US4105451A
Expired / Lapsed
US
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Photothermographic material, composition and process
Assignee: Eastman Kodak Co
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Filing: 1976-12-22
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Granted: 1978-08-08
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Expires: 1996-12-22
Abstract
Abstract An improved photothermographic material can be prepared by sequentially mixing the following components: (1) a dispersion comprising a 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole or 2-mercaptobenzoselenazole compound and a silver salt of certain heterocyclic thiones with (2) a reducing agent solution, (3) a binder, and (4) a silver halide photosensitive composition containing a spectral sensitizing dye, such as a symmetrical or unsymmetrical thiosulfato substituted benzimidazolocarbocyanine dye. A photothermographic material containing the described components can provide a developed image after imagewise exposure by merely heating the material to moderately elevated temperatures.
Inventors
- 👤 James G. Smith
- 👤 Ralph C. Reed
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-29 21:16
CPC Classifications
G; G03; G03C; G03C1/00; G03C1/494; G03C1/498
Claims Analysis
Total Claims: 49
Claim 1
Independent Claim
80 words
A method of preparing a photothermographic composition comprising sequentially mixing the following components: (1) a dispersion comprising a 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole or 2-mercaptobenzoselenazole compound and a silver salt of a heterocyclic thione represented by the formula: ##STR10## wherein R' represents atoms completing a five-member heterocyclic nucleus and Z is alkylene containing 1 to 30 carbon atoms, (2) a reducing agent solution comprising a reducing agent, (3) a binder, and (4) a silver halide photosensitive composition containing a spectral sensitizing dye.
Claim 2
Independent Claim
80 words
A method of preparing a photothermographic composition comprising sequentially mixing the following components: (1) a dispersion comprising a 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole or 2-mercaptobenzoselenazole compound and a silver salt of a heterocyclic thione represented by the formula: ##STR10## wherein R' represents atoms completing a five-member heterocyclic nucleus and Z is alkylene containing 1 to 30 carbon atoms, (2) a reducing agent solution comprising a reducing agent, (3) a binder, and (4) a silver halide photosensitive composition containing a spectral sensitizing dye.
Claim 3
Dependent Claim
17 words
A method as in claim 1 wherein said silver halide contains at least 30 mole percent iodide.
Claim 4
Dependent Claim
15 words
A method as in claim 1 wherein said silver halide consists essentially of silver iodide.
Claim 5
Dependent Claim
15 words
A method as in claim 1 wherein said surfactant consists essentially of a paraisononylphenoxypolyglycidol surfactant.
Claim 6
Dependent Claim
15 words
A method as in claim 1 wherein said binder consists essentially of an acrylamide polymer.
Claim 7
Dependent Claim
30 words
A method as in claim 1 wherein said binder is an acrylamide polymer selected from the group consisting of poly(acrylamide), poly(acrylamide-co-2-acetoacetoxyethyl methacrylate), poly(acrylamide-co-α-chloroacrylic acid), poly(acrylamide-co-1-vinylimidazole), poly(vinyl alcohol), and combinations thereof.
Claim 8
Dependent Claim
23 words
A method as in claim 1 wherein said component (2) also comprises a toning agent that is a combination of 3-mercapto-1,2,4-triazole and 2,4-dimercaptopyrimidine.
Claim 9
Dependent Claim
15 words
A method as in claim 1 wherein said reducing agent is a polyhydroxybenzene reducing agent.
Claim 10
Dependent Claim
22 words
A method as in claim 1 wherein said silver salt of a heterocyclic thione consists essentially of a silver salt of 3-carboxymethyl-4-methyl-4-thiazoline-2-thione.
Claim 11
Dependent Claim
47 words
A method as in claim 1 also comprising heating said silver halide photosensitive composition containing a spectral sensitizing dye for about 5 to about 30 minutes at a temperature within the range of about 50 to about 90° C before mixing it with other of said components.
Claim 12
Independent Claim
90 words
A method of preparing a photothermographic composition comprising sequentially mixing the following components: (1) a dispersion comprising a 2-mercaptobenzothiazole,2-mercaptobenzimidazole, 2-mercaptobenzoxazole or 2-mercaptobenzoselenazole compound and a silver salt of a heterocyclic thione represented by the formula: ##STR11## wherein R' represents atoms completing a five-member heterocyclic nucleus and Z is alkylene containing 1 to 30 carbon atoms, (2) a reducing agent solution comprising a reducing agent, (3) a binder, and (4) a silver halide photosensitive composition containing a spectral sensitizing dye consisting essentially of a symmetrical or unsymmetrical thiosulfatoalkyl substituted benzimidazolocarbocyanine dye.
