US3885968A - Thermally developable light-sensitive material - Google Patents
Thermally developable light-sensitive material Download PDFInfo
- Publication number
- US3885968A US3885968A US474635A US47463574A US3885968A US 3885968 A US3885968 A US 3885968A US 474635 A US474635 A US 474635A US 47463574 A US47463574 A US 47463574A US 3885968 A US3885968 A US 3885968A
- Authority
- US
- United States
- Prior art keywords
- silver
- light
- sensitive material
- laurate
- material according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000000463 material Substances 0.000 title claims abstract description 73
- -1 silver halide Chemical class 0.000 claims abstract description 40
- 229910052709 silver Inorganic materials 0.000 claims abstract description 39
- 239000004332 silver Substances 0.000 claims abstract description 39
- MNMYRUHURLPFQW-UHFFFAOYSA-M silver;dodecanoate Chemical compound [Ag+].CCCCCCCCCCCC([O-])=O MNMYRUHURLPFQW-UHFFFAOYSA-M 0.000 claims abstract description 32
- OIZSSBDNMBMYFL-UHFFFAOYSA-M silver;decanoate Chemical compound [Ag+].CCCCCCCCCC([O-])=O OIZSSBDNMBMYFL-UHFFFAOYSA-M 0.000 claims abstract description 28
- AZEPWULHRMVZQR-UHFFFAOYSA-M lithium;dodecanoate Chemical compound [Li+].CCCCCCCCCCCC([O-])=O AZEPWULHRMVZQR-UHFFFAOYSA-M 0.000 claims abstract description 27
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 150000001875 compounds Chemical class 0.000 claims abstract description 17
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 16
- 239000011230 binding agent Substances 0.000 claims abstract description 15
- 230000003197 catalytic effect Effects 0.000 claims abstract description 7
- 239000010410 layer Substances 0.000 claims description 21
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 10
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 8
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 8
- 229910052751 metal Chemical group 0.000 claims description 7
- 239000002184 metal Chemical group 0.000 claims description 7
- DIKBFYAXUHHXCS-UHFFFAOYSA-N bromoform Chemical compound BrC(Br)Br DIKBFYAXUHHXCS-UHFFFAOYSA-N 0.000 claims description 6
- OKJPEAGHQZHRQV-UHFFFAOYSA-N iodoform Chemical compound IC(I)I OKJPEAGHQZHRQV-UHFFFAOYSA-N 0.000 claims description 6
- 229930185605 Bisphenol Natural products 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- 125000004429 atom Chemical group 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 230000003287 optical effect Effects 0.000 claims description 4
- 150000002989 phenols Chemical class 0.000 claims description 4
- HJUGFYREWKUQJT-UHFFFAOYSA-N tetrabromomethane Chemical compound BrC(Br)(Br)Br HJUGFYREWKUQJT-UHFFFAOYSA-N 0.000 claims description 4
- RLUFBDIRFJGKLY-UHFFFAOYSA-N (2,3-dichlorophenyl)-phenylmethanone Chemical compound ClC1=CC=CC(C(=O)C=2C=CC=CC=2)=C1Cl RLUFBDIRFJGKLY-UHFFFAOYSA-N 0.000 claims description 3
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 claims description 3
- YAQLSKVCTLCIIE-UHFFFAOYSA-N 2-bromobutyric acid Chemical compound CCC(Br)C(O)=O YAQLSKVCTLCIIE-UHFFFAOYSA-N 0.000 claims description 3
- LDLCZOVUSADOIV-UHFFFAOYSA-N 2-bromoethanol Chemical compound OCCBr LDLCZOVUSADOIV-UHFFFAOYSA-N 0.000 claims description 3
- 229910021612 Silver iodide Inorganic materials 0.000 claims description 3
- SJOOOZPMQAWAOP-UHFFFAOYSA-N [Ag].BrCl Chemical compound [Ag].BrCl SJOOOZPMQAWAOP-UHFFFAOYSA-N 0.000 claims description 3
- NZHXEWZGTQSYJM-UHFFFAOYSA-N [bromo(diphenyl)methyl]benzene Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)(Br)C1=CC=CC=C1 NZHXEWZGTQSYJM-UHFFFAOYSA-N 0.000 claims description 3
- 229950005228 bromoform Drugs 0.000 claims description 3
- 150000002484 inorganic compounds Chemical class 0.000 claims description 3
- 229910010272 inorganic material Inorganic materials 0.000 claims description 3
- 150000004780 naphthols Chemical class 0.000 claims description 3
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 claims description 3
- 229940045105 silver iodide Drugs 0.000 claims description 3
- RKSOPLXZQNSWAS-UHFFFAOYSA-N tert-butyl bromide Chemical compound CC(C)(C)Br RKSOPLXZQNSWAS-UHFFFAOYSA-N 0.000 claims description 3
- OWFYEPUNLDMRJB-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethyl-2-sulfanylideneimidazolidin-4-one Chemical compound CC1(C)N(Cl)C(=S)N(Cl)C1=O OWFYEPUNLDMRJB-UHFFFAOYSA-N 0.000 claims description 2
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 claims description 2
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 239000006224 matting agent Substances 0.000 claims description 2
- 150000002894 organic compounds Chemical class 0.000 claims description 2
- 150000002896 organic halogen compounds Chemical class 0.000 claims description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical group [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 2
- 239000003381 stabilizer Substances 0.000 claims description 2
- JBWKIWSBJXDJDT-UHFFFAOYSA-N triphenylmethyl chloride Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)(Cl)C1=CC=CC=C1 JBWKIWSBJXDJDT-UHFFFAOYSA-N 0.000 claims description 2
- FSWBNXJTOAUDKN-UHFFFAOYSA-N 1,3-dibromo-5,5-dimethyl-2-sulfanylideneimidazolidin-4-one Chemical compound CC1(C)N(Br)C(=S)N(Br)C1=O FSWBNXJTOAUDKN-UHFFFAOYSA-N 0.000 claims 1
- 239000011241 protective layer Substances 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- 239000000243 solution Substances 0.000 description 19
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 15
- 239000000975 dye Substances 0.000 description 15
- 238000000034 method Methods 0.000 description 14
- 235000014113 dietary fatty acids Nutrition 0.000 description 11
- 239000000194 fatty acid Substances 0.000 description 11
- 229930195729 fatty acid Natural products 0.000 description 11
- 150000004665 fatty acids Chemical class 0.000 description 11
- 239000000839 emulsion Substances 0.000 description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 9
- 230000001235 sensitizing effect Effects 0.000 description 8
- 239000005639 Lauric acid Substances 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 150000003378 silver Chemical class 0.000 description 7
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 6
- 238000011161 development Methods 0.000 description 6
- 239000004815 dispersion polymer Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 229940100892 mercury compound Drugs 0.000 description 6
