterns were printed on the back of the sample articles via hand spreads. 3M Scotch Magic™ Tape (Cat. 810) loops were made and placed on the face side of the article. The articles were placed face side down and secured to the coated side of a 12 inch (30 cm) by 20 inch (51 cm) piece of C-weight olive brown paper with the tape loops, obtained from Wausau Paper Company, Wausau, WI, subsequently saturated with a styrene -butadiene rubber, in order to make it waterproof. A framed stencil or mesh was placed over the article. Approximately lOg of epoxy/acrylate make coat resin, with purple pigment and at 70°F (21.°1C), was spread over the mesh by securing the frame at the top end with one hand and using a urethane squeegee at a 10-15 degree angle with the other to draw the resin across the mesh. The framed mesh was then carefully removed, revealing a dot pattern on the back of the article. The article, still attached to the paper, was then taped to a 12 inch (30 cm) by 20 inch (51 cm) metal panel. The article was cured by passing the panel once through a UV processor, available from American Ultraviolet Company, Murray Hill, New Jersey, using two V-bulbs in sequence operating at 400 W/inch (157.5 W/cm) and a web speed of 58ft/min (17.68 m/min), corresponding to a total dose of approximately 510 mJ/cm2. The above procedure was used to prepare Examples A-C.
Example A was created utilizing a 3 mil (76.2 μηι) thick polyester stencil having a regular pattern of offset rows of 0.015 inch (0.038 cm) diameter holes spaced apart on 0.305 inch (0.775 cm) centers. For reference, exemplary regular patterns of offset rows of dots spaced apart on known centers are depicted in Figures 13 and 17.
Example B was created utilizing a 1 mil (25.4 μηι) thick stainless steel stencil with 0.030 inch (.076 cm) diameter holes randomly spaced. For reference, a exemplary randomly spaced dot distribution is depicted in Figure 12.
Example C was created utilizing a 305 mesh having a regular pattern of offset rows of 0.012 inch (0.031 cm) diameter holes spaced apart on 0.0265 inch (0.0673 cm) centers.
Abrading Procedure - Example D
Example D was created via abrading the back of the article, by hand, with a maroon 3M Scotchbrite™ pad, back and forth five times with sufficient pressure to create a unidirectional pattern of abrasions. For reference, a schematic representation of a unidirectional pattern of abrasions is depicted in Figure 18.
Surface Finish Measurement
The surface finish of a work piece is defined by Rz and Ra. Rz is determined by calculating the arithmetic average of the magnitude of the departure (or distance) of the five tallest peaks of the profile from the meanline and by calculating the average of the magnitude of the departure (or distance) of the five lowest valleys of the profile from its meanline. These two averages are then added together to determine Rz. Ra, is the arithmetic mean of the magnitude of the departure (or distance) of the profile from its meanline. Both Rz and Ra were measured in three places on each of two replicates using a profilometer, available under the trade designation "SURTRONIC 3+ PROFILOMETER" from Taylor Hobson, Inc., Leicester, England. The length of scan was 0.03 inches (0.0762 centimeters). For puroposes of the examples herein, Rz was used for Feature Height "D."
For the sake of comparison with the feature height of the other Examples herein, the standard surface finish units for Rz (microinches) are converted to micrometers in Table I. A non- abraded film of the same type was measured by the same technique to have an Rz of 35 microinches (0.89 μιη). Lamination Procedure - Examples E-F
Example E was created using 3M Super 77™ Multi Purpose Spray Adhesive to attach an embossed liner, which has a cross hatch pattern, to the back of the article. The dimensions of the cross hatch pattern of Example E are listed in Table I. Exemplary cross hatch patterns (in this case squares) are schematically depicted in Figures 14-16. The liner was applied, starting at the leading edge, using a hand roller to ensure smooth attachment.
Example F was created using 3M Super 77™ Multi Purpose Spray Adhesive to attach a film, which has a cross hatch pattern, to the back of the article. The film was applied, starting at the leading edge, using a hand roller to ensure smooth attachment.
Examples A-F are summarized in Table I below.
Table I.
Summary of Examples A-F
Figure imgf000019_0001
Example Preparation for Air Release Structure - Examples G-D'
To create Examples G-D', a 6.9 mil (175.3 μηι) polyester film, primed on one surface with an ink-receptive layer was utilized. A structure was created on the back side (the second major surface) of the film by using a flexographic printing process. A flexographic printing plate with a four up pattern was utilized to create four patterns simultaneously. The four patterns are listed in Table II below. The printed films were sheeted into 7.5 inch by 10 inch sheets each containing two of the four patterns. These sheets were then subjected to the six different coating conditions ("Trials") according to Table III below. The feature height was subsequently measured in the laboratory using an automated micrometer (Precision Micrometer Model #49-60 manufactured by TESTING MACHINES, INC., Amityville, NY).
As used in Table III, the terms "Anilox Screen Count," "Anilox Cell Volume," "LPI," and
"BCM" refer characteristics of an Anilox roll used to transfer ink from an ink reservoir to a flexographic printing plate, as would be known to those skilled in the art of flexographic printing. Anilox Screen Count refers to the number of cells per linear inch ("LPI"). Screen count is measured at the angle of engraving, and can be provided in a range from, for example, 50 LPI to 1200 LPI. Anilox Cell Volume refers to the volume of one cell in units of billionth cubic microns ("BCM").
Two different coating materials were used in the flexographic printed examples herein. For instance, the white ink used in Trials 1 -3 was NUVAFLEW 34 SERIES OPAQUE PRIME WHITE, Product Code 3405, available from ZELLER GMELIN RPrNTING INKS of Richmond, Virginia. However, it is anticipated that any coating material could be used to provide sufficient air egress and lack of pattern transfer. Different coating materials may be selected to provide or avoid other characteristics. For example, the tactile varnish used in Trials 4-6 imparted a tactile stickiness or friction to the air release structure such that the samples, when stacked upon one another (as they might be for packaging purposes), did not readily slide relative to one another. This characteristic may be beneficial in some applications, or may not be desired in others. It is anticipated that a user could choose the coating material according to their particular need. Table II.
