Thermally developable materials with improved backside layers
View Patent ↗Thermally developable materials such as photothermographic and thermographic materials have a backside conductive layer with increased conductive efficiency. This backside conductive layer is a buried conductive coating and is overcoated with a layer that contains a smectite clay modified with a quaternary ammonium compound.
1. A thermally developable material that comprises a support having on one side thereof, one or more thermally developable imaging layers comprising a binder and in reactive association, a non-photosensitive source of reducible silver ions, and a reducing agent composition for said non-photo-sensitive source reducible silver ions, and
having disposed on the backside of said support a non-imaging backside conductive layer comprising one or more binder polymers, and a first layer disposed over said non-imaging backside conductive layer,
wherein said first layer comprises a smectite clay modified with a quaternary ammonium compound.
2. The thermally developable material of claim 1 wherein said smectite clay is a montmorillonite clay.
3. The thermally developable material of claim 1 wherein said quaternary ammonium compound is represented by Structure III:
wherein R 1 represents hydrogen, or substituted or unsubstituted alkyl groups having 1 to 6 carbon atoms, R 2 represents substituted or unsubstituted alkyl groups having 1 to 6 carbon atoms, R 3 is a linear or branched saturated or unsaturated, substituted or unsubstituted alkyl group having 1 to 22 carbon atoms or a substituted or unsubstituted benzyl group, R 4 is a linear or branched saturated or unsaturated, substituted or unsubstituted alkyl group having 12 to 22 carbon atoms, and X − is an anion.
4. The thermally developable material of claim 1 wherein said quaternary ammonium compound is represented by Structure III:
wherein R 1 and R 2 each independently represent substituted or unsubstituted alkyl groups having from 1 to 6 carbon atoms, R 3 represent a substituted or unsubstituted benzyl group, a tallow group or dihydrogenated tallow group, R 4 represents a tallow group or dihydrogenated tallow group, and X − is chloride.
5. The thermally developable material of claim 1 wherein said quaternary ammonium compound is dimethyl-di(hydrogenated-tallow) ammonium chloride.
6. The thermally developable material of claim 1 wherein said modified montmorillonite clay is present in an amount of from about 0.5 to about 5 weight % of the total dry binder weight.
7. The material of claim 1 wherein said first layer has a dry thickness of from about 1 to about 7 μm.
8. The material of claim 1 wherein said backside conductive layer comprises a metal oxide that is present in said backside conductive layer in an amount of from about 0.05 to about 1 g/m 2 and said one or more binder polymers are present in an amount of from about 20 to about 60 weight %.
9. The material of claim 1 wherein said backside conductive layer has a dry thickness of from about 0.05 to about 1.1 μm.
10. The material of claim 1 wherein said backside conductive layer and said first layer have been formulated in organic solvents and have been simultaneously coated.
11. The material of claim 1 wherein said backside conductive layer comprises a conductive polymer.
12. The material of claim 1 wherein said backside conductive layer comprises a metal oxide that is a non-acicular metal antimonate.
13. The material of claim 12 wherein said non-acicular metal antimonate has a composition represented by the following Structure I or II:
M +2 Sb +5 2 O 6 (I)
wherein M is zinc, nickel, magnesium, iron, copper, manganese, or cobalt,
M a +3 Sb +5 O 4 (II)
wherein M a is indium, aluminum, scandium, chromium, iron, or gallium.
14. The material of claim 12 wherein said non-acicular metal antimonate is composed of zinc antimonate (ZnSb 2 O 6 ).
15. The material of claim 1 wherein:
a) said first layer comprises a film-forming polymer and said smectite clay comprises a montmorillonite clay modified with a quaternary ammonium compound, and
b) said non-imaging backside conductive layer is interposed between said support and said first layer and directly adhering said first layer to said support, said non-imaging backside conductive layer comprises a metal oxide in a mixture of two or more polymers that include a first polymer serving to promote adhesion of said backside conductive layer directly to said support, and a second polymer that is different than and forms a single phase mixture with said first polymer,
wherein said film-forming polymer of said first layer and said second polymer of said backside conductive layer are the same or different polyvinyl acetal resins, polyester resins, cellulosic polymers, maleic anhydride-ester copolymers, or vinyl polymers.
16. The material of claim 15 wherein said film-forming polymer of said first layer and said second polymer of said backside conductive layer are the same or different polyvinyl acetal resin or cellulosic ester polymer.
17. The material of claim 16 wherein said film-forming polymer of said first layer and said second polymer of said backside conductive layer are both polyvinyl butyral, or cellulose acetate butyrate.
