Stock material or miscellaneous articles – Composite – Of polyamidoester
Reexamination Certificate
2002-02-15
2003-12-09
Seidieck, James J. (Department: 1711)
Stock material or miscellaneous articles
Composite
Of polyamidoester
C428S423300, C428S425600
Reexamination Certificate
active
06660390
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to articles having a printed surface as well as flexible coating and film compositions that are printable in combination with exhibiting stain resistance. The composition comprises a hard component having an elongation of less than about 150%, a soft component having an elongation of greater than about 200%, and preferably a cross-linking agent. The hard component preferably comprises a hydroxy functional thermoplastic polyurethane, hydroxy functional acrylic polymer, polymeric polyol or mixture thereof. The soft component preferably comprises a hydroxy functional thermoplastic urethane, non-reactive urethane, polymeric polyol, or mixture thereof; whereas the cross-linking agent is preferably an isocyanate.
BACKGROUND OF THE INVENTION
During the manufacture of various retroreflective articles such as signs and personal protection apparel, a surface of a retroreflective sheeting construction is often coated with an ink receptive coating that can be printed upon with ink. A water-borne urethane, commercially available from ICI Resins (or Zeneca Resins) Wilmington, Mass. under the trade designation “Neorez R-960” that has been combined with an aziridine cross-linker, also commercially available from ICI Resins, under the trade designation “CX-100” is a representative ink-receptive coating. This ink receptive coating is not stain resistance when contacted with highly plasticized polyvinyl chloride comprising fluorescent yellow dye.
In general, to enhance the durability and stain resistance of printed articles and articles, a protective cover film or top coat is often applied over the ink graphic. In order to contribute the desired properties, the protective cover film or top coat typically comprises a highly cross-linked polymer. An exemplary top coat is a polyurethane composition that is the reaction product of a hydroxy functional acrylic polymer, a polyester polyol, an aliphatic polyisocyanate, and a catalyst. This top coat, although flexible and stain resistant, is not print receptive.
Industry would find advantage in flexible compositions that are suitable for films and coatings that are printable and stain resistant, eliminating the need for an ink receptive coating in combination with a protective top coat or cover film.
SUMMARY OF THE INVENTION
The present invention relates to a composition that exhibits a synergistic combination of flexibility, printability, and stain resistance. The composition is suitable for use as a coating on a substrate or as a free-standing film, ranging in thickness from about 5 microns to about 125 microns. In preferred embodiments the composition exhibits good surface slip and/or is transparent.
In one embodiment, the present invention is an article comprising a layer, such as a coating or a film, the layer comprising the reaction product of a hard component having an elongation up to about 150%; a soft component having an elongation ranging from about 200% to about 800% after cross-linking; and a cross-linking agent. The layer may further comprise an ink on said layer. The Shore Hardness of the hard component is preferably at least about 40 D and more preferably at least about 70 D. The hard component has functionality and preferably comprises a first polyurethane polymer, an acrylic polymer, polymeric polyol or mixture thereof. The soft component has functionality and preferably comprises a second polyurethane polymer, a polymeric polyol, or mixture thereof. The polymeric polyol of both the soft and hard component is preferably a polyester polyol.
In another embodiment, the present invention is an article comprising a layer, such as a coating or film, comprising a composition comprising at least one first polymer having an elongation up to about 150% and at least one second polymer having an elongation ranging from about 200% to about 600%. The layer may further comprise an ink on said layer. The first polymer preferably comprises a first polyurethane polymer, an acrylic polymer, or mixture thereof. The second polymer comprises a second polyurethane polymer. The composition is substantially free of a cross-linking agent and is thus unreactive.
In another embodiment, the present invention relates to an article comprising a printable polymeric layer; wherein said polymeric layer is soluble in at least one solvent comprising acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, propylene glycol methyl ether acetate, ethyl acetate, propylene glycol methyl ether and mixtures thereof; and wherein said polymeric layer is flexible and stain resistant. The printable polymeric layer is insoluble in at least one solvent comprising ethanol, isopropanol, toluene, xylene, kerosene, gasoline, and mineral spirits.
Particularly for 100% solids systems, the hard component and soft component are preferably thermoplastic. Further, the previously described articles may further comprise a substrate. The article may also further comprise at least one bonding layer. The bonding layer is typically disposed between the printed layer and the substrate. In other embodiments, the previously described articles may further comprise a colorant in the substrate, inventive coating, bonding layer, and/or as a separate color layer.
The film and coating composition of the invention is suitable for use on a variety of articles and in particular as a surface layer on retroreflective sheeting.
In another embodiment, the present invention is a composition comprising a hard component comprising a first thermoplastic polyurethane polymer, an acrylic polymer, polymeric polyol, or mixture thereof; the hard component having functionality and an elongation up to about 150%; a soft component comprising a second thermoplastic polyurethane polymer, optionally having functionality and an elongation ranging from about 200% to about 600% after cross-linking, wherein the ratio of the hard component to soft component ranges from about 2:3 to 1:9; and at least one isocyanate. The Shore D Hardness of the hard component is at least about 40 and preferably at least about 70. The weight ratio of the hard component to the soft component ranges from about 1:2 to 1:6. The hard component preferably has an elongation of less than 50%. The soft component preferably has an elongation of greater than about 300%. The hard component is preferably a polyester polyol, ranging in number average molecular from 1000 to 10,000 g/mole. The composition may further comprise a monofunctional slip additive such as a hydroxy functional silicone.
DETAILED DESCRIPTION OF THE INVENTION
“Article” refers to a free-standing film or a laminate comprising a coated substrate.
“Hard component” refers to a polymer having an elongation of less than about 150%, and preferably an elongation of less than about 100% according to ASTM D-412.
“Soft component” refers to a polymer having an elongation of greater than about 200%, and preferably an elongation of greater than about 300% according to ASTM D-412. Further, the elongation of the soft component is typically less than about 800%. In the case of reactive compositions, the soft component may be a non-film forming liquid and thus exhibits the target elongation after cross-linking. In such instances, the elongation of the soft component can be determined by combining appropriate amounts of cross-linker and soft component, curing the soft component, and measuring the elongation of the cured soft component according to ASTM D-412.
“Polymer” and “polymeric” refers to a material comprising 10 or more repeating units. Polymers typically have a number average molecular weight (Mn) of at least 1000 g/mole in the case of polymeric polyols (e.g. polyester polyols, acrylic polyols) and at least 5000 to 6000 g/mole in the case of thermoplastic polyurethanes and acrylic polymers.
In addition to the elongation, the hard component, as well as the mixture of hard and soft components, preferably can be characterized by a hardness that can be measured and reported with reference to the Shore D Hardness scale. The Shore D Hardness is prefe
Fischer Carolyn A.
Ribar Travis B.
Seidieck James J.
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