Summary of Pattern Types for Flexographic Printed Examples G-D'
Figure imgf000020_0001
Table III.
Summary of Trial Types for Flexographic Printed Examples G-D'
Figure imgf000021_0001
To assess for air release and pattern transfer in Examples A-D', a film as in CFA-1 herein was adhered to the textured surface of each article by hand (mimicking the manual procedure that would be used by a painter in a body shop), attempting to apply even pressure. Bubbles were assessed by visually identifying and measuring, whereupon a rating was given to each example according to Table IV. Pattern transfer was assessed by whether the underlying feature pattern - or a portion thereof - could be identified with the unaided eye through the color match article when firmly applied to the release liner. Any amount of pattern transfer caused the example to receive a "Yes" in Table V, however some nominal degree of pattern transfer may be acceptable in practice. Results are summarized in Table V below.
Table IV.
Air Release Ratings Description
Figure imgf000021_0002
Table V.
Air Release and Pattern Transfer Results
Figure imgf000022_0001
The asterisks in Table V denote Examples that exhibited both acceptable air egress and no pattern transfer. Again, it is believed that these results may change with color match articles having differing film characteristics, and the selected Examples are therefore not intended to limit the scope of the disclosure.
It should be noted that, although abraded Example D did not exhibit sufficient air egress, other abraded examples were created and exhibited sufficient air egress without causing pattern transfer. For example, samples of the same film as used for Example D were abraded, measured to have an Rz (Feature Height "D") in a range from 1 1.4 μηι to 32.2 μηι, and were found to exhibit sufficient air egress and lack of pattern transfer when testing with a CFA-1 color match article.
The color-matching article can optionally comprise a first color layer disposed on the first major surface of the substrate. The first color layer can comprise one or more layers of ink or primer coatings. In some embodiments, the first color layer comprises a white or gray ink printed onto the first major surface of the substrate. The inks and primers can be solvent-based, water-based or 100 % solids. In some embodiments, the inks and primers are free of contaminants or flow control additives that can influence the wet-out of paint on the surface of the first color layer or adhesion of paint onto the surface of the first color layer, e.g. low-surface-energy components such as silicones, fluorochemicals, polyolefins, but in some embodiments, the inks may comprise minor amounts, for example, less than 0.5% by weight, of these contaminants. In some embodiments, the inks and primers contain no deliberately- added low-surface-energy components such as silicones, fluorochemicals, or polyolefins. In some embodiments, the inks or primers contain trace or nominal levels of low-surface-energy components such as silicones, fluorochemicals, and polyolefins. The color-matching articles can be supplied as pre-colored films that are colored with typical primer colors for the desired end use. In some embodiments, colors for the ink or primer layers include white, light gray (Pantone PMS 421), medium gray (Pantone PMS 423), and dark gray (Pantone PMS 425). Exemplary printing inks can be obtained from Zeller-Gmelin Printing Inks (Germany) and Flint Group (USA).
In some embodiments, the color-matching article has a total average edge thickness (i.e. the combined thickness of the substrate, the adhesive layer, and any optional layers, including the first color layer) ranging from 1.0 to 12.0 mils (25.4 μηι to 304.8 μηι). In some embodiments, the color- matching article has a total an average edge thickness of 10 mil or less, such as 9 mil or less, 8 mil of less, 7 mil or less, 6 mil or less. This edge thickness allows better assessment of the paint formulation by avoiding edge effects caused by thicker articles. The edge thickness may be measured by any suitable method such as, for example, using thickness gauges.
The color-matching articles of the present invention are flexible such that they are capable of conforming to two dimensional compound surfaces (e.g., surfaces with non-planar surface topography). In some embodiments, the color-matching articles are flexible enough to conform to contours of the target surface. Color-matching articles having sufficient flexibility to conform to two-dimensional compound surfaces and the contours of the target surface include color-matching articles having a drape of 3 inches (7.62 cm) or less according to the Flexibility Test described in the Examples below.
The color-matching articles of the present invention can be releasably adhered to a release liner as part of a color-matching system. The release liners described herein comprise a base layer. The base layer can comprise a paper, a film, or a composite of a paper and a film. In some embodiments, the base layer provides the rigidity needed for the method of application. For example when a spray technique is used to apply the paint formulation to the color-matching article, the rigidity of the base layer may resist the force of the sprayed paint. In some embodiments, for example for a spray application, a 10 to 20 point board is may be used. In some embodiments the base layer is calendared so at least on one side of the base layer is smooth. In some embodiments, the base layer may be a film. A variety of film compositions may be used. In some embodiments, e.g. where the paint requires curing, the film chemistry of the base layer is compatible with the curing and the painting process. Exemplary films can include films of polyester, polybutyl phthalate, polycarbonate, polystyrene, polypropylenes, polyethylenes, polyvinyl chloride, polyvinyl acetate, acrylic, polyurethanes, copolymers thereof, or multilayer composites thereof. In some embodiments, paper and film may be laminated together or a film can be coated on the paper to provide the balance of properties required for the desired application. In some embodiments, the base layer is transparent. In some embodiments, the base layer is achromic, while in some embodiments, the base layer is colored. In some embodiments, the base layer comprises less than 0.5% by weight of silicones, fluorochemicals, or polyolefins. In some embodiments, the base layer contains no deliberately-added low-surface-energy components such as silicones, fluorochemicals, or polyolefins. In some embodiments, the base layer contains trace or nominal levels of low-surface- energy components such as silicones, fluorochemicals, and polyolefins. In some embodiments, the base layer is essentially free of or contain no low-surface-energy components such as silicones, fluorochemicals, and polyolefins.