18. The material of claim 15 wherein said first polymer is a polyvinyl acetal, cellulosic ester polymer, polyvinyl chloride, polyvinyl acetate, epoxy resin, polyester resin, polystyrene, polyacrylonitrile, polycarbonate, acrylate or methacrylate polymer, maleic anhydride ester copolymer, and butadiene-styrene polymer.
19. The material of claim 15 wherein said backside conductive layer comprises a single-phase mixture of a polyester resin with either polyvinyl butyral or cellulose acetate butyrate.
20. The material of claim 1 wherein said non-photosensitive source of reducible silver ions is a silver salt of an aliphatic carboxylate or a mixture of silver salts of aliphatic carboxylates, at least one of which is silver behenate.
21. The material of claim 1 that is a non-photosensitive thermographic material.
22. The material of claim 1 wherein said first layer is the outermost backside layer.
23. The material of claim 1 wherein said first layer is intermediate said backside conductive layer and an outermost protective layer.
24. A thermally developable material that comprises a support having on one side thereof, one or more thermally developable imaging layers comprising a binder and in reactive association, a non-photosensitive source of reducible silver ions, and a reducing agent composition for said non-photo-sensitive source reducible silver ions, and
having disposed on the backside of said support, a non-imaging backside conductive layer comprising a conductive metal oxide in a one or more binder polymers, and a first layer disposed over said non-imaging backside conductive layer, said non-imaging backside conductive layer and said first layer having been coated simultaneously,
wherein said first layer comprises a montmorillonite clay modified with a quaternary ammonium compound.
25. The thermally developable material of claim 24 wherein said quaternary ammonium compound is represented by Structure III:
wherein R 1 represents hydrogen, or substituted or unsubstituted alkyl groups having 1 to 6 carbon atoms, R 2 represents substituted or unsubstituted alkyl groups having 1 to 6 carbon atoms, R 3 is a linear or branched saturated or unsaturated, substituted or unsubstituted alkyl group having 1 to 22 carbon atoms or a substituted or unsubstituted benzyl group, R 4 is a linear or branched saturated or unsaturated, substituted or unsubstituted alkyl group having 12 to 22 carbon atoms, and X − is an anion.
26. The thermally developable material of claim 24 wherein said quaternary ammonium compound is represented by Structure III:
wherein R 1 and R 2 each independently represent substituted or unsubstituted alkyl groups having from 1 to 6 carbon atoms, R 3 represent a substituted or unsubstituted benzyl group, a tallow group or dihydrogenated tallow group, R 4 represents a tallow group or dihydrogenated tallow group, and X − is chloride.
27. The material of claim 24 wherein said metal oxide is a non-acicular metal antimonate and said quaternary ammonium compound is dimethyl-di(hydrogenated-tallow) ammonium chloride.
28. A photothermographic material that comprises a support having on one side thereof, one or more thermally developable imaging layers comprising a binder and in reactive association, a photosensitive silver halide, a non-photosensitive source of reducible silver ions, and a reducing agent composition for said non-photosensitive source reducible silver ions, and
having disposed on the backside of said support, a simultaneously coated first layer and a non-imaging backside conductive layer:
a) said first layer comprising a film-forming polymer, and a smectite clay modified with a quaternary ammonium compound,
b) interposed between said support and said first layer and directly adhering said first layer to said support, said non-imaging backside conductive layer comprising a mixture of two or more polymers that include a first polymer serving to promote adhesion of said backside conductive layer directly to said support, and a second polymer that is different than and forms a single phase mixture with said first polymer, wherein:
1) said backside conductive layer has a water electrode resistivity measured at 21.1° C. and 50% relative humidity of 1×10 12 ohms/sq or less,
2) the total amount of mixture of two or more polymers in said backside conductive layer is at least 20 weight %,
3) said backside conductive layer comprises a conductive metal oxide or conductive polymer,
4) said film-forming polymer of said first layer and said second polymer of said backside conductive layer are the same or different polyvinyl acetal resins, polyester resins, cellulosic polymers, maleic anhydride-ester copolymers, or vinyl polymers,
5) said modified smectite clay is present in an amount of from about 0.5 to about 5 weight % of said dried first layer, and
6) said first layer has a dry thickness of from about 1 to about 7 μm.
29. The material of claim 28 wherein said photosensitive silver halide is one or more preformed silver halides and said non-photosensitive source of reducible silver ions comprises silver behenate.
30. The material of claim 28 comprising an antihalation composition in one or more backside layers.
31. The material of claim 28 wherein said backside conductive layer and said first layer have been formulated in and simultaneously coated out of a hydrophobic organic solvent.
32. The material of claim 31 wherein said organic solvent comprises methyl ethyl ketone.
33. The material of claim 32 wherein said organic solvent comprises a mixture of methyl ethyl ketone and up to 25% methanol.