- 150000002731 mercury compounds Chemical class 0.000 description 6
- 239000000123 paper Substances 0.000 description 6
- IJAPPYDYQCXOEF-UHFFFAOYSA-N phthalazin-1(2H)-one Chemical compound C1=CC=C2C(=O)NN=CC2=C1 IJAPPYDYQCXOEF-UHFFFAOYSA-N 0.000 description 6
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- AQRYNYUOKMNDDV-UHFFFAOYSA-M silver behenate Chemical compound [Ag+].CCCCCCCCCCCCCCCCCCCCCC([O-])=O AQRYNYUOKMNDDV-UHFFFAOYSA-M 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 108010010803 Gelatin Proteins 0.000 description 4
- 241000282414 Homo sapiens Species 0.000 description 4
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 4
- 239000012964 benzotriazole Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229920002678 cellulose Polymers 0.000 description 4
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 4
- 229920000159 gelatin Polymers 0.000 description 4
- 239000008273 gelatin Substances 0.000 description 4
- 235000019322 gelatine Nutrition 0.000 description 4
- 235000011852 gelatine desserts Nutrition 0.000 description 4
- CVHZOJJKTDOEJC-UHFFFAOYSA-N saccharin Chemical compound C1=CC=C2C(=O)NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-N 0.000 description 4
- 229940081974 saccharin Drugs 0.000 description 4
- 235000019204 saccharin Nutrition 0.000 description 4
- 239000000901 saccharin and its Na,K and Ca salt Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229920001747 Cellulose diacetate Polymers 0.000 description 3
- 239000001856 Ethyl cellulose Substances 0.000 description 3
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 3
- 239000001913 cellulose Substances 0.000 description 3
- 229920006217 cellulose acetate butyrate Polymers 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 3
- 229920001249 ethyl cellulose Polymers 0.000 description 3
- 235000019325 ethyl cellulose Nutrition 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 3
- 239000004926 polymethyl methacrylate Substances 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 229920002689 polyvinyl acetate Polymers 0.000 description 3
- 239000011118 polyvinyl acetate Substances 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 229910001961 silver nitrate Inorganic materials 0.000 description 3
- ORYURPRSXLUCSS-UHFFFAOYSA-M silver;octadecanoate Chemical compound [Ag+].CCCCCCCCCCCCCCCCCC([O-])=O ORYURPRSXLUCSS-UHFFFAOYSA-M 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- QWBBPBRQALCEIZ-UHFFFAOYSA-N 2,3-dimethylphenol Chemical compound CC1=CC=CC(O)=C1C QWBBPBRQALCEIZ-UHFFFAOYSA-N 0.000 description 2
- ICKWICRCANNIBI-UHFFFAOYSA-N 2,4-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C(C(C)(C)C)=C1 ICKWICRCANNIBI-UHFFFAOYSA-N 0.000 description 2
- UIAFKZKHHVMJGS-UHFFFAOYSA-N 2,4-dihydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1O UIAFKZKHHVMJGS-UHFFFAOYSA-N 0.000 description 2
- HXDOZKJGKXYMEW-UHFFFAOYSA-N 4-ethylphenol Chemical compound CCC1=CC=C(O)C=C1 HXDOZKJGKXYMEW-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 241000251468 Actinopterygii Species 0.000 description 2
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 2
- 229920000623 Cellulose acetate phthalate Polymers 0.000 description 2
- 229920008347 Cellulose acetate propionate Polymers 0.000 description 2
- DQEFEBPAPFSJLV-UHFFFAOYSA-N Cellulose propionate Chemical compound CCC(=O)OCC1OC(OC(=O)CC)C(OC(=O)CC)C(OC(=O)CC)C1OC1C(OC(=O)CC)C(OC(=O)CC)C(OC(=O)CC)C(COC(=O)CC)O1 DQEFEBPAPFSJLV-UHFFFAOYSA-N 0.000 description 2
- 229920002284 Cellulose triacetate Polymers 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 206010034960 Photophobia Diseases 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 2
- 229920002433 Vinyl chloride-vinyl acetate copolymer Polymers 0.000 description 2
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 229940081734 cellulose acetate phthalate Drugs 0.000 description 2
- 229920006218 cellulose propionate Polymers 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229920001688 coating polymer Polymers 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- MLFHJEHSLIIPHL-UHFFFAOYSA-N isoamyl acetate Chemical compound CC(C)CCOC(C)=O MLFHJEHSLIIPHL-UHFFFAOYSA-N 0.000 description 2
- 208000013469 light sensitivity Diseases 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- ZYIBVBKZZZDFOY-UHFFFAOYSA-N phloxine O Chemical compound O1C(=O)C(C(=C(Cl)C(Cl)=C2Cl)Cl)=C2C21C1=CC(Br)=C(O)C(Br)=C1OC1=C(Br)C(O)=C(Br)C=C21 ZYIBVBKZZZDFOY-UHFFFAOYSA-N 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 235000015170 shellfish Nutrition 0.000 description 2
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 description 2
- 229940071536 silver acetate Drugs 0.000 description 2
- NGBNXJUWQPLNGM-UHFFFAOYSA-N silver;azane Chemical compound N.[Ag+] NGBNXJUWQPLNGM-UHFFFAOYSA-N 0.000 description 2
- BTURAGWYSMTVOW-UHFFFAOYSA-M sodium dodecanoate Chemical compound [Na+].CCCCCCCCCCCC([O-])=O BTURAGWYSMTVOW-UHFFFAOYSA-M 0.000 description 2
- 229940082004 sodium laurate Drugs 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- QGKMIGUHVLGJBR-UHFFFAOYSA-M (4z)-1-(3-methylbutyl)-4-[[1-(3-methylbutyl)quinolin-1-ium-4-yl]methylidene]quinoline;iodide Chemical compound [I-].C12=CC=CC=C2N(CCC(C)C)C=CC1=CC1=CC=[N+](CCC(C)C)C2=CC=CC=C12 QGKMIGUHVLGJBR-UHFFFAOYSA-M 0.000 description 1
- KAKVFSYQVNHFBS-UHFFFAOYSA-N (5-hydroxycyclopenten-1-yl)-phenylmethanone Chemical compound OC1CCC=C1C(=O)C1=CC=CC=C1 KAKVFSYQVNHFBS-UHFFFAOYSA-N 0.000 description 1
- VFNKZQNIXUFLBC-UHFFFAOYSA-N 2',7'-dichlorofluorescein Chemical compound O1C(=O)C2=CC=CC=C2C21C1=CC(Cl)=C(O)C=C1OC1=C2C=C(Cl)C(O)=C1 VFNKZQNIXUFLBC-UHFFFAOYSA-N 0.000 description 1
- FLLRQABPKFCXSO-UHFFFAOYSA-N 2,5-ditert-butyl-4-methoxyphenol Chemical compound COC1=CC(C(C)(C)C)=C(O)C=C1C(C)(C)C FLLRQABPKFCXSO-UHFFFAOYSA-N 0.000 description 1
- CDMGNVWZXRKJNS-UHFFFAOYSA-N 2-benzylphenol Chemical compound OC1=CC=CC=C1CC1=CC=CC=C1 CDMGNVWZXRKJNS-UHFFFAOYSA-N 0.000 description 1
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 1
- XIRDTMSOGDWMOX-UHFFFAOYSA-N 3,4,5,6-tetrabromophthalic acid Chemical compound OC(=O)C1=C(Br)C(Br)=C(Br)C(Br)=C1C(O)=O XIRDTMSOGDWMOX-UHFFFAOYSA-N 0.000 description 1
- FVQBNGXOHJYGMZ-UHFFFAOYSA-N 3,5-ditert-butyl-2,6-dihydroxybenzoic acid Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=C(O)C(C(O)=O)=C1O FVQBNGXOHJYGMZ-UHFFFAOYSA-N 0.000 description 1