The release liners can optionally further comprise a varnish layer. The optional varnish layer can comprise a low-adhesion backsize layer. Suitable materials for forming low adhesion backsize layer are known in the art and may be selected, for example, with reference to the type of pressure sensitive adhesive chosen for adhesive layer. Low-adhesion backsize materials include, for example, long chain branched polymers (e.g., copolymers of alkyl acrylate and acrylic acid, stearyl methacrylate-acrylonitrile copolymer), polyvinyl carbamates (e.g., polyvinyl N-octadecyl carbamate), fiuorocarbon polymers, and amines. In some embodiments, the release layer is achromic so that it does not impart color to the color-matching article. In some embodiments, the components in the low adhesion backsize layer do not migrate or contaminate the paint preparation area.
Examples of low adhesion backsize materials are reported, for example, in Chapters 23-24 of Satas, Handbook of Pressure Sensitive Adhesive Technology, 2nd Edition, 1989, Van Nostrand Reinhold (ISBN 0-442-28026-2). In some embodiments, the paint formulation can adhere to the optional varnish layer after the varnish layer has been applied to the base layer and cured.
In some embodiments, the optional varnish layer contains no deliberately-added low- surface- energy components such as silicones, fluorochemicals, or polyolefms. In some
embodiments, the varnish layer contains trace or nominal levels of low-surface-energy components such as silicones, fluorochemicals, and polyolefms. In some embodiments, the varnish layer is essentially free of or contains no low-surface-energy components such as silicones, fluorochemicals, and polyolefms. In some embodiments, the optional varnish layer comprises less than 0.5% by weight of silicones, fluorochemicals, or polyolefms.
Because the base layer and optional varnish layer of the release liner comprise less than
0.5% by weight of silicones, fluorochemicals, or polyolefms; contain trace or nominal levels of silicones, fluorochemicals, or polyolefms; or are essentially free of silicones, fluorochemicals, or polyolefms, or the paint formulations can adhere to the release liner, for example in embodiments of the method where the paint formulation is applied to at least a portion of the release liner. In addition, the paint adheres strongly, e.g., the paint formulation will not be removed from the release liner by the adhesive of the color-matching article if the color-matching article is placed back on the release liner over the painted portion of the release liner and subsequently removed.
In some embodiments, the release liner optionally comprises a pattern layer disposed on at least a portion of the release liner. In some embodiments (e.g., Fig. 2B), the pattern layer may be disposed between at least a portion of the first major surface of the base layer and the optional varnish layer. In some embodiments (Fig. 2C), the pattern layer may be disposed on at least a portion of the second major surface of the base layer. In some embodiments (Fig. 2E), the pattern layer may be disposed between at least a portion of the second major surface of the base layer and the optional second color layer. In some embodiments, the pattern layer may comprise ink and may be applied to the base layer or pattern layer by any known method for forming an image on a base film, including, for example, screen printing, electrographic printing, offset printing, flexographic printing, gravure printing, inkjet printing, or thermal mass transfer printing.
In some embodiments, the release liner further comprises an optional second color layer. In some embodiments (e.g., Figs. 2D-2E), the second color layer may be disposed on at least a portion of the second major surface of the base layer. In some embodiments, the second color layer may comprise ink and may be applied to the base layer or pattern layer by any known method for forming an image on a base film, including, for example, screen printing, electrographic printing, offset printing, flexographic printing, gravure printing, inkjet printing, or thermal mass transfer printing.
In some embodiments, the pattern layer and the second color layer together provide a contrast ratio of 0.6 to 1.0. The contrast ratio is calculated by measuring the CIE Lab color values over a white substrate and over a black substrate in the reflectance mode. The ratio of the L* value over the black substrate to L* value over the white substrate is calculated to produce a contrast ratio. This is a common measure of opacity.
The release liner is typically more rigid than the color-matching article. In some embodiments, the release liner is sufficiently rigid to withstand the pressure of a paint spray gun. In some embodiments, the release liner is rigid enough such that it exhibits a drape of greater than 5 inches (12.7 cm) according to the Flexibility Test described in the Examples below.
Illustrative embodiments of the color-matching articles, systems, and methods are discussed and reference has been made to some possible variations. These and other variations and modifications in the invention will be apparent to those skilled in the art without departing from the scope of the invention, and it should be understood that this invention is not limited to the illustrative embodiments set forth herein. Accordingly, the invention is to be limited only by the claims provided below and equivalents thereof.
Examples
Unless otherwise noted, all reagents were obtained or are available from fine chemical vendors, such as Sigma- Aldrich Company, St. Louis, Missouri or may be synthesized by known methods. Unless otherwise reported, all ratios are by weight percent. As reported herein, room temperature is defined as approximately 70 - 75°F (21.1 - 23.9°C). The following abbreviations are used to describe the examples:
°C: degrees Centigrade
cm: centimeter
°F: degrees Fahrenheit
HVLP: high volume low pressure
L: liter
mil: 10"3 inches
min: minute
mL: milliliter
mm: millimeter
μηι: micrometer
RH: relative humidity
As reported herein, room temperature is defined as approximately 70 - 75°F (21.1 - 23.9°C).
The following abbreviations are used to describe materials used in the examples:
ATT-9415: A double-sided adhesive transfer tape, having opposing low- and high- tack adhesive layers, part number "09415", obtained from 3M Company, St. Paul, Minnesota. ATT-9457: An adhesive transfer tape, having a high-tack adhesive coated on a double-sided release liner, part number "09457", obtained from 3M Company.
RNK-2600: A 2 mil (50.8 μηι) clear polyester film, having a single-sided primed surface, obtained under the trade designation "HOSTAPHAN RNK-2600" from Mitsubishi Films, Greer, South Carolina.
WCS: A double-sided smooth calendared 10-point board white cardstock, obtained from
Meyers Printing, Brooklyn Center, Minnesota, having on one side a printed text pattern by means of a model "Hewlett Packard PHOTOSMART C4780" ink jet printer.
7717SW: A single, silicone-free, adhesive layer sandwiched between optically clear and white pigmented 2-mil (50.8 μηι) polyester films, obtained under the trade designation "7717SW" from 3M Company.
