Film forming mixtures, image bearing films and image bearing retroreflective sheeting
First Claim
1. A polyurethane film-forming mixture comprising(A) an aliphatic polyurethane derived from an aliphatic polyisocyanate and a polyester polyol prepared from a mixture comprising at least one polyol component and at least one dicarboxylic acid or anhydride component selected from the group consisting of phthalic acid or anhydride, adipic acid, azelaic acid, suberic acid and cyclohexane dicarboxylic acid provided that when the dicarboxylic acid or anhydride component comprises a mixture of acids and/or anhydrides, isophthalic acid or anhydride is not the major dicarboxylic acid or anhydride present in the mixture, and(B) at least one hydroxy-containing imidazoline represented by the formula ##STR7## wherein R is an aliphatic group containing from about 10 to about 22 carbon atoms and R1 is an alkylene group containing from 1 to about 3 carbon atoms.
1 Assignment
0 Petitions
Accused Products
Abstract
Aliphatic polyurethane film forming mixtures, image bearing aliphatic polyurethane films, and image bearing retroreflective sheeting having such image bearing films are described. The image-bearing aliphatic polyurethane films of the invention comprise an aliphatic polyurethane film derived from a film-forming mixture comprising (A) an aliphatic polyurethane, and (B) at least one hydroxy-containing imidazoline surfactant represented by the formula ##STR1## wherein R is an aliphatic group containing from about 10 to about 22 carbon atoms and R1 is an alkylene group containing from 1 to about 3 carbon atoms, said film having printed thereon either a monocolor image and a clear overcoat or a multicolor image with or without a clear overcoat wherein the monocolor image is derived from at least one UV radiation curable ink which is cured prior to application of the clear overcoat, and the multicolor image is derived from at least two UV radiation curable inks applied sequentially with curing after each ink application and before application of any clear overcoat. The retroreflective sheetings described herein and having the image bearing aliphatic urethane cover sheets or films may be enclosed lens or encapsulated lens retroreflective sheetings. The images may be single color images or multicolor images derived from UV radiation curable inks and, the images optionally coated with a UV cured clear overcoat.
116 Citations
63 Claims
-
1. A polyurethane film-forming mixture comprising
(A) an aliphatic polyurethane derived from an aliphatic polyisocyanate and a polyester polyol prepared from a mixture comprising at least one polyol component and at least one dicarboxylic acid or anhydride component selected from the group consisting of phthalic acid or anhydride, adipic acid, azelaic acid, suberic acid and cyclohexane dicarboxylic acid provided that when the dicarboxylic acid or anhydride component comprises a mixture of acids and/or anhydrides, isophthalic acid or anhydride is not the major dicarboxylic acid or anhydride present in the mixture, and (B) at least one hydroxy-containing imidazoline represented by the formula ##STR7## wherein R is an aliphatic group containing from about 10 to about 22 carbon atoms and R1 is an alkylene group containing from 1 to about 3 carbon atoms.
-
4. An image bearing aliphatic polyurethane film comprising an aliphatic polyurethane film derived from a film-forming mixture comprising
(A) an aliphatic polyurethane, and (B) at least one hydroxy-containing imidazoline represented by the formula ##STR8## wherein R is an aliphatic group containing from about 10 to about 22 carbon atoms and R1 is an alkylene group containing from 1 to about 3 carbon atoms, said film having printed thereon either a monocolor image and a clear overcoat or a multicolor image with or without a clear overcoat wherein the monocolor image is derived from at least one UV radiation curable ink which is cured prior to application of the clear overcoat, and the multicolor image is derived from at least two UV radiation curable inks applied sequentially with curing after each ink application and before application of any clear overcoat. - View Dependent Claims (5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17)
-
11. The film of claim 10 wherein the dicarboxylic acid (ii) is adipic acid and (iii) is phthalic acid and/or phthalic acid anhydride.
-
12. The film of claim 9 wherein the polyol component (A-2) contains (iv) from about 70 to about 90 mole percent of 1,6-hexanediol and (v) from about 10 to about 30 mole percent of at least one higher hydric polyol.
-
13. The film of claim 12 wherein the higher hydric polyol is selected from the group consisting of trimethylol propane, glycerol, pentaerythritol, and mixtures thereof.
-
14. The film of claim 4 wherein the film-forming mixture also comprises
(C) cellulose acetate butyrate. -
15. The film of claim 14 wherein the cellulose acetate butyrate contains from about 30% to about 60% of butyryl groups.
-
16. The film of claim 4 wherein the film-forming mixture also comprises
(D) at least one non-reactive solvent. -
17. The film of claim 4 wherein the clear overcoat film is derived from a clear UV curable film-forming mixture.
-
18. A multicolor image bearing aliphatic polyurethane film comprising an aliphatic polyurethane film derived from a film-forming mixture comprising
(A) an aliphatic polyurethane, (B) at least one hydroxy-containing imidazoline represented by the formula ##STR9## wherein R is an aliphatic group containing from about 10 to about 22 carbon atoms and R1 is an alkylene group containing from 1 to about 3 carbon atoms, and said film having printed thereon a multicolor image derived from at least two UV radiation curable inks applied sequentially with curing after each ink application. - View Dependent Claims (19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32)
-
25. The film of claim 24 wherein the dicarboxylic acid (ii) is adipic acid and (iii) is phthalic acid and/or phthalic acid anhydride.
-
26. The film of claim 23 wherein the polyol component (A-2) contains (iv) from about 70 to about 90 mole percent of 1,6-hexanediol and (v) from about 10 to about 30 mole percent of at least one higher hydric polyol.
-
27. The film of claim 26 wherein the higher hydric polyol is selected from the group consisting of trimethylol propane, glycerol, pentaerythritol, and mixtures thereof.