- TXFPEBPIARQUIG-UHFFFAOYSA-N 4'-hydroxyacetophenone Chemical compound CC(=O)C1=CC=C(O)C=C1 TXFPEBPIARQUIG-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- WEMYXYMZQRSPIA-UHFFFAOYSA-N 4-(2,4-dihydroxyphenyl)sulfanylbenzene-1,3-diol Chemical compound OC1=CC(O)=CC=C1SC1=CC=C(O)C=C1O WEMYXYMZQRSPIA-UHFFFAOYSA-N 0.000 description 1
- XIIIHRLCKLSYNH-UHFFFAOYSA-N 4-Hexyloxyphenol Chemical compound CCCCCCOC1=CC=C(O)C=C1 XIIIHRLCKLSYNH-UHFFFAOYSA-N 0.000 description 1
- PBBGSZCBWVPOOL-HDICACEKSA-N 4-[(1r,2s)-1-ethyl-2-(4-hydroxyphenyl)butyl]phenol Chemical compound C1([C@H](CC)[C@H](CC)C=2C=CC(O)=CC=2)=CC=C(O)C=C1 PBBGSZCBWVPOOL-HDICACEKSA-N 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N 4-nonylphenol Chemical compound CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- ZUTYZAFDFLLILI-UHFFFAOYSA-N 4-sec-Butylphenol Chemical compound CCC(C)C1=CC=C(O)C=C1 ZUTYZAFDFLLILI-UHFFFAOYSA-N 0.000 description 1
- 235000021357 Behenic acid Nutrition 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
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- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- FJWGYAHXMCUOOM-QHOUIDNNSA-N [(2s,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6s)-4,5-dinitrooxy-2-(nitrooxymethyl)-6-[(2r,3r,4s,5r,6s)-4,5,6-trinitrooxy-2-(nitrooxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-3,5-dinitrooxy-6-(nitrooxymethyl)oxan-4-yl] nitrate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O)O[C@H]1[C@@H]([C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@@H](CO[N+]([O-])=O)O1)O[N+]([O-])=O)CO[N+](=O)[O-])[C@@H]1[C@@H](CO[N+]([O-])=O)O[C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O FJWGYAHXMCUOOM-QHOUIDNNSA-N 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
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- 229940116226 behenic acid Drugs 0.000 description 1
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- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 229940114055 beta-resorcylic acid Drugs 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- YXVFYQXJAXKLAK-UHFFFAOYSA-N biphenyl-4-ol Chemical compound C1=CC(O)=CC=C1C1=CC=CC=C1 YXVFYQXJAXKLAK-UHFFFAOYSA-N 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
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- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
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- 235000001671 coumarin Nutrition 0.000 description 1
- 125000000332 coumarinyl group Chemical group O1C(=O)C(=CC2=CC=CC=C12)* 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- RGLYKWWBQGJZGM-ISLYRVAYSA-N diethylstilbestrol Chemical compound C=1C=C(O)C=CC=1C(/CC)=C(\CC)C1=CC=C(O)C=C1 RGLYKWWBQGJZGM-ISLYRVAYSA-N 0.000 description 1
- 229960000452 diethylstilbestrol Drugs 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- POULHZVOKOAJMA-UHFFFAOYSA-M dodecanoate Chemical compound CCCCCCCCCCCC([O-])=O POULHZVOKOAJMA-UHFFFAOYSA-M 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- SEACYXSIPDVVMV-UHFFFAOYSA-L eosin Y Chemical compound [Na+].[Na+].[O-]C(=O)C1=CC=CC=C1C1=C2C=C(Br)C(=O)C(Br)=C2OC2=C(Br)C([O-])=C(Br)C=C21 SEACYXSIPDVVMV-UHFFFAOYSA-L 0.000 description 1
- IINNWAYUJNWZRM-UHFFFAOYSA-L erythrosin B Chemical compound [Na+].[Na+].[O-]C(=O)C1=CC=CC=C1C1=C2C=C(I)C(=O)C(I)=C2OC2=C(I)C([O-])=C(I)C=C21 IINNWAYUJNWZRM-UHFFFAOYSA-L 0.000 description 1
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- 150000002344 gold compounds Chemical class 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229950001996 hexestrol Drugs 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229940117955 isoamyl acetate Drugs 0.000 description 1
- 229940070765 laurate Drugs 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229960001078 lithium Drugs 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- BRMYZIKAHFEUFJ-UHFFFAOYSA-L mercury diacetate Chemical compound CC(=O)O[Hg]OC(C)=O BRMYZIKAHFEUFJ-UHFFFAOYSA-L 0.000 description 1
- NGYIMTKLQULBOO-UHFFFAOYSA-L mercury dibromide Chemical compound Br[Hg]Br NGYIMTKLQULBOO-UHFFFAOYSA-L 0.000 description 1
- DZVCFNFOPIZQKX-LTHRDKTGSA-M merocyanine Chemical compound [Na+].O=C1N(CCCC)C(=O)N(CCCC)C(=O)C1=C\C=C\C=C/1N(CCCS([O-])(=O)=O)C2=CC=CC=C2O\1 DZVCFNFOPIZQKX-LTHRDKTGSA-M 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- VYQNWZOUAUKGHI-UHFFFAOYSA-N monobenzone Chemical compound C1=CC(O)=CC=C1OCC1=CC=CC=C1 VYQNWZOUAUKGHI-UHFFFAOYSA-N 0.000 description 1
- 229960000990 monobenzone Drugs 0.000 description 1
- 239000005445 natural material Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 150000002916 oxazoles Chemical class 0.000 description 1
- 150000002941 palladium compounds Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000003058 platinum compounds Chemical class 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920006289 polycarbonate film Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920003225 polyurethane elastomer Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229940065287 selenium compound Drugs 0.000 description 1
- 150000003343 selenium compounds Chemical class 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000010129 solution processing Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 150000001629 stilbenes Chemical class 0.000 description 1
- 235000021286 stilbenes Nutrition 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- JRFBNCLFYLUNCE-UHFFFAOYSA-N zinc;oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[O-2].[Ti+4].[Zn+2] JRFBNCLFYLUNCE-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/494—Silver salt compositions other than silver halide emulsions; Photothermographic systems ; Thermographic systems using noble metal compounds
- G03C1/498—Photothermographic systems, e.g. dry silver
- G03C1/49836—Additives
- G03C1/49845—Active additives, e.g. toners, stabilisers, sensitisers
Definitions
- ABSTRACT A thermally developable light-sensitive material comprising a support having thereon at least one layer containing: (a) silver laurate or silver caprate; (b) a catalytic amount of a light-sensitive silver halide or a compound capable of forming a light-sensitive silver halide by the reaction thereof with the organic silver salt (a); (c) a reducing agent; ((1) a binder; and (e) lithium laurate.