SC160-10: A 4 mil (101.6 μηι), white polyvinyl chloride film having, on one surface, a removable acrylic adhesive covered by a silicone treated paper release liner, obtained under the trade designation "SCOTCHCAL 160-10" from 3M Company.
CT 180-31 : A light grey 2 mil (50.8 μηι) cast polyvinyl chloride film having, on one surface, a removable acrylic adhesive covered by a silicone release liner, obtained under the trade designation "CONTROLTAC GRAPHIC MARKING SYSTEM 180-31" from 3M Company.
IJ180CV3- 10: A white 2 mil (50.8 μηι) cast polyvinyl chloride film having, on one surface, a microstructured adhesive layer, obtained under the trade designation "CONTROLTAC GRAPHIC MARKING SYSTEM IJ180CV3-10" from 3M Company.
Release Surface 1 (RS-1)
102 grams of octadecylacylate (ODA) (50% solids in ethyl acetate), 1 1 grams of methyl acrylate (MA), 25 grams of acrylonitrile (AN), 13 grams of acrylic acid (AA), 0.5 grams of 2,2'- azobisisobutyronitrile (AIBN) and 182 grams of ethyl acetate were added to a 1 -quart (946.4 mL) amber colored glass bottle at room temperature. The mixture was purged with nitrogen at 1 L/min for 3 minutes, the bottle sealed and then tumbled in a constant temperature water bath at 65°C for 48 hours. The resulting acrylic polymer was cooled to 21°C and diluted to 2.5% by weight solids with toluene. The polymer solution was then coated onto a paper sprayout card, type "ARMC463 2/1 1" obtained from PPG Industries, Pittsburgh, Pennsylvania, using an "RDS04" type Meyer rod from RD Specialties, Webster, New York, and dried for 60 minutes at room temperature.
Release Surface 2 (RS-2)
The liner was removed from one side of the ATT-9457 transfer tape and the exposed adhesive face of the tape manually laminated to printed side of the WCS cardstock at room temperature by means of a laminator, model "LS950", from 3M Company. The release liner was removed from the opposing surface of the transfer tape and the film assembly then manually laminated to the non- primed surface of the RNK-2600N film. Feed tension during lamination was balanced to prevent curl and trapping bubbles of the laminated assembly.
Release Surface 3 (RS-3)
A 7 mil (177.8 μηι) polyester film, primed on one surface with an ink-receptive layer. A horizontal line pattern was produced on one surface of the film using a black fine point permanent marker pen, trade designation "SHARPIE" from Newell Rubbermaid Products, Oak Park, Illinois. The pattern was then spray coated with two successive coats of a white primer, type "RUST-OLEUM
PAINTPLUS, PART No. 249058" from Rust-Oleum Corporation, Vernon Hills, Illinois, drying for 5 minutes at room temperature between each application, then allowed to dry for an additional 2 hours.
Colored Film Assembly 1 (CFA-1)
A commercial flexographic printer applied two layers of a UV curable white ink to the optically clear polyester film of 7717SW, cured the ink, then applied one layer of a translucent UV curable gray ink that matched PANTONE PMS 421 LIGHT GRAY, and again cured the ink.
Colored Film Assembly 2 (CFA-2)
A 24 by 24 inch (60.96 by 60.96 cm) sheet of SC160-1 was sprayed with a gray primer, type "RUST-OLEUM PAINTER'S TOUCH ULTRACOVER FLAT GRAY, PART No. 249088" at room temperature, allowed to partially dry for 5 minutes, after which a second coat was applied and the sheet dried for an additional 2 hours. The sheet was then converted into 4 by 6 inch (10.16 by 15.24 cm) segments. Colored Film Assembly 3 (CFA-3)
The release liner was removed from a 4 by 6 inch (10.16 by 15.24 cm) sheet of the CT180-31 film and laminated to the non-adhesive surface of an equally sized sheet of IJ180CV3- 10 film, by means of the LS950 laminator at room temperature. The laminated assembly was then converted into a 3.5 by 6 inch (8.89 by 15.24 cm) sheet.
Colored Film Assembly 4 (CFA-4)
The liner was removed from one side of a 6 by 30 inch (15.24 by 76.20 cm) sheet of the ATT-9415 and the non-primed surface of a 6 by 30 inch (17.78 by 76.20 cm) sheet of RNK-2600N polyester film manually laminated to the transfer tape of by means of the LS950 laminator at room temperature. The non-primed face of the RNK-2600N film was then sprayed with the Part No.
249088 flat gray primer at room temperature, allowed to partially dry for 5 minutes, after which a second coat was applied and the sheet dried for an additional 2 hours. Example 1
A sheet of CFA-2 was trimmed to 3.75 by 6 inches (9.53 by 15.24 cm), the liner removed, and the sheet centrally positioned over a 4.25 by 6.5 inch (10.80 by 16.51 cm) sheet of RS-1, thereby providing an exposed 0.25 inch (10.16 mm) border of the release surface. The assembly was then laminated at room temperature by means of the LS950 laminator.
Example 2
The procedure generally described in Example 1 was repeated, wherein both the CFA-2 and RS- 1 were trimmed to 3.5 by 5.5 inches (8.89 by 13.97 cm), thereby eliminating the exposed border of the release surface.
Example 3
The procedure generally described in Example 1 was repeated, wherein the CFA-2 was replaced by CFA-3.
Example 4
The procedure generally described in Example 2 was repeated, wherein the CFA-2 was replaced with CFA-3.
Example 5
The procedure generally described in Example 1 was repeated, wherein the CFA-2 was replaced with CFA-4. Example 6
The procedure generally described in Example 1 was repeated, wherein the CFA-2 was replaced with CFA-5.
Example 7
The procedure generally described in Example 1 was repeated, wherein the CFA-2 was replaced with CFA-1 and the RS-1 was replaced with RS-2.