Claim 13
Independent Claim
90 words
A method of preparing a photothermographic composition comprising sequentially mixing the following components: (1) a dispersion comprising a 2-mercaptobenzothiazole,2-mercaptobenzimidazole, 2-mercaptobenzoxazole or 2-mercaptobenzoselenazole compound and a silver salt of a heterocyclic thione represented by the formula: ##STR11## wherein R' represents atoms completing a five-member heterocyclic nucleus and Z is alkylene containing 1 to 30 carbon atoms, (2) a reducing agent solution comprising a reducing agent, (3) a binder, and (4) a silver halide photosensitive composition containing a spectral sensitizing dye consisting essentially of a symmetrical or unsymmetrical thiosulfatoalkyl substituted benzimidazolocarbocyanine dye.
Claim 14
Dependent Claim
18 words
A method as in claim 11 wherein said spectral sensitizing dye consists essentially of anhydro-5,5'-6,6'-tetrachloro-1,1'-diethyl-3,3'-bis(thiosulfatopropyl)-benzimidazolocarbocyanine hydroxide, sodium salt.
Claim 15
Dependent Claim
44 words
A method as in claim 11 wherein said photosensitive composition contains a spectral sensitizing concentration of said spectral sensitizing dye that is within the range of about 1 g to about 9 g of said spectral sensitizing dye per mole of said silver halide.
Claim 16
Dependent Claim
16 words
A method as in claim 11 wherein said halide contains at least 30 mole percent iodide.
Claim 17
Dependent Claim
14 words
A method as in claim 11 wherein said halide consists essentially of silver iodide.
Claim 18
Dependent Claim
15 words
A method as in claim 11 wherein said binder consists essentially of an acrylamide polymer.
Claim 19
Dependent Claim
30 words
A method as in claim 11 wherein said binder is an acrylamide polymer selected from the group consisting of poly(acrylamide), poly(acrylamide-co-2-acetoacetoxyethyl methacrylate), poly(acrylamide-co-α-chloroacrylic acid), poly(acrylamide-co-1-vinylimidazole), poly(vinyl alcohol), and combinations thereof.
Claim 20
Dependent Claim
23 words
A method as in claim 11 wherein said component (2) also comprises a toning agent that is a combination of 3-mercapto-1,2,4-triazole and 2,4-dimercaptopyrimidine.
Claim 21
Dependent Claim
22 words
A method as in claim 11 wherein said silver salt of a heterocyclic thione consists essentially of a silver salt of 3-carboxymethyl-4-methyl-4-thiazolidine-2-thione.
Claim 22
Independent Claim
77 words
A method of preparing a photothermographic composition comprising sequentially mixing the following components: (1) a dispersion comprising 2-mercaptobenzothiazole and a silver salt of 3-carboxymethyl-4-methyl-4-thiazoline-2-thione, (2) a reducing agent solution comprising t-butylhydroquinone or isopropylhydroquinone with a toning agent consisting essentially of a combination of 3-mercapto-1,2,4-triazole with 2,4-dimercaptopyrimidine, (3) a polymeric binder consisting essentially of poly(acrylamide-co-1-vinylimidazole), (4) a para-isononylphenoxypolyglycidol surfactant, and (5) a silver iodide photosensitive emulsion containing a spectral sensitizing dye consisting essentially of anhydro-5,5'-6,6'-1,1'-diethyl-3,3'-bis(3-thiosulfatopropyl)-benzimidazolocarbocyanine hydroxide, sodium salt.
Claim 23
Independent Claim
77 words
A method of preparing a photothermographic composition comprising sequentially mixing the following components: (1) a dispersion comprising 2-mercaptobenzothiazole and a silver salt of 3-carboxymethyl-4-methyl-4-thiazoline-2-thione, (2) a reducing agent solution comprising t-butylhydroquinone or isopropylhydroquinone with a toning agent consisting essentially of a combination of 3-mercapto-1,2,4-triazole with 2,4-dimercaptopyrimidine, (3) a polymeric binder consisting essentially of poly(acrylamide-co-1-vinylimidazole), (4) a para-isononylphenoxypolyglycidol surfactant, and (5) a silver iodide photosensitive emulsion containing a spectral sensitizing dye consisting essentially of anhydro-5,5'-6,6'-1,1'-diethyl-3,3'-bis(3-thiosulfatopropyl)-benzimidazolocarbocyanine hydroxide, sodium salt.
Claim 24
Dependent Claim
42 words
A method as in claim 20 wherein said silver iodide photosensitive emulsion is heated for about 5 to about 30 minutes at a temperature within the range of about 50° to about 90° C before mixing it with other of said components.