- the present invention relates to a thermally developable light-sensitive material and, more particularly, it is concerned with a thermally developable light-sensitive material having less fogging at the unexposed areas upon being heated (hereinafter referred to as heat fog).
- the silver halide light-sensitive material used in this mehtod must be subjected, after imagewise exposure, to a development processing using a developer and to the several processing steps of stopping, fixing,, washing, stabilizing, etc., in order to prevent the developed image from becoming discolored or faded under normal illumination and also to prevent the nondeveloped area (hereinafter referred to as background") thereof from becoming blackened.
- a light-sensitive element comprising mainly a silver salt such as the silver salt of a long-chain aliphatic carboxylic acid (e.g., silver behenate, etc.), the silver salt of saccharin, the silver salt of benzotriazole, or the like and a catalytic amount of silver halide is used.
- a silver salt such as the silver salt of a long-chain aliphatic carboxylic acid (e.g., silver behenate, etc.), the silver salt of saccharin, the silver salt of benzotriazole, or the like and a catalytic amount of silver halide is used.
- thermally developable light-sensitive materials which have thus far been suggested which contain a composition comprising a silver salt of fatty acid, a reducing agent and a catalytic amount of silver halide
- heat development after imagewise exposure not only blackens the exposed areas but also darkens the unexposed areas as well, thus causing the so-called fog.
- heating is conducted to only such extent that the unexposed areas are not darkened, the exposed areas are not blackened sufficiently to obtain images with a good contrast. Therefore, the darkening of the unexposed areas must be eliminated when heat development is sufficiently conducted.
- the silver salts of higher fatty acids such as silver behenate or silver stearate, silver salt of benzotriazole and silver salt of saccharin are suitable as the imageforming compounds.
- a large quantity of solvent and a large-sized production apparatus is required due to the low solubility of the starting materials; behenic acid or behenic acid salts and stearic acid or stearic acid salts in such solvents as water and methanol, which entails a serious increase in production costs.
- the silver salts of fatty acids possess the above-described defects.
- the silver salts of lower chain length fatty acids such as silver acetate tend to be blackened when exposed to room light due to their light sensitivity. Therefore, the white areas in the processed light-sensitive material become darkened to such an extent that the image areas become impossible to discern. Therefore, the silver salts of fatty acids of a medium chain length are expected to be preferable.
- particularly silver laurate and silver caprate are suitable.
- the silver salts of fatty acids higher than lauric acid posses the same defects as the above-described silver behenate in no small degree.
- the silver salts of fatty acids lower than capric acid are not preferred since the starting materials therefor have an offensive odor and posses the defects of silver acetate in no small degree.
- silver laurate has also been believed to be poor in stability to light.
- this light stability has now been found to be improved by improving the process for producing silver laurate and the light sensitive composition. The same applies to silver caprate.
- An object of the present invention is to provide a thermally developable light-sensitive material using silver laurate or silver caprate.
- Another object of the present invention is to provide a thermally developable light-sensitive material which has less fog upon heat development after imagewise exposure of the light-sensitive material.
- lithium laurate is effective for attaining the above-described objects.
- the present invention provides a thermally developable light-sensitive material comprising a support having thereon at least one layer containing: (a) silver laurate or silver caprate; (b) a catalytic amount of a light-sensitive silver halide or a compound capable of forming a light-sensitive silver halide by the reaction thereof with the organic silver salt (a); (c) a reducing agent; (d) a binder; and (e) lithium laurate.
- the amount of lithium laurate, componenet (e), used is about 0.0l mol to mols, preferably 0.1 to 2 mols, per 1 mol of silver laurate or silver caprate.
- lithium laurate commercially available lith ium laurate of a special grade or that prepared by reacting lithium ion with lauric acid or a lauric acid salt, such as sodium laurate or potassium laurate, can be used.
- a precipitate of lithium laurate can be obtained by adding an aqueous solution of lithium nitrate to an aqueous solution of sodium laurate.
- a precipitate of lithium laurate can be obtained by adding an aqueous solution of lithium hydroxide to a metharol solution of lauric acid.
- the lithium laurate can be present during the formation of the silver laurate or silver caprate, or the lithium laurate can be added after the formation of the silver laurate or silver caprate, before or after the formation of the silver hallde. Also, the lithium laurate can be added after components (a) to (b) are all added. Furthermore, it can be present in another layer adjacent the layer containing the silver laurate or silver caprate, although the effects thereof are reduced.
- compositions which can be used as component (b) in the present invention there are (1) compounds capable of forming a light-sensitive silver halide by the reaction thereof with the above-described organic silver salt (a) and (2) silver halide.
- Specific examp s ui" 1) are inorganic compounds represented'fiy the general formula;
- logen compounds such as triphenylmethyl bromide, 2-bromo-2-methylpropane, 2-bromobutyric acid, 2- bromoethanol, dichlorobenzophenone, iodoform, bromoform, carbon, tetrabromide, an N-haloacetamide, l,3, -dibromo-5 ,5-dimethylthiohydantoin, 1,3- dichloro-S, S-dimethylthiohydantoin, etc.
- the silver halide of compound (2) can be silver cloride, silver bromiodide, silver clorobromoiodide, silver chlorobromide and silver iodide.
- a suitable particle size can range from about 0.001 p. to 0.5 u, preferably 0.03 p. to 0.2 u.
- a silver halide containing more than about 50 mol percent bromide is preferred.
- Emulsions containing a light-sensitive silver halide can be prepared in any conventional manner known in the field of photography.
- emulsions there are illustrated, for example, an emulsion prepared by the single jet method, an emulsion prepared by the double jet method (e.g., a Lippmann emulsion), an ammoniacal emulsion, a thiocyanateor thioether-ripened emulsion, the emulsions described in, e.g., US. Pat. Nos. 2,222,264, 3,320,069, 3,271,157, etc., and the like.
- the silver halide which can be used in the present invention can be sensitized with chemical sensitizers such as a reducing agent, sulfur, a selenium compound, a gold compound, a platinum compound, a palladium compound, or a combination thereof.
- chemical sensitizers such as a reducing agent, sulfur, a selenium compound, a gold compound, a platinum compound, a palladium compound, or a combination thereof.
- Suitable procedures therefor are described in e.g., US. Pat. Nos. 2,623,499, 2,399,083, 3,297,447 and 3,297,446.