Example 8
The procedure generally described in Example 2 was repeated, wherein the CFA-2 was replaced with CFA- 1 and the RS- 1 was replaced with RS-2. Example 9
The procedure generally described in Example 7 was repeated, wherein the RS-2 was replaced with RS-3. Example 10
The procedure generally described in Example 7 was repeated, wherein the RS-2 was replaced with RS-3.
Test Methods
Paint Adhesion Tests
a. Solvent Based Paint Adhesion Test
A silver colored solvent based automotive paint, type "DELTRON 2000 BASECOAT", matching Color Code 5451 , from PPG Industries in Strongsville, Ohio, was mixed in a disposable paint cup assembly, trade designation "PPS", from 3M Company. The paint was then sprayed onto the example using a model "SATA JET 4000 NR" HVLP paint gun from Sata GmbH, Komwestheim, Germany, employing a 1.3 mm tip at 30 psi (206.8 kPa) gauge pressure and 8 - 10 psi (55.2 - 69.0 kPa) air cap pressure, at room temperature. After 5 minutes a second coat was applied and the example dried for 60 minutes. Two coats of "DC3000 SERIES DELTRON HIGH VELOCITY CLEARCOAT", in a 4: 1 by volume ratio of clearcoat to "DCH3085" hardener, both obtained from PPG Industries, were then applied in a similar fashion to the paint coats, after which the example was dried for 2 hours at room temperature. A piece of adhesive tape, trade designation "MAGIC TAPE 91 1" from 3M Company, was firmly applied to the painted film surface and, in the case of the odd numbered examples, including the painted exposed released layer. The tape was then manually peeled off at a rate of approximately 230 cm/min and the percentage area of paint removed by the tape recorded. b. Water Based Paint Adhesion Test
The process generally described in the solvent based paint adhesion test was repeated, wherein the solvent based silver paint was replaced with a water based version, type "ENVIROBASE", again matching PPG Color code 5451.
Results for the paint adhesion tests are reported in Table 1. TABLE 1
Figure imgf000031_0001
180 Degree Peel Adhesion Tests
a. Painted Panel : Film Adhesive Layer
A black painted steel test panel having a "DUPONT RK 8148" clearcoat finish, was obtained from ACT Laboratories, Inc., Hillsdale, Michigan. The adhesive side of a 1 by 4 inch (2.54 by 10.16 cm) example was positioned over the test panel such that approximately 3 inches (7.62 cm) of the adhesive coated example contacted the clearcoat surface and the remaining 2.54 cm extended beyond the edge of the panel. The example was then manually laminated to the test panel using a rubber roller at an approximate force of between 3-5 Kg, after which it was conditioned at room temperature and 50% RH for 2 hours. The extended portion of the example was clamped to the sensor of a model "SP- 102C 3090 adhesion test instrument, obtained from IMASS, Inc., Accord, Massachusetts. The force required to peel the example off the panel at an angle of 180 degrees, at a panel speed of 30.48 cm/min, over a 2 second interval, was then measured. b. Humidity Conditioned Release Layer : Film Adhesive Layer A 1 by 4 inch (2.54 x 10.16 cm) example was conditioned at room temperature and 50% RH for 24 hours. A 1-inch (2.54 cm) length of the release layer was peeled back from the example and fastened to the platen of the adhesion test instrument. The instrument sensor was then fastened to the exposed 1-inch (2.54 cm) length of adhesive coated film and the force required to peel the example off the panel at an angle of 180 degrees, at a panel speed of 228.6 cm/min, over a 2 second interval, was measured. c. Thermally Conditioned Release Layer : Film Adhesive Layer
The procedure generally described in the humidity conditioned peel test was repeated, wherein the example was thermally conditioned for 24 hours at 70°C rather than humidity conditioned at room temperature and 50% RH.
Results for 180 degree peel adhesion tests are reported in Table 2.
TABLE 2
Figure imgf000032_0001
Color Measurement
CIE 1976 L*a*b* values of the examples were measured over standard black and white substrates using a "MODEL MA681 1" spectrophotometer, obtained from X-Rite Corporation, Granville, Michigan, under D65 illumination, 12 mm viewing area and a 10 degree viewing angle. The contrast ration was calculated as a function of opacity in the reflectance mode. Results are listed in Table 3. TABLE 3
Figure imgf000033_0001
Solvent Resistance Test
The resiliency of the colored film assembly (CFA) adhesive to a commercial solvent was evaluated as follows. Ten drops of solvent, obtained under the trade designation "R859 WAX AND GREASE REMOVER" from AkzoNobel N.V., Amsterdam, the Netherlands, formed an approximately one inch (2.54 cm) diameter pool on the backside of the CFA sample. The solvent was then allowed to reside for 5 minutes at room temperature. Wearing a neoprene glove, the test area was manually rubbed with the index finger until the adhesive was removed. The time taken to remove the adhesive, and the ease with which it was removed, subjectively rated on a scale of 1 - 5, with 5 being the easiest, were recorded. Results are listed in Table 4.
TABLE 4
Figure imgf000033_0002
Drape Test
The ability of the film to conform to the contours of a vehicle was evaluated as follows. A 1 by 8 inch (2.54 by 20.32 cm) elongate strip of material was laid flat on a wood panel, its narrower edge aligned coterminous with the rim of the panel. The elongate strip was then slowly pushed beyond, and perpendicular to, the rim of the panel, until the edge of the strip deflected down 0.5 inches (1.27 cm) due to gravity. The distance the elongate strip extended beyond the panel rim was subsequently recorded. Subjectively, a film that deflected down 0.5 inches (1.27 cm) when extended less than 3 inches (7.62 cm) was considered flexible. Results are listed in Table 5. TABLE 5
Figure imgf000034_0001
Contamination Test
Confirmation that the color matching films do not impart contaminants or defects to a test panel was determined as follows. A water based silver paint was prepared using "ENVIROBASE" type base components, obtained from PPG Industries, Strongville, Ohio, according to PPG color code 5451. The color matching films were applied to a test panel and removed. The silver paint was then applied to the test areas using a model "NR 4000" spray gun with a 1.3 mm tip, obtained from SATA GmbH & Co., KG, Kornwestheim, Germany. Gauge pressure was set at 30 psi (206.8 kPa). None of the exemplary color matching films caused defects as evidenced by coating defects, including non wetted areas and non uniform appearance.