Claim 25
Dependent Claim
80 words
A photothermographic element comprising a support having thereon in reactive association: (a) a 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole or 2-mercaptobenzoselenazole compound, (b) a silver salt of a heterocyclic thione represented by the formula: ##STR12## wherein R' represents atoms completing a five-member heterocyclic nucleus and Z is alkylene containing 1 to 30 carbon atms, (c) a reducing agent, (d) a binder, (e) a photosensitive silver halide emulsion, and (f) a spectral sensitizing dye that is a symmetrical or unsymmetrica thiosulfatoalkyl substituted benzimidazolocarbocyanine dye.
Claim 26
Dependent Claim
80 words
A photothermographic element comprising a support having thereon in reactive association: (a) a 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole or 2-mercaptobenzoselenazole compound, (b) a silver salt of a heterocyclic thione represented by the formula: ##STR12## wherein R' represents atoms completing a five-member heterocyclic nucleus and Z is alkylene containing 1 to 30 carbon atms, (c) a reducing agent, (d) a binder, (e) a photosensitive silver halide emulsion, and (f) a spectral sensitizing dye that is a symmetrical or unsymmetrica thiosulfatoalkyl substituted benzimidazolocarbocyanine dye.
Claim 27
Dependent Claim
39 words
A photothermographic element as in claim 22 comprising a spectral sensitizing concentration of said dye that is within the range of about 1 g to about 9 g of said spectral sensitizing dye per mole of said silver halide.
Claim 28
Dependent Claim
73 words
A photothermographic composition comprising: (a) a 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole or 2-mercaptobenzoselenazole compound, (b) a silver salt of a heterocyclic thione represented by the formula: ##STR13## wherein R' represents atoms completing a five-member heterocyclic nucleus and Z is alkylene containing 1 to 30 carbon atoms, (c) a reducing agent, (d) a binder, (e) a photosensitive silver halide emulsion, and (f) a spectral sensitizing dye that is a symmetrical or unsymmetrical thiosulfatoalkyl substituted benzimidazolocarbocyanine dye.
Claim 29
Dependent Claim
73 words
A photothermographic composition comprising: (a) a 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole or 2-mercaptobenzoselenazole compound, (b) a silver salt of a heterocyclic thione represented by the formula: ##STR13## wherein R' represents atoms completing a five-member heterocyclic nucleus and Z is alkylene containing 1 to 30 carbon atoms, (c) a reducing agent, (d) a binder, (e) a photosensitive silver halide emulsion, and (f) a spectral sensitizing dye that is a symmetrical or unsymmetrical thiosulfatoalkyl substituted benzimidazolocarbocyanine dye.
Claim 30
Dependent Claim
15 words
A photothermographic composition as in claim 24 wherein said dye is anhydro-5,5'-6,6'-tetrachloro-1,1'-diethyl-3,3'-bis(3-thiosulfatopropyl)-benzimidazolocarbocyanine hydroxide, sodium salt.
Claim 31
Dependent Claim
37 words
A photothermographic composition as in claim 24 comprising a spectral sensitizing concentration of said dye that is within the range of about 1 g to about 9 g of said dye per mole of said silver halide.
Claim 32
Dependent Claim
18 words
A photothermographic composition as in claim 24 wherein said silver halide contains at least 30 mole percent iodide.
Claim 33
Dependent Claim
16 words
A photothermographic composition as in claim 24 wherein said silver halide consists essentially of silver iodide.
Claim 34
Dependent Claim
12 words
A photothermographic composition as in claim 24 also comprising a polyglycidol surfactant.
Claim 35
Dependent Claim
12 words
A photothermographic composition as in claim 24 also comprising a para-isononylphenoxypolyglycidol surfactant.
Claim 36
Dependent Claim
16 words
A photothermographic composition as in claim 24 wherein said binder consists essentially of an acrylamide polymer.
Claim 37
Dependent Claim
32 words
A photothermographic composition as in claim 24 wherein said binder is an acrylamide polymer selected from the group consisting of poly(acrylamide), poly(acrylamide-co-2-acetoacetoxyethyl methacrylate), poly (acrylamide-co-α-chloroacrylic acid), poly(acrylamide-co-1-vinylimidazole), poly(vinyl alcohol), and combinations thereof.
Claim 38
Dependent Claim
17 words
A photothermographic composition as in claim 24 wherein said reducing agent consists essentially of t-butylhydroquinone or isopropylhydroquinone.
Claim 39
Dependent Claim
23 words
A photothermographic composition as in claim 24 wherein said silver salt of a heterocyclic thione consists essentially of a silver salt of 3-carboxymethyl-4-methyl-4-thiazoline-2-thione.