- component (b) can be used alone or as a combination of two or more.
- Component (b) is suitably added in an amount of from 0.01 mol to 0.5 mol, preferably 0.02 mol, per 1 mol of the silver laurate or silver caprate of component (a). If the amount of the component (b) is less than the lower limit of this range, the sensitivity is reduced while if the amount exceeds the upper limit of the range, the non-image areas of the heat-developed material are gradually blackened upon leaving the material under room light, which can spoil the contrast between the image areas and non-image areas.
- reducing agents must be selected which are suitable for reducing the silver salt of component (a) to form images upon heating the light-sensitive material in the presence of exposed silver halide catalyst.
- reducing agents are substituted phenols, naphthols, substituted or unsubstituted bisphenols, hydroquinone monoethers, and the like.
- a substituted phenol or a substituted bisphenol is preferred.
- sorcin 2,4-dihydroxyphenylsulfide, 5,7-dihyroxy-4- methylcoumarin, p-methoxyphenol 2-t-butyl-4- methoxyphenol, p-phenylphenol, p-t-butylphen ol B-naphthol, 2,4,5-trimethylphenol bisphenol A, 2,5-dit-butyl-4-methoxyphenol, hydroquinone mono-npropyl ether, hydroquinone mono-n-hexyl ether, 2,3- dimethylphenol, 2,4-di-t-butylphenol, N,N-di(4- hydrozyphenoyl)urea, and the like.
- These reducing agents can also be used as a combination of two or more.
- the reducing agent used in the present invention is added in an amount of 0.1 to 5 mols, preferably of 0.5 to 1.5 mols, per 1 mol of the silver laurate or silver caprate of component (a).
- components (a), (b), (c) and (e) are preferably dispersed in a binder (d), and are coated on a support. Also, a part or all of these layers can be coated as separate layers.
- a binder any of those binders which have heretofore been used in this field can be used.
- Hydrophobic binders are usually preferable, but hydrophilic binders can also be used.
- Transparent or semi-transparent binders are preferred and illustrative examples are, e.g., natural substances such as gelatin, gelatin derivatives, a mixture thereof with a latex-type vinyl polymer, a cellulose derivative, etc., and synthetic polymer materials.
- gelatin examples include gelatin, phthaloylated gelatin, polyvinyl butyral, polyacrylamide, cellulose acetate butyrate, cellulose acetate propionate polymethyl methacrylate, polyvinyl pyrrolidone, polystyrene, ethyl cellulose, polyvinyl chloride, rubber chloride, polyisobutylene, butadiene-styrene copolymers, vinyl chloride-vinyl acetate copolymers, vinyl acetate, vinyl chloride-maleic acid copolymers, polyvinyl alcohol, polyvinyl acetate, benzyl cellulose, cellulose diacetate, cellulose triacetate cellulose propionate, cellulose acetate phthalate, and the like.
- binders are polyvinylbutyral, polyvinylacetate, ethylcellulose, polymethyl-methacrylate and celluloseacetatebutyrate.
- the weight ratio of the binder to the silver laurate or silver caprate of component (a) is suitably about 4:1 to about 1:4, preferably 2:1 to 1:2.
- supports are a cellulose nitrate film, a cellulose ester film, a polyvinyl acetal film, a polystyrene film, a polyethylene terephthalate film, a polycarbonate film, glass, paper, metal, and the like.
- a support paper subjected to a processing to impart hydrophilicity e.g., to a surface-treating with polyvinyl alcohol, is suitable.
- papers sizing-processed. with saccharides are suitable.
- the suitable amount of the above-described binder dispersion to be coated on a support is about 0.2 to 3 g/m (calculated as silver), more preferably, 0.4 to 2 g/m. If the amount coated is less than 0.2 g/m sufficient image density cannot be obtained while if the amount coated is greater than 3 g/m the production cost is increased.
- An anti-static layer or an electroconductive layer can be provided on the thermally developable lightsensitive material used for the practice of the invention. Also, an anti-halation substance and an anti-halation dye can be incorporated in the material.
- thermally developable light-sensitive material used in the practice of the present invention can further be incorporated if desired, a matting agent such as starch, titanium dioxide zinc oxide, silica, etc.
- a matting agent such as starch, titanium dioxide zinc oxide, silica, etc.
- flucrescent brightening agents such as the stilbenes, triazines, oxazoles, coumarines, etc. can be incorporated in the material.
- optically sensitizing dyes which have heretofore been used for silver halide emulsions can advantageously be used so as to impart increased light sensitivity to the thermally developable light-sensitive material of the present invention.
- Suitable optical sensitizing dyes are disclosed for example, in U.S. Pat. No. 3,457,075.
- optical sensitization can be effected by adding a sensitizing dye as an organic solvent solution or a dispersion.
- Suitable optical sensitizers are, e.g., cyanine dyes, merocyanine dyes, rhodacyanine dyes styryl dyes, Erythrosine, Eosine, tetrachloro tetrabromofluorescein, 2 ',7 dichlorofluorescein or like acidic dyes.
- the amount of these dyes can range from about 10 mol to about l0 mol per 1 mol of the silver laurate or silver caprate of component (a).
- additives such as a toning agent (e.g., phthalazinone, etc.), a stabilizing agent (compound capable of preventing discoloration of images with the lapse of time after image formation (e.g., benzenesulfonic acid, p-toluenesulfonic acid, tetrabromophthalic acid, tetrabromophthalic acid anhydride, etc.) can be incorporated in the thermally developable light-sensitive layer.
- a toning agent e.g., phthalazinone, etc.
- a stabilizing agent compound capable of preventing discoloration of images with the lapse of time after image formation
- a top-coating polymer layer can be provided on the lightsensitive layer.
- the film thickness of the top-coating polymer layer can suitably range from about 1 p. to 20 t.
- Suitable polymers are, e.g., polyvinyl chloride, polyvinyl acetate, vinyl chloridevinyl acetate copolymers, polyvinyl butyral, polystyrene, polymethyl methacrylate, polyurethane rubber, xylene resins, benzyl cellulose, ethyl cellulose, cellulose acetate butyrate, cellulose diacetate, cellulose triacetate, polyvinylidene chloride, chlorinated polypropylene, polyvinyl pyrrolidone, cellulose propionate, polyvinyl formal, cellulose acetate phthalate, polycarbonate, cellulose acetate propionate, and the like.
- the thermally developable light-sensitive layer and the top-coating layer to be used in the practice of the present invention can be applied to a support using various coating methods including a dip-coating method, an air knife-coating method, a curtain-coating method, and an extrusion coating method using a hopper as described in U.S. Pat. No. 2,681,294. If desired, two or more layers can be applied at the same time.