Various modifications and alterations to this invention will become apparent to those skilled in the art without departing from the scope and spirit of this invention. It should be understood that this invention is not intended to be unduly limited by the illustrative embodiments and examples set forth herein and that such examples and embodiments are presented by way of example only with the scope of the invention intended to be limited only by the claims set forth herein as follows. All references cited in this disclosure are herein incorporated by reference in their entirety.
Following are exemplary embodiments of a bis(glyoxime)-transition metal complexes and moisture indicators made therewith according to aspects of the present invention.
Embodiment 1 is a repositionable color-matching article comprising:
a flexible substrate having a first major surface and a second major surface disposed opposite the first major surface; and
a pressure-sensitive adhesive layer disposed upon the second major surface of the substrate; wherein the adhesive layer comprises a clean removal adhesive. Embodiment 2 is a color-matching article according to embodiment 1 , further comprising a first color layer disposed upon the first major surface of the substrate. Embodiment 3 is a color-matching article according to any one of embodiments 1 or 2, wherein the clean removal adhesive is solvent resistant according to the Solvent Resistance Test.
Embodiment 4 is the color-matching article of any one of embodiments 1 to 3, wherein the adhesive is self-wetting.
Embodiment 5 is a color-matching article according to any one of embodiments 1 to 4, wherein the adhesive comprises a silicone-free, urea-based adhesive.
Embodiment 6 is a color-matching article according to any one of embodiments 1 to 5, wherein the article has an average edge thickness of 10 mils or less.
Embodiment 7 is a color-matching article according to any one of claims 1 to 6, wherein the article exhibits a drape of 3 inches (7.62 cm) or less according to the Flexibility Test. Embodiment 8 is a color-matching system comprising the color-matching article according to any one of embodiments 1 to 7; and a release liner;
wherein the release liner comprises:
a base layer having a first major surface and a second major surface disposed opposite the first major surface; and
wherein the adhesive layer of the color-matching article is releasably adhered to the first major surface of the release liner; and
wherein the release liner comprises less than 0.5% silicone by weight.
Embodiment 9 is a color-matching system according to embodiment 8, wherein the release liner further comprises a varnish layer disposed on the first major surface of the base layer.
Embodiment 10 is a color-matching system according to any one of embodiments 8 or 9, wherein the release liner further comprises a pattern layer. Embodiment 1 1 is a color-matching system according to embodiment 10, wherein the pattern layer is disposed on at least a portion of the second major surface of the base layer. Embodiment 12 is a color-matching system according to embodiment 10, wherein the pattern layer is disposed on at least a portion of the first major surface of the base layer.
Embodiment 13 is a color-matching system according to any one of embodiments 8 to 12, wherein the release liner further comprises a second color layer disposed on the second major surface of the base layer, the pattern layer, or combinations thereof.
Embodiment 14 is a color-matching system according to any one of embodiments 8 to 13, wherein one or more edges of the release liner extend beyond one or more edges of the color- matching article.
Embodiment 15 is a color-matching kit comprising:
the color-matching system of any one of embodiments 8-13; and
an applicator.
Embodiment 16 is a color-matching kit of embodiment 15, wherein the applicator is selected from a squeegee or a roller.
Embodiment 17 is a color-matching kit of any one of embodiments 15-16, further comprising a clear-coat-simulating article, a clear-coat formulation, or a clear-coat-simulating formulation.
Embodiment 18 is a method of color-matching a paint formulation to a target surface having a color, the method comprising:
(a) applying the paint formulation over at least a portion of the repositionable color- matching article of any one of embodiments 1-7 or 32;
(b) adhering the color-matching article to a portion of the target surface with the adhesive layer;
(c) comparing the paint formulation on the color-matching article to the target surface; and (d) determining whether the paint formulation on the color-matching article closely matches the color of the target surface.
Embodiment 19 is a method according to embodiment 18, further comprising the step of: (bl) adhering a clear-coat-simulating article or applying a clear-coat formulation or clear- coat-simulating formulation over the color-matching article. Embodiment 20 is a method according to any one of embodiments 18 or 19, further comprising:
(e) removing the color-matching article from the target surface, wherein upon removal, no contaminants remain on the target surface according to the Contamination Test.
Embodiment 21 is a method according to embodiment 20, further comprising:
(f) repeating steps (a)-(c) or (a)-(e).
Embodiment 22 is a method of color-matching a paint formulation to a target surface having a color, the method comprising:
(a) applying the paint formulation over at least a portion of the color-matching article of the color-matching system of any one of embodiments 8 to 14 or 33;
(b) removing the color-matching article from the release liner;
(c) adhering the color-matching article to a portion of the target surface with the adhesive layer;
(d) comparing the paint formulation on the color-matching article to the target surface; and
(e) determining whether the paint formulation on the color-matching article closely matches the color of the target surface.
Embodiment 23 is a method according to embodiment 22, wherein step (a) further comprises applying the paint formulation over at least a portion of the release liner; and wherein the paint formulation adheres to the release liner. Embodiment 24 is a method according to any one of embodiments 22 or 23, further comprising the step of:
(cl) adhering a clear-coat-simulating article over the color-matching article.
Embodiment 25 is a method according to any one of embodiments 22 to 24, further comprising:
(f) removing the color-matching article from the target surface.
Embodiment 26 is a method according to embodiment 25, further comprising:
(g) repeating steps (a)-(e), or (a)-(f).
Embodiment 27 is a method according to any one of embodiments 22 to 26, wherein the release liner comprises a pattern layer, further comprising: (al) assessing visibility of the pattern layer through the paint layer.
