Heat-sensitive record material
The invention describes an improved heat-sensitive recording material comprising a substrate having coated thereon a thermally-sensitive color-forming composition in one or more layers. The thermally sensitive color forming composition comprises a chromgenic dye precursor, an acidic developer material and a first binder material, and at least one protective layer comprising a dimer form of benzotriazole, namely, 2,2′-methylenebis(6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol) dispersed in a second binder material, wherein the first binder material and the second binder material can be the same or different. Preferably 2,2′-methylenebis(6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol) is dispersed in both the protective layer and the thermally sensitive color forming layer or layers. The thermally sensitive record material is remarkably resistant to scuffing, has a high degree of background whiteness, is resistant to printhead dusting and is remarkably resistant to fade as compared to other systems with other UV absorbers. The dimer form surprisingly contributes to a significant increase in coating hardness, reduced scuffing, reduced printhead contamination and dramatically increased resistance to fade as compared to the benzotriazoles taught in the art for record material applications.
1 . A heat-sensitive recording material comprising a substrate having coated thereon a thermally-sensitive color-forming composition in one or more layers, the thermally sensitive color forming composition comprising a chromogenic dye precursor, an acidic developer material and a first binder material, and at least one protective layer comprising 2,2′-methylenebis(6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol) dispersed in a second binder material, wherein the first binder material and the second binder material can be the same or different.
2 . The heat sensitive recording material according to claim 1 wherein the 2,2′-methylenebis(6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol) is at from 0.1 to 75 weight percent based on weight of the protective layer.
3 . The heat sensitive recording material according to claim 1 wherein the thermally sensitive color forming composition includes in addition bis(3-allyl-4-hydroxyphenyl)sulfone.
4 . The heat sensitive recording material according to claim 1 wherein the bis(3-allyl-4-hydroxyphenyl)sulfone is at from 5 weight percent to 75 weight percent based on weight of the thermally sensitive color forming composition.
5 . The heat sensitive recording material according to claim 1 wherein the thermally sensitive color forming composition in addition includes a sensitizer.
6 . The heat sensitive recording material according to claim 5 wherein the sensitizer is selected from 1,2-diphenoxyethane, acetoacet-o-toluidine, dimethyl terephthalate, p-benzylbiphenyl, phenyl-1-hydroxy-2-naphthoate.
7 . The heat sensitive recording material according to claim 1 wherein the 2,2′-methylenebis(6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol) is dispersed in a polymeric binder coated over the layer of thermally sensitive color forming composition.
8 . The heat sensitive recording material according to claim 1 wherein the 2,2′-methylenebis(6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol) in addition is an additive in the thermally sensitive color forming composition.
9 . The heat sensitive recording material according to claim 1 wherein the first and second binder materials are each independently selected from polyvinyl alcohol, polyvinyl acetate and polyacrylate.
10 . The heat sensitive recording material according to claim 1 wherein the protective layer of 2,2′-methylenebis(6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol) dispersed in polymeric binder has a mean elastic modulus of at least 14.46 GPa.
11 . The heat sensitive record material according to claim 10 wherein the record material has a whiteness value, measured by a Technidyne Color Touch 2-Model ISO Δb* following UV irradiation of four hours, of less than 4.2.
12 . The heat sensitive record material according to claim 1 wherein the elastic modulus of the protective layer in at least 14 and the change in whiteness value Δb* following UV exposure for four hours, measured by a Technidyne Color Touch 2-Model ISO of less than 4.2.
13 . A heat-sensitive recording material comprising a substrate having coated thereon a thermally-sensitive color-forming composition in one or more layers, the thermally sensitive color forming composition comprising a chromogenic dye precursor, an acidic developer material, a dimer material of the structure
and a first binder material.
14 . The heat sensitive recording material according to claim 13 wherein the 2,2′-methylenebis(6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol) is at from 0.1 to 40 weight percent based on weight of the protective layer.
15 . The heat sensitive recording material according to claim 13 wherein the thermally sensitive color forming composition includes in addition bis(3-allyl-4-hydroxyphenyl)sulfone.
16 . The heat sensitive recording material according to claim 13 wherein the bis(3-allyl-4-hydroxyphenyl)sulfone is at from 0.1 weight percent to 80 weight percent based on weight of the thermally sensitive color forming composition.
17 . The heat sensitive recording material according to claim 13 wherein the thermally sensitive color forming composition in addition includes a sensitizer.
18 . The heat sensitive record material according to claim 13 wherein the elastic modulus of the protective layer is at least 14 GPa and the whiteness value Δb* following UV exposure for four hours, measured by a Technidyne Color Touch 2-Model ISO is less than 4.2.
19 . The heat sensitive recording material according to claim 13 wherein the 2,2′-methylenebis(6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol) is dispersed in a second binder material coated over the layer of thermally sensitive color forming composition.
20 . The heat sensitive recording material according to claim 19 wherein the 2,2′-methylenebis(6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol) in addition is an additive in the thermally sensitive color forming composition.
21 . The heat sensitive recording material according to claim 19 wherein the first and second binder materials are each independently selected from polyvinyl alcohol, polyvinyl acetate and polyacrylate.
22 . The heat sensitive recording material according to claim 19 wherein the protective layer of 2,2′-methylenebis(6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol) dispersed in polymeric binder has a mean elastic modulus of at least 14.46 GPa.
23 . The heat sensitive record material according to claim 19 wherein the record material has a whiteness value Δb* measured by a Technidyne Color Touch 2-Model ISO following UV exposure of four hours, of less than 4.2.