- the above-described thermally developable lightsensitive material can be developed, after being exposed, e.g., for about 10 second to 10 seconds, to radiation from a xenon lamp, a tungsten lamp a mercury lamp or like light source by merely heating the light-sensitive material. Heating temperatures of about to 180 C, more preferably, C to C, are suitable for such development. Higher or lower temperatures can be selected within the above-described range by prolonging or shortening the heating time appropriately.
- the developing time is usually from 1 second to about 60 seconds.
- the light-sensitive material of the present invention can be contacted with a simple heating plate or the like or with a heated drum, or, in some cases, the material can be passed through a heated space.
- the material can be heated using high frequency induction heating or using a laser beam.
- the thermally developable light-sensitive material in accordance with the present invention has less heat fog in the unexposed areas when development-processed after imagewise exposure.
- EXAMPLE 1 A solution prepared by dissolving 8.6 g ofcapric acid in 100 ml of isoamyl acetate was maintained at 5C and while stirring with a stirrer 50 ml of an aqueous solution of a silver ammonium complex salt (cooled to 5C) containing 8.5 g of silver nitrate was added thereto over a 30 second period to react the capric acid with the silver ion.
- spindle-shaped silver caprate crystals of a length of about 3 uand a width of about 0.2 u were obtained
- the resulting silver salt was washed successively with water and methanol. Thereafter, 3.0 g of polyvinyl butyral and ml of isopropyl alcohol were added to 2.1 g of the silver caprate and dispersed using a ball mill to prepare a polymer dispersion of the silver salt.
- thermoly developable light-sensitive coating solution To 20 g of this polymer dispersion of the silver salt were added the following components to prepare a thermally developable light-sensitive coating solution. This solution was applied to a paper support in a silver amount of 1.0 g per 1 m of the support to prepare Thermally Developable Light-Sensitive Material (A).
- Thermally Developable Light-Sensitive Material (8) not containing lithium laurate and Thermally Developable Light- Sensitive Material (C) containing conventionally known mercuric acetate in place of the lithium laurate of the present invention were prepared in the similar manner.
- lithium laurate of the present invention reduces the heat fog and provides sufficient image density, i.e., images with good contrast are obtained.
- EXAMPLE 2 The procedures described in Example 1 were repeated except for using 2 g oflithium laurate. When the resulting sample was exposed and heat-developed under the same conditions as described in Example 1, an image of an image density of 1.18 (maximum density area) and a non-image density of 0.17 (heat-fogged area) (reflection density) was obtained.
- EXAMPLE 3 11 grams of lauric acid was dissolved in 100 ml of butyl acetate and while maintaining the solution at 10C, 100 ml of a dilute nitric acid aqueous solution (pH at 25C: 2.0) was added thereto under stirring with a stirrer. Then, while continuing the stirring, 50 ml of an aqueous solution (cooled to 0C) of a silver ammonium complex salt containing 8.5 g of silver nitrate was added thereto over a 1 minute period to react the lauric acid with the silver ion. Thus, spindle-shaped silver laurate crystals of a length of about 1 u and a width of 0.05 p. were obtained.
- the resulting silver salt was washed successively, with water and methanol. Thereafter, 3.0 g of polyvinyl butyral and 20ml of isopropyl alcohol were added to 2.7 g of the silver laurate and dispersed using a ball mill to prepare a polymer dispersion of the silver salt.
- Each of these Light-Sensitive Materials (A), (B) and (C) was exposed to a radiation from a tungsten light source (using a step wedge) to impart an exposure of 500,000 lx' sec. Thereafter, the materials were heated at 120C for 20 seconds for development. Thus stepwise images were obtained.
- lithium laurate of the present invention reduces heat fog and provides sufficient image density, i.e., images having good contrast were obtained.
- EXAMPLE 4 EXAMPLE 5 grams of lauric acid and 2 g of sodium hydroxide were dissolved in 200 ml of water. Then, 100 ml of toluene containing dissolved therein 3 g of lauric acid was added thereto and stirred with a-stirrer to emulsify (800 rpm, 5 minutes). While continuing the stirring, a silver aqueous solution (8.5 g of silver nitrate plus 50 cc of water) was added thereto over a 60 second period to produce silver laurate.
- the silver laurate thus precipitated was collected.
- 30 grams of polyvinyl butyral and 200 ml of isopropyl alcohol were added thereto and dispersed in a ball mill to prepare a silver laurate polymer dispersion.
- To this silver laurate polymer dispersion were added the following components to prepare a thermally developable light-sensitive composition. This was then coated on a paper support in a silver amount of 0.7 g per 1 m of the support to prepare a thermally developable lightsensitive material.
- Example 5 The same result as described in Example 5 was obtained except that the sensitivity was less than l/50th that in Example 5, and the color of the image was brown.
- a thermally developable light-sensitive material comprising a support having thereon at least one layer containing: (a) silver laurate or silver caprate; (b) a catalytic amount of a light-sensitive silver halide or a compound capable of forming a light-sensitive silver halide by the reaction thereof with said organic silver salt (a); (c) a reducing agent; (d) a binder; and (e) lithium laurate.
- photosensitive silver halide is silver chloride, silver bromoiodide, silver chlorobromoiodide, silver chlorobromide or silver iodide.
- M is a hydrogen atom, an ammonium group or a metal atom
- X is a halogen atom
- n is 1 when M is a hydrogen atom or an ammonium group and when M is a metal atom, n is equal to the valence of the metal, and an organic compound.
- the light-sensitive material according to claim 3 wherein the organic halogen compound is triphenylmethyl chloride, triphenylmethyl bromide, 2-bromo-2- methylpropane, 2-bromo-butyric acid, 2- bromoethanol, dichlorobenzophenone, iodoform, bromoform, carbon tetrabromide, an N-haloacetamide, 1,3-dibromo-5 ,S-dimethylthiohydantoin, or 1,3- dichloro-5,5-dimethyl thiohydantoin 5.
- the amount of the photosensitive silver halide component (b) ranges from about 0.01 to 0.5 mole per mole of said silver laurate or silver caprate of component (a).
- naphthol a substituted naphthol, a substituted or unsubstituted bisphenol or a hydroquinone monoether.
- weight ratio of the binder component (d) to said silver laurate or silver caprate of component (a) ranges from about 4:l to 1:4.
Abstract
A thermally developable light-sensitive material comprising a support having thereon at least one layer containing: (a) silver laurate or silver caprate; (b) a catalytic amount of a lightsensitive silver halide or a compound capable of forming a lightsensitive silver halide by the reaction thereof with the organic silver salt (a); (c) a reducing agent; (d) a binder; and (e) lithium laurate.
Description
United States Patent Ikenoue et al.