Claim 40
Dependent Claim
86 words
A photothermographic composition comprising: (a) 2-mercaptobenzothiazole, (b) a silver salt of 3-carboxymethyl-4-methyl-4-thiazoline-2-thione, (c) a reducing agent consisting essentially of t-butylhydroquinone or isopropylhydroquinone, (d) a toning agent consisting essentially of a combination of 3-mercapto-1,2,4-triazole and 2,4-dimercaptopyrimidine, (e) a polymeric binder consisting essentially of poly(acrylamide-co-1-vinylimidazole), (f) a photosensitive silver halide containing at least 30 mole percent iodide, and (g) a spectral sensitizing concentration of anhydro-5,5'-6,6'-tetrachloro-1,4'-diethyl-3,3'-bis(3-thiosulfatopropyl)-benzimidazolocarbocyanine hydroxide, sodium salt that is within the range of 1 g to 9 g of said dye per mole of said silver halide.
Claim 41
Dependent Claim
86 words
A photothermographic composition comprising: (a) 2-mercaptobenzothiazole, (b) a silver salt of 3-carboxymethyl-4-methyl-4-thiazoline-2-thione, (c) a reducing agent consisting essentially of t-butylhydroquinone or isopropylhydroquinone, (d) a toning agent consisting essentially of a combination of 3-mercapto-1,2,4-triazole and 2,4-dimercaptopyrimidine, (e) a polymeric binder consisting essentially of poly(acrylamide-co-1-vinylimidazole), (f) a photosensitive silver halide containing at least 30 mole percent iodide, and (g) a spectral sensitizing concentration of anhydro-5,5'-6,6'-tetrachloro-1,4'-diethyl-3,3'-bis(3-thiosulfatopropyl)-benzimidazolocarbocyanine hydroxide, sodium salt that is within the range of 1 g to 9 g of said dye per mole of said silver halide.
Claim 42
Dependent Claim
93 words
A photothermographic element comprising a support having thereon a layer comprising: (a) 2-mercaptobenzothiazole, (b) a silver salt of 3-carboxymethyl-4-methyl-4-thiazoline-2-thione, (c) a reducing agent consisting essentially of t-butylhydroquinone or isopropylhydroquinone, (d) a toning agent consisting essentially of a combination of 3-mercapto-1,2,4-triazole and 2,4-dimercaptopyrimidine, (e) a polymeric binder consisting essentially of poly(acrylamide-co-1-vinylimidazole), (f) a photosensitive silver halide containing at least 30 mole percent iodide, and (g) a spectral sensitizing concentration of anhydro-5,5'-6,6'-tetrachloro-1,1'-diethyl-3,3'-bis(3-thiosulfatopropyl)-benzimidazolocarbocyanine hydroxide, sodium salt that is within the range of 1 g to 9 g of said dye per mole of said silver halide.
Claim 43
Dependent Claim
93 words
A photothermographic element comprising a support having thereon a layer comprising: (a) 2-mercaptobenzothiazole, (b) a silver salt of 3-carboxymethyl-4-methyl-4-thiazoline-2-thione, (c) a reducing agent consisting essentially of t-butylhydroquinone or isopropylhydroquinone, (d) a toning agent consisting essentially of a combination of 3-mercapto-1,2,4-triazole and 2,4-dimercaptopyrimidine, (e) a polymeric binder consisting essentially of poly(acrylamide-co-1-vinylimidazole), (f) a photosensitive silver halide containing at least 30 mole percent iodide, and (g) a spectral sensitizing concentration of anhydro-5,5'-6,6'-tetrachloro-1,1'-diethyl-3,3'-bis(3-thiosulfatopropyl)-benzimidazolocarbocyanine hydroxide, sodium salt that is within the range of 1 g to 9 g of said dye per mole of said silver halide.
Claim 44
Dependent Claim
77 words
A photothermographic element comprising a support having thereon a layer comprising (a) a 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole or 2-mercaptobenzoselenazole compound, (b) a silver salt of a heterocyclic thione represented by the formula: ##STR14## wherein R' represents atoms completing a five-member heterocyclic nucleus and Z is alkylene containing 1 to 30 carbon atoms, (c) a reducing agent, (d) a binder, (e) a photosensitive silver halide emulsion, and (f) a spectral sensitizing dye containing essentially of anhydro-5,5'-6,6'-tetrachloro-1,4'-diethyl-3,3'-bis(3-thiosulfatopropyl)-benzimidazolocarbocyanine hydroxide, sodium salt.