Embodiment 28 is a method according to any one of embodiments 18-27, wherein the target surface comprises a surface topography, wherein the color-matching article conforms to the surface topography upon adhering the color-matching articles to a portion of the target surface with the adhesive layer.
Embodiment 29 is a method according to embodiment 28, wherein the surface topography is non-planar.
Embodiment 30 is a method according to any one of embodiments 18-29, wherein in step (a) the paint formulation is applied over at least a portion of the first major surface of the substrate to form a paint layer on the color-matching article. Embodiment 31 is a method according to any one of embodiments 18-29, wherein the color- matching article further comprises a first color layer disposed on the first major surface of the substrate and wherein in step (a) the paint formulation is applied over at least a portion of the first color layer to form a paint layer on the color-matching article. Embodiment 32 is a repositionable color-matching article of any of embodiments 1-7 wherein the adhesive layer comprises an air release structure.
Embodiment 33 is a color-matching system of any of embodiments 8-14 or 32 wherein the release liner comprises an air release structure.
Embodiments 34 is a color matching system of embodiment 33 wherein the air release structure is disposed on at least one of the first major surface or the second major surface.
Embodiment 35 is a color-matching kit comprising the color-matching system of embodiment 34 and an applicator.
Embodiment 36 is a color matching system component comprising an air release structure on a major surface thereof. Embodiment 37 is a component as in embodiment 36 wherein the air release structure comprises discrete protrusions having an average feature size in a range from 300 micrometers to 1800 micrometers. Embodiment 38 is a component as in any of embodiments 36-37 wherein the air release structure comprises discrete protrusions having an average feature height in a range from 1 micrometer to 60 micrometers.
Embodiment 39 is a component as in any of embodiments 36-38 wherein the air release structure comprises discrete protrusions having an average center-to-center spacing in a range from 500 micrometers to 900 micrometers. Embodiment 40 is a component as in any of embodiments 36-39 wherein the air release structure comprises discrete protrusions having an average feature-to-feature spacing in a range from 20 micrometers to 1200 micrometers.
Embodiment 41 is a component as in any of embodiments 36-40 wherein the component is one of a color matching article or a release liner.
Embodiment 42 is a component as in any of embodiments 37-41 wherein the discrete protrusions are arranged on the major surface in one of a regular pattern of offset rows, a regular pattern of aligned rows, a randomly distributed pattern, or a cross hatch pattern.
Embodiment 43 is a component as in any of embodiments 37-42 wherein the discrete protrusions are formed by one of screen printing, electrographic printing, offset printing, flexographic printing, gravure printing, inkjet printing, thermal mass transfer printing, embossing, microreplication, or combinations thereof.
Embodiment 44 is a component as in embodiment 36 wherein the air release structure comprises a plurality of abrasions.
Embodiment 45 is a component as in embodiment 44 wherein the abrasions result in an average feature height in a range from 10 micrometer to 50 micrometers.
Embodiment 46 is a component as in any of embodiments 44-45 wherein the component is one of a color matching article or a release liner. Embodiment 47 is a color matching system comprising
a component as in any of embodiments 36-46, wherein the component is a release liner; and a color matching article. Embodiment 48 is a release liner comprising a major surface and an air release structure disposed on the major surface, the air release structure comprising a plurality of discrete features comprising:
an average feature size in a range from 500 μιη to 700 μιη;
an average center-to-center feature spacing in a range from 500 μιη to 800 μιη;
an average feature-to-feature spacing in a range from 40 μιη to 80 μιη; and
an average feature height in a range from 2 μιη to 8 μιη.
Embodiment 49 is the release liner as in embodiment 48 wherein the plurality of discrete protrusions comprises a regular pattern of features.
Embodiment 50 is a release liner as in any of embodiments 48-49 wherein the discrete protrusions comprises a regular pattern of offset rows of circular dots.

Claims

What is claimed is:
1. A repositionable color-matching article comprising:
a flexible substrate having a first major surface and a second major surface disposed opposite the first major surface; and
a pressure-sensitive adhesive layer disposed upon the second major surface of the substrate; wherein the adhesive layer comprises a clean removal adhesive.
2. The color-matching article of claim 1, further comprising a first color layer disposed upon the first major surface of the substrate.
3. The color-matching article of any one of claims 1 or 2, wherein the clean removal adhesive is solvent resistant according to the Solvent Resistance Test.
4. The color-matching article of any one of claims 1 to 3, wherein the adhesive is self-wetting.
5. The color-matching article of any one of claims 1 to 4, wherein the adhesive comprises a silicone-free, urea-based adhesive.
6. The color-matching article of any one of claims 1 to 5, wherein the article has an average edge thickness of 10 mils or less.
7. The color-matching article of any one of claims 1 to 6, wherein the article exhibits a drape of 3 inches (7.62 cm) or less according to the Flexibility Test.
8. A color-matching system comprising the color-matching article of any one of claims 1 to 7; and a release liner;
wherein the release liner comprises:
a base layer having a first major surface and a second major surface disposed opposite the first major surface; and wherein the adhesive layer of the color-matching article is releasably adhered to the first major surface of the release liner; and
wherein the release liner comprises less than 0.5% silicone by weight.
9. The color-matching system of claim 8, wherein the release liner further comprises a varnish layer disposed on the first major surface of the base layer.
10. The color-matching system of any one of claims 8 or 9, wherein the release liner further comprises a pattern layer.
1 1. The color-matching system of claim 10, wherein the pattern layer is disposed on at least a portion of the second major surface of the base layer.
12. The color-matching system of claim 10, wherein the pattern layer is disposed on at least a portion of the first major surface of the base layer.
13. The color-matching system of any one of claims 8 to 12, wherein the release liner further comprises a second color layer disposed on the second major surface of the base layer, the pattern layer, or combinations thereof.
14. The color-matching system of any one of claims 8 to 13, wherein one or more edges of the release liner extend beyond one or more edges of the color-matching article.