[451 May 27, 1975 THERMALLY DEVELOPABLE LIGHT-SENSITIVE MATERIAL Inventors: Shinpei lkenoue; Takao Masuda, both of Asaka, Japan Assignee: Fuji Photo Film Co., Ltd.,
Kanagawa, Japan Filed: May 30, 1974 Appl. No.2 474,635
US. Cl. 96/67; 96/109; 96/114; 96/114.l;96/114.6
Int. Cl. G03c 1/02; G03c 1/34 Field of Search... 96/1 14.1, 114.6, 109, 48 HD, 96/67 References Cited UNITED STATES PATENTS l/1974 Hartman et a1. 96/48 l-lD Primary Examiner-Norman G. Torchin Assistant ExaminerAlfonso T. SuroPico Attorney, Agent, or FirmSughrue, Rothwell, Mion, Zinn & Macpeak [57] ABSTRACT A thermally developable light-sensitive material comprising a support having thereon at least one layer containing: (a) silver laurate or silver caprate; (b) a catalytic amount of a light-sensitive silver halide or a compound capable of forming a light-sensitive silver halide by the reaction thereof with the organic silver salt (a); (c) a reducing agent; ((1) a binder; and (e) lithium laurate.
12 Claims, No Drawings THERMALLY DEVELOPABLE LIGHT-SENSITIVE M ATERIAL BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermally developable light-sensitive material and, more particularly, it is concerned with a thermally developable light-sensitive material having less fogging at the unexposed areas upon being heated (hereinafter referred to as heat fog).
2. Description of the Prior Art Heretofore, the photographic method using silver halide has been the most widely been practiced, since this method provides excellent sensitivity, gradation and similar photographic properties as compared with the electrophotographic method, the diazo-type photographic method, and the like.
However, the silver halide light-sensitive material used in this mehtod must be subjected, after imagewise exposure, to a development processing using a developer and to the several processing steps of stopping, fixing,, washing, stabilizing, etc., in order to prevent the developed image from becoming discolored or faded under normal illumination and also to prevent the nondeveloped area (hereinafter referred to as background") thereof from becoming blackened. Therefore, difficulties in that processing of such a material is time consuming and very laborsome, in that human body is exposed to danger in the handling of the chemicals therefor, and in that the processing rooms and workers hands and clothes are stained exist Therefore, in the photographic method using silver halide, improvements such that the material can be processed in a dry state without solution-processing and such that the processed images can be maintained stable are very desirable.
For this purpose, various attempts have so far been made. One of them is an attempt, as described in Japanese Patent Publication Nos. 26582/69, 12700/70. 22185/70, and 41865/71, and U.S. Pat. Nos. 3,152,904, 3,457,075 and 3,635,719, etc., to use a thermally developable light-sensitive material. In this attempt, a light-sensitive element comprising mainly a silver salt such as the silver salt of a long-chain aliphatic carboxylic acid (e.g., silver behenate, etc.), the silver salt of saccharin, the silver salt of benzotriazole, or the like and a catalytic amount of silver halide is used.
However, in the thermally developable light-sensitive materials which have thus far been suggested which contain a composition comprising a silver salt of fatty acid, a reducing agent and a catalytic amount of silver halide, heat development after imagewise exposure not only blackens the exposed areas but also darkens the unexposed areas as well, thus causing the so-called fog. Of course, if heating is conducted to only such extent that the unexposed areas are not darkened, the exposed areas are not blackened sufficiently to obtain images with a good contrast. Therefore, the darkening of the unexposed areas must be eliminated when heat development is sufficiently conducted.
The incorporation of a mercury ion-providing compound so as to prevent the darkening of unexposed areas, the so-called heat fog, is known, as described in Japanese Patent Publication No. llll3/72. However, as is well-known, mercury compounds are very poisonous and, when a mercury compound containing lightsensitive material is licked, e.g., by babies, there is a great possibility of the mercury compound being ingested into the human body to damage the health of the human being. In addition, since this type of lightsensitive material is developed by heating to C to C, there is the possibility of scattering mercury. Furthermore, in the step of re-using waste lightsensitive materials containing the mercury compounds as reclaimed paper, there is the possibility of the mercury compounds being discharged into rivers. In this case, the mercury compound accumulates in fish and shellfish, leading to damage of the health of human beings consumming the fish and shellfish.
On the other hand, it has heretofore been believed that the silver salts of higher fatty acids such as silver behenate or silver stearate, silver salt of benzotriazole and silver salt of saccharin are suitable as the imageforming compounds. However, in the production of the silver salts of higher fatty acids such as silver behenate or silver stearate in a great quantity, a large quantity of solvent and a large-sized production apparatus is required due to the low solubility of the starting materials; behenic acid or behenic acid salts and stearic acid or stearic acid salts in such solvents as water and methanol, which entails a serious increase in production costs. Also, with the silver salt of benzotriazole and silver salt of saccharin, production cost is increased since the starting materials, benzotriazole and saccharin, are more expensive than fatty acids. In addition, there are no particularly excellent advantages in the photographic properties of these latter materials. Therefore, it is desirable to use a silver salt of fatty acid.
As the silver salt of fatty acids, the silver salts of higher fatty acids such as silver behenate and silver stearate possess the above-described defects. On the other hand, the silver salts of lower chain length fatty acids such as silver acetate tend to be blackened when exposed to room light due to their light sensitivity. Therefore, the white areas in the processed light-sensitive material become darkened to such an extent that the image areas become impossible to discern. Therefore, the silver salts of fatty acids of a medium chain length are expected to be preferable. Thus, it has been found that particularly silver laurate and silver caprate are suitable. The silver salts of fatty acids higher than lauric acid posses the same defects as the above-described silver behenate in no small degree. On the other hand, the silver salts of fatty acids lower than capric acid are not preferred since the starting materials therefor have an offensive odor and posses the defects of silver acetate in no small degree.
Additionally, as is describe in U.S. Pat. No. 3,457,075, silver laurate has also been believed to be poor in stability to light. However, this light stability has now been found to be improved by improving the process for producing silver laurate and the light sensitive composition. The same applies to silver caprate.
SUMMARY OF THE INVENTION An object of the present invention is to provide a thermally developable light-sensitive material using silver laurate or silver caprate.
Another object of the present invention is to provide a thermally developable light-sensitive material which has less fog upon heat development after imagewise exposure of the light-sensitive material.
As a result of extensive investigations, it has been found that lithium laurate is effective for attaining the above-described objects.
That is, the present invention provides a thermally developable light-sensitive material comprising a support having thereon at least one layer containing: (a) silver laurate or silver caprate; (b) a catalytic amount of a light-sensitive silver halide or a compound capable of forming a light-sensitive silver halide by the reaction thereof with the organic silver salt (a); (c) a reducing agent; (d) a binder; and (e) lithium laurate.
DETAILED DESCRIPTION OF THE INVENTION The amount of lithium laurate, componenet (e), used is about 0.0l mol to mols, preferably 0.1 to 2 mols, per 1 mol of silver laurate or silver caprate.
As the lithium laurate, commercially available lith ium laurate of a special grade or that prepared by reacting lithium ion with lauric acid or a lauric acid salt, such as sodium laurate or potassium laurate, can be used. For example, a precipitate of lithium laurate can be obtained by adding an aqueous solution of lithium nitrate to an aqueous solution of sodium laurate. Also, a precipitate of lithium laurate can be obtained by adding an aqueous solution of lithium hydroxide to a metharol solution of lauric acid.