Claim 45
Dependent Claim
77 words
A photothermographic element comprising a support having thereon a layer comprising (a) a 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole or 2-mercaptobenzoselenazole compound, (b) a silver salt of a heterocyclic thione represented by the formula: ##STR14## wherein R' represents atoms completing a five-member heterocyclic nucleus and Z is alkylene containing 1 to 30 carbon atoms, (c) a reducing agent, (d) a binder, (e) a photosensitive silver halide emulsion, and (f) a spectral sensitizing dye containing essentially of anhydro-5,5'-6,6'-tetrachloro-1,4'-diethyl-3,3'-bis(3-thiosulfatopropyl)-benzimidazolocarbocyanine hydroxide, sodium salt.
Claim 46
Dependent Claim
115 words
A process of developing and stabilizing an image in an imagewise exposed photothermographic element comprising a support having thereon a layer comprising (a) a 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole or 2-mercaptobenzoselenazole compound, (b) a silver salt of a heterocyclic thione represented by the formula: ##STR15## wherein R' represents atoms completing a five-member heterocyclic nucleus and Z is alkylene containing 1 to 30 carbon atoms, (c) a reducing agent, (d) a binder, (e) a photosensitive silver halide emulsion, and (f) a spectral sensitizing dye that is a symmetrical or unsymmetrical thiosulfatoalkyl substituted benzimidazolocarbocyanine dye comprising heating said element to a temperature within the range of about 100° to about 200° C until an image is developed and stabilized.
Claim 47
Dependent Claim
115 words
A process of developing and stabilizing an image in an imagewise exposed photothermographic element comprising a support having thereon a layer comprising (a) a 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole or 2-mercaptobenzoselenazole compound, (b) a silver salt of a heterocyclic thione represented by the formula: ##STR15## wherein R' represents atoms completing a five-member heterocyclic nucleus and Z is alkylene containing 1 to 30 carbon atoms, (c) a reducing agent, (d) a binder, (e) a photosensitive silver halide emulsion, and (f) a spectral sensitizing dye that is a symmetrical or unsymmetrical thiosulfatoalkyl substituted benzimidazolocarbocyanine dye comprising heating said element to a temperature within the range of about 100° to about 200° C until an image is developed and stabilized.
Claim 48
Dependent Claim
128 words
A process of developing and stabilizing an image in an imagewise exposed photothermographic element comprising a support having thereon a layer comprising (a) 2-mercaptobenzothiazole, (b) a silver salt of 3-carboxymethyl-4-methyl-4-thiazoline-2-thione, (c) a reducing agent consisting essentially of t-butylhydroquinone or isopropylhydroquinone, (d) a toning agent consisting essentially of a combination of 3-mercapto-1,2,4-triazole and 2,4-dimercaptopyrimidine, (e) a polymeric binder consisting essentially of poly(acrylamide-co-1-vinylimidazole), (f) a photosensitive silver halide containing at least 30 mole percent iodide, and (g) a spectral sensitizing concentration of anhydro-5,5'-6,6'-tetrachloro-1,1'-diethyl-3,3'-bis(3-thiosulfatopropyl)-benzimidazolocarbocyanine hydroxide, sodium salt that is within the range of 1 g to 9 g of said dye per mole of said silver halide comprising heating said element to a temperature within the range of about 140° to about 170° C until an image is developed and stabilized.
Claim 49
Dependent Claim
128 words
A process of developing and stabilizing an image in an imagewise exposed photothermographic element comprising a support having thereon a layer comprising (a) 2-mercaptobenzothiazole, (b) a silver salt of 3-carboxymethyl-4-methyl-4-thiazoline-2-thione, (c) a reducing agent consisting essentially of t-butylhydroquinone or isopropylhydroquinone, (d) a toning agent consisting essentially of a combination of 3-mercapto-1,2,4-triazole and 2,4-dimercaptopyrimidine, (e) a polymeric binder consisting essentially of poly(acrylamide-co-1-vinylimidazole), (f) a photosensitive silver halide containing at least 30 mole percent iodide, and (g) a spectral sensitizing concentration of anhydro-5,5'-6,6'-tetrachloro-1,1'-diethyl-3,3'-bis(3-thiosulfatopropyl)-benzimidazolocarbocyanine hydroxide, sodium salt that is within the range of 1 g to 9 g of said dye per mole of said silver halide comprising heating said element to a temperature within the range of about 140° to about 170° C until an image is developed and stabilized.
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USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1981-08-07 | 1982-02-06 | 1982-08-08 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1985-08-07 | 1986-02-06 | 1986-08-08 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1989-08-07 | 1990-02-06 | 1990-08-08 | $7700.00 | Window Closed / Lapsed |