-
28. The film of claim 18 wherein the film-forming mixture also comprises
(C) cellulose acetate butyrate. -
29. The film of claim 28 wherein the cellulose acetate butyrate contains from about 30% to about 60% of butyryl groups.
-
30. The film of claim 18 wherein the film-forming mixture also comprises
(D) at least one non-reactive solvent. -
31. The film of claim 18 wherein a clear overcoat film is applied over the multicolor image.
-
32. The film of claim 31 wherein the clear overcoat film is derived from a UV radiation curable clear film-forming mixture.
-
33. Retroreflective sheeting having a multicolor image bearing aliphatic polyurethane cover sheet obtainable from a film-forming mixture comprising
(A) an aliphatic polyurethane, (B) at least one hydroxy-containing imidazoline represented by the formula ##STR10## wherein R is an aliphatic group containing from about 10 to about 22 carbon atoms and R1 is an alkylene group containing from 1 to about 3 carbon atoms, and (C) cellulose acetate butyrate said cover sheet having printed thereon a multicolor image derived from at least two UV radiation curable inks applied sequentially with curing after each ink application. - View Dependent Claims (34, 35, 36, 37, 38, 39, 40, 41, 42, 43)
-
39. The sheeting of claim 38 wherein the dicarboxylic acid (ii) is adipic acid and (iii) is phthalic acid and/or phthalic acid anhydride.
-
40. The sheeting of claim 37 wherein the polyol component (A-2) contains (iv) from about 70 to about 90 mole percent of 1,6-hexanediol and (v) from about 10 to about 30 mole percent of at least one higher hydric polyol.
-
41. The sheeting of claim 40 wherein the higher hydric polyol is selected from the group consisting of trimethylol propane, glycerol, pentaerythritol, and mixtures thereof.
-
42. The sheeting of claim 33 wherein the cellulose acetate butyrate contains from about 30% to about 60% of butyryl groups.
-
43. The sheeting of claim 33 wherein the film-forming mixture also comprises
(D) at least one non-reactive solvent.
-
44. A multicolor image bearing embedded lens retroreflective sheeting comprising
(A) a monolayer of transparent microsphere lenses; -
(B) a polymeric spacing layer underlying and contacting the bottom surfaces of the lenses and having a back surface that is spaced from the bottom surfaces of the lenses; (C) a reflective layer having its top surface in contact with the back surface of the spacing layer; and (D) an aliphatic polyurethane cover sheet overlying and conforming the top surface of the lenses and having a flat top surface, said cover sheet being derived from a film-forming mixture comprising (D-1) an aliphatic polyurethane, (D-2) at least one hydroxy-containing imidazoline represented by the formula ##STR11## wherein R is an aliphatic group containing from about 10 to about 22 carbon atoms and R1 is an alkylene group containing from 1 to about 3 carbon atoms, and (D-3) cellulose acetate butyrate, said cover sheet having printed thereon a multicolor image derived from at least two UV radiation curable inks applied sequentially with curing after each ink application. - View Dependent Claims (45, 46, 47, 48, 49, 50, 51, 52, 53)
-
50. The sheeting of claim 44 wherein the cellulose acetate butyrate contains from about 30% to about 60% by weight of butyryl groups.
-
51. The sheeting of claim 44 wherein the film-forming mixture of (D) also comprises
(D-4) at least one non-reactive solvent other than (D-3). -
52. The sheeting of claim 51 wherein the solvent (D4) is selected from the group consisting of butyl acetate, toluene, pm acetate and mixtures thereof.
-
53. The sheeting of claim 44 also comprising
(E) a pressure-sensitive adhesive layer underlying the reflective layer (C), and, optionally, (F) a release layer underlying and in contact with the adhesive layer.
-
-
54. An image bearing encapsulated-lens retroreflective sheeting comprising (1) a base sheet that comprises a monolayer of retroreflective elements partially embedded in a binder layer;
- (2) a cover sheet disposed in spaced relationship from the layer of retroreflective elements; and
(3) a network of intersecting bonds that extend between said cover sheet and said base sheet and comprise binder material thermo-formed at the point of contact between said bonds and said cover sheet to form a plurality of cells within which retroreflective elements are hermetically sealed and to adhere the base sheet to the cover sheet, wherein the cover sheet comprises an image bearing aliphatic polyurethane film comprising an aliphatic polyurethane film derived from a film-forming mixture comprising(A) an aliphatic polyurethane, and (B) at least one hydroxy-containing imidazoline represented by the formula ##STR12## wherein R is an aliphatic group containing from about 10 to about 22 carbon atoms and R1 is an alkylene group containing from 1 to about 3 carbon atoms, said film having printed thereon either a monocolor image and a clear overcoat or a multicolor image with or without a clear overcoat wherein the monocolor image is derived from at least one UV radiation curable ink which is cured prior to application of the clear overcoat, and the multicolor image is derived from at least two UV radiation curable inks applied sequentially with curing after each ink application and before application of any clear overcoat. - View Dependent Claims (55, 56, 57, 58, 59, 60, 61, 62, 63)
-
60. The sheeting of claim 54 wherein the cellulose acetate butyrate contains from about 30% to about 60% by weight of butyryl groups.
-
61. The sheeting of claim 54 wherein the film-forming mixture of (D) also comprises
(D-4) at least one non-reactive solvent other than (D-3). -
62. The sheeting of claim 61 wherein the solvent (D-4) is selected from the group consisting of butyl acetate, toluene, and mixture thereof.
-
63. The sheeting of claim 54 also comprising
(E) a pressure-sensitive adhesive layer underlying the reflective layer (C), and, optionally, (F) a release layer underlying and in contact with the adhesive layer.
- (2) a cover sheet disposed in spaced relationship from the layer of retroreflective elements; and
Specification