34. A black-and-white photothermographic material that comprises a transparent polymeric support having on one side thereof one or more thermally developable imaging layers comprising predominantly one or more hydrophobic binders, and in reactive association, preformed photosensitive silver bromide or silver iodobromide present as tabular and/or cubic grains, a non-photo-sensitive source of reducible silver ions that includes silver behenate, a reducing agent composition for said non-photosensitive source reducible silver ions comprising a hindered phenol, and a protective layer disposed over said one or more thermally developable imaging layers, and
having disposed on the backside of said support, a simultaneously coated backside protective layer and a non-imaging backside conductive layer:
a) said backside protective layer comprising a film-forming polymer that is cellulose acetate butyrate, an antihalation composition, and a montmorillonite clay modified with a hydrogenated tallow ammonium compound,
b) interposed between said support and said backside protective layer and directly adhering said backside protective layer to said support, said non-imaging backside conductive layer comprising non-acicular metal antimonate in a mixture of two or more polymers that include a first polymer serving to promote adhesion of said conductive layer directly to said support, and a second polymer that is different than and forms a single phase mixture with said first polymer,
wherein said first polymer of said backside conductive layer is a polyester and said second polymer of said backside conductive layer is polyvinyl butyral or cellulose acetate butyrate, and said modified montmorillonite clay is present in an amount of from about 1 to about 3 weight % of the total dry binder weight of said first layer, and said first layer has a dry thickness of from about 2 to about 5 μm, and
wherein said non-acicular metal antimonate clusters are composed of zinc antimonate (ZnSb 2 O 6 ) that is present at a coverage of from about 0.1 to about 0.3 g/m 2 , the dry thickness of said backside conductive layer is from about 0.1 to about 0.2 μm, the weight % of said polymer mixture in said backside conductive layer is from about 25 to about 35 weight %, and said backside conductive layer has a water electrode resistivity measured at 21.1° C. and 50% relative humidity of less than about 1×10 11 ohms/sq, and
said montmorillonite clay is modified with an ammonium compound having one of the following Structures HTA-1 through HTA-5,
wherein HT represents hydrogenated tallow and T represents Tallow.
35. A method of forming a visible image comprising:
(A) imagewise exposing the material of claim 1 that is a photothermo-graphic material to electromagnetic radiation to form a latent image,
(B) simultaneously or sequentially, heating said exposed photothermo-graphic material to develop said latent image into a visible image.
36. The method of claim 35 wherein said photothermographic material comprises a transparent support and said image-forming method further comprises:
(C) positioning said imaged, heat-developed photothermographic material with the visible image thereon between a source of imaging radiation and an imageable material that is sensitive to said imaging radiation, and
(D) thereafter exposing said imageable material to said imaging radiation through the visible image in said exposed and heat-developed photothermo-graphic material to provide an image in said imageable material.
37. The method of claim 35 wherein said photothermographic material is imaged at an exposure wavelength greater than 700 nm.
38. The method of claim 35 comprising using said visible image for a medical diagnosis.
39. A method of forming a visible image comprising thermal imaging of the material of claim 1 that is a thermographic material.
40. The method of claim 39 wherein said thermographic material comprises a transparent support and said image-forming method further comprises:
(C) positioning said imaged, heat-developed thermographic material with the visible image thereon between a source of imaging radiation and an imageable material that is sensitive to said imaging radiation, and
(D) thereafter exposing said imageable material to said imaging radiation through the visible image in said exposed and heat-developed thermographic material to provide an image in said imageable material.
41. A method of forming a visible image comprising:
(A) imagewise exposing the material of claim 28 to electromagnetic radiation to form a latent image,
(B) simultaneously or sequentially, heating said exposed photothermo-graphic material to develop said latent image into a visible image.
42. A method of preparing a thermally developable material that comprises a support having on one side thereof, one or more thermally developable imaging layers comprising a binder and in reactive association, a non-photosensitive source of reducible silver ions, and a reducing agent composition for said non-photosensitive source reducible silver ions, comprising:
simultaneously coating on the backside of said support and out of the same or different organic solvents, both a non-imaging backside conductive formulation comprising a conductive metal oxide in one or more binder polymers, and a first layer formulation comprising a smectite clay modified with a quaternary ammonium compound, to provide first layer over a non-imaging backside conductive layer,
1) said backside conductive layer, when dried, having a water electrode resistivity measured at 21.1° C. and 50% relative humidity of 1×10 12 ohms/sq or less,
2) the total dry amount of said one or more binder polymers in said backside conductive layer is at least 20 weight %, and
3) said conductive metal oxide is present in an amount of less than 1 g/m 2 ,
4) said modified smectite clay is present in an amount of from about 0.5 to about 5 weight % of the total dry binder weight in said first layer, and
5) said first layer has a dry thickness of from about 1 to about 7 μm.