15. A color-matching kit comprising:
the color-matching system of any one of claims 8-13; and
an applicator.
16. The color-matching kit of claim 15, wherein the applicator is selected from a squeegee or a roller.
17. The color-matching kit of any one of claims 15-16, further comprising a clear-coat- simulating article, a clear-coat formulation, or a clear-coat-simulating formulation.
18. A method of color-matching a paint formulation to a target surface having a color, the method comprising:
(a) applying the paint formulation over at least a portion of the repositionable color- matching article of any one of claims 1-7 or 32;
(b) adhering the color-matching article to a portion of the target surface with the adhesive layer;
(c) comparing the paint formulation on the color-matching article to the target surface; and (d) determining whether the paint formulation on the color-matching article closely matches the color of the target surface.
19. The method of claim 18, further comprising the step of:
(bl) adhering a clear-coat-simulating article or applying a clear-coat formulation or clear- coat-simulating formulation over the color-matching article.
20. The method of any one of claims 18 or 19, further comprising:
(e) removing the color-matching article from the target surface, wherein upon removal, no contaminants remain on the target surface according to the Contamination Test.
21. The method of claim 20, further comprising:
(f) repeating steps (a)-(c) or (a)-(e).
22. A method of color-matching a paint formulation to a target surface having a color, the method comprising:
(a) applying the paint formulation over at least a portion of the color-matching article of the color-matching system of any one of claims 8 to 14 or 33
(b) removing the color-matching article from the release liner;
(c) adhering the color-matching article to a portion of the target surface with the adhesive layer; (d) comparing the paint formulation on the color-matching article to the target surface; and
(e) determining whether the paint formulation on the color-matching article closely matches the color of the target surface.
23. The method of claim 22, wherein step (a) further comprises applying the paint formulation over at least a portion of the release liner; and wherein the paint formulation adheres to the release liner.
24. The method of any one of claims 22 or 23, further comprising the step of:
(cl) adhering a clear-coat-simulating article over the color-matching article.
25. The method of any one of claims 22 to 24, further comprising:
(f) removing the color-matching article from the target surface.
26. The method of claim 25, further comprising:
(g) repeating steps (a)-(e), or (a)-(f).
27. The method of any one of claims 22 to 26, wherein the release liner comprises a pattern layer, further comprising:
(al) assessing visibility of the pattern layer through the paint layer.
28. The method of any one of claims 18-27, wherein the target surface comprises a surface topography, wherein the color-matching article conforms to the surface topography upon adhering the color-matching articles to a portion of the target surface with the adhesive layer.
29. The method of claim 28, wherein the surface topography is non-planar.
30. The method of any one of claims 18-29, wherein in step (a) the paint formulation is applied over at least a portion of the first major surface of the substrate to form a paint layer on the color- matching article.
31. The method of any one of claims 18-29, wherein the color-matching article further comprises a first color layer disposed on the first major surface of the substrate and wherein in step (a) the paint formulation is applied over at least a portion of the first color layer to form a paint layer on the color-matching article.
32. The repositionable color-matching article of any of claims 1-7 wherein the adhesive layer comprises an air release structure.
33. The color-matching system of any of claims 8- 14 or 32 wherein the release liner comprises an air release structure.
34. The color matching system of claim 33 wherein the air release structure is disposed on at least one of the first major surface or the second major surface.
35. A color-matching kit comprising the color-matching system of claim 34 and an applicator.
36. A color matching system component comprising an air release structure on a major surface thereof.
37. The component of claim 36 wherein the air release structure comprises discrete protrusions having an average feature size in a range from 300 micrometers to 1800 micrometers.
38. The component of any of claims 36-37 wherein the air release structure comprises discrete protrusions having an average feature height in a range from 1 micrometer to 60 micrometers.
39. The component of any of claims 36-38 wherein the air release structure comprises discrete protrusions having an average center-to-center spacing in a range from 500 micrometers to 900 micrometers.
40. The component of any of claims 36-39 wherein the air release structure comprises discrete protrusions having an average feature-to-feature spacing in a range from 20 micrometers to 1200 micrometers.
41. The component of any of claims 36-40 wherein the component is one of a color matching article or a release liner.
42. The component of any of claims 37-41 wherein the discrete protrusions are arranged on the major surface in one of a regular pattern of offset rows, a regular pattern of aligned rows, a randomly distributed pattern, or a cross hatch pattern.
43. The component of any of claims 37-42 wherein the discrete protrusions are formed by one of screen printing, electrographic printing, offset printing, flexographic printing, gravure printing, inkjet printing, thermal mass transfer printing, embossing, microreplication, or combinations thereof.
44. The component of claim 36 wherein the air release structure comprises a plurality of abrasions.
45. The component of claim 44 wherein the abrasions result in an average feature height in a range from 10 micrometer to 50 micrometers.
46. The component of any of claims 43-45 wherein the component is one of a color matching article or a release liner.
47. A color matching system comprising a component as in any of claims 36-46, wherein the component is a release liner, and a color matching article.
48. A release liner comprising a major surface and an air release structure disposed on the major surface, the air release structure comprising a plurality of discrete features comprising:
an average feature size in a range from 500 μηι to 700 μηι;
an average center-to-center feature spacing in a range from 500 μηι to 800 μηι;
an average feature-to-feature spacing in a range from 40 μηι to 80 μηι; and
an average feature height in a range from 2 μηι to 8 μηι.
49. The release liner of claim 48 wherein the plurality of discrete protrusions comprises a regular pattern of features.
50. The release liner of any of claims 48-49 wherein the discrete protrusions comprises a regular pattern of offset rows of circular dots.
PCT/US2015/014717 2014-02-07 2015-02-06 Paint color evaluation system that facilitates examination of color at multiple angles and locations on a vehicle WO2015120212A1 (en)

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US201461937278P 2014-02-07 2014-02-07
US61/937,278 2014-02-07
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