As to the addition of lithium laurate, the lithium laurate can be present during the formation of the silver laurate or silver caprate, or the lithium laurate can be added after the formation of the silver laurate or silver caprate, before or after the formation of the silver hallde. Also, the lithium laurate can be added after components (a) to (b) are all added. Furthermore, it can be present in another layer adjacent the layer containing the silver laurate or silver caprate, although the effects thereof are reduced.
As compounds which can be used as component (b) in the present invention, there are (1) compounds capable of forming a light-sensitive silver halide by the reaction thereof with the above-described organic silver salt (a) and (2) silver halide. Specific examp s ui" 1) are inorganic compounds represented'fiy the general formula;
logen compounds such as triphenylmethyl bromide, 2-bromo-2-methylpropane, 2-bromobutyric acid, 2- bromoethanol, dichlorobenzophenone, iodoform, bromoform, carbon, tetrabromide, an N-haloacetamide, l,3, -dibromo-5 ,5-dimethylthiohydantoin, 1,3- dichloro-S, S-dimethylthiohydantoin, etc. are also included within the scope of the aforesaid compound l The silver halide of compound (2) can be silver cloride, silver bromiodide, silver clorobromoiodide, silver chlorobromide and silver iodide. A suitable particle size can range from about 0.001 p. to 0.5 u, preferably 0.03 p. to 0.2 u. A silver halide containing more than about 50 mol percent bromide is preferred.
Emulsions containing a light-sensitive silver halide can be prepared in any conventional manner known in the field of photography. As such emulsions, there are illustrated, for example, an emulsion prepared by the single jet method, an emulsion prepared by the double jet method (e.g., a Lippmann emulsion), an ammoniacal emulsion, a thiocyanateor thioether-ripened emulsion, the emulsions described in, e.g., US. Pat. Nos. 2,222,264, 3,320,069, 3,271,157, etc., and the like.
The silver halide which can be used in the present invention can be sensitized with chemical sensitizers such as a reducing agent, sulfur, a selenium compound, a gold compound, a platinum compound, a palladium compound, or a combination thereof. Suitable procedures therefor are described in e.g., US. Pat. Nos. 2,623,499, 2,399,083, 3,297,447 and 3,297,446.
The above-described compounds employed as component (b) can be used alone or as a combination of two or more. Component (b) is suitably added in an amount of from 0.01 mol to 0.5 mol, preferably 0.02 mol, per 1 mol of the silver laurate or silver caprate of component (a). If the amount of the component (b) is less than the lower limit of this range, the sensitivity is reduced while if the amount exceeds the upper limit of the range, the non-image areas of the heat-developed material are gradually blackened upon leaving the material under room light, which can spoil the contrast between the image areas and non-image areas.
As the reducing agent which can be used as component (c) in the present invention, reducing agents must be selected which are suitable for reducing the silver salt of component (a) to form images upon heating the light-sensitive material in the presence of exposed silver halide catalyst. Such reducing agents are substituted phenols, naphthols, substituted or unsubstituted bisphenols, hydroquinone monoethers, and the like. A substituted phenol or a substituted bisphenol is preferred.
More specifically, examples of the above-illustrated compounds are given below: 1 l -bis-( 4- hydroxyphenyl) cyclohexane, l,l-bis-(5-chloro-2- hydroxyphenyl)methane, diethylstilbestrol, hexestrol, 2,2-bis-(3,5-dibromo-4-hydroxyphenyl)propane, 2,2- bis-(4-hydroxyphenyl)propane, a-phenyl-o-cresol, hydroquinone monobenzylether, p-nonyl phenol, poctylphenol, p-ethylphenol, p-sec-butylphenol, p-tamylphenol, p-acetylphenol, 2-acetacetyl-4- methylphenol, l-(2-quinolyl)-3-methyl-5-pyrazolone, l-chloro-2,4-dihydroxybenzene, 3 ,5-di-t-butyl-2,6- dihydroxybenzoic acid, 2,4-dihydroxybenzoic acid, re-
sorcin, 2,4-dihydroxyphenylsulfide, 5,7-dihyroxy-4- methylcoumarin, p-methoxyphenol 2-t-butyl-4- methoxyphenol, p-phenylphenol, p-t-butylphen ol B-naphthol, 2,4,5-trimethylphenol bisphenol A, 2,5-dit-butyl-4-methoxyphenol, hydroquinone mono-npropyl ether, hydroquinone mono-n-hexyl ether, 2,3- dimethylphenol, 2,4-di-t-butylphenol, N,N-di(4- hydrozyphenoyl)urea, and the like.
These reducing agents can also be used as a combination of two or more.
Generally speaking, the reducing agent used in the present invention is added in an amount of 0.1 to 5 mols, preferably of 0.5 to 1.5 mols, per 1 mol of the silver laurate or silver caprate of component (a).
In the present invention, components (a), (b), (c) and (e) are preferably dispersed in a binder (d), and are coated on a support. Also, a part or all of these layers can be coated as separate layers. As such a binder, any of those binders which have heretofore been used in this field can be used. Hydrophobic binders are usually preferable, but hydrophilic binders can also be used. Transparent or semi-transparent binders are preferred and illustrative examples are, e.g., natural substances such as gelatin, gelatin derivatives, a mixture thereof with a latex-type vinyl polymer, a cellulose derivative, etc., and synthetic polymer materials.
Specific examples include gelatin, phthaloylated gelatin, polyvinyl butyral, polyacrylamide, cellulose acetate butyrate, cellulose acetate propionate polymethyl methacrylate, polyvinyl pyrrolidone, polystyrene, ethyl cellulose, polyvinyl chloride, rubber chloride, polyisobutylene, butadiene-styrene copolymers, vinyl chloride-vinyl acetate copolymers, vinyl acetate, vinyl chloride-maleic acid copolymers, polyvinyl alcohol, polyvinyl acetate, benzyl cellulose, cellulose diacetate, cellulose triacetate cellulose propionate, cellulose acetate phthalate, and the like. These can be used as a combination of two or more as the case may be. Preferred binders are polyvinylbutyral, polyvinylacetate, ethylcellulose, polymethyl-methacrylate and celluloseacetatebutyrate. The weight ratio of the binder to the silver laurate or silver caprate of component (a) is suitably about 4:1 to about 1:4, preferably 2:1 to 1:2.
As the support which can be used in the invention, wide variety of materials can be used. Representative examples of supports are a cellulose nitrate film, a cellulose ester film, a polyvinyl acetal film, a polystyrene film, a polyethylene terephthalate film, a polycarbonate film, glass, paper, metal, and the like. Where an organic solvent is used in the emulsion layer, a support paper subjected to a processing to impart hydrophilicity, e.g., to a surface-treating with polyvinyl alcohol, is suitable. Also, papers sizing-processed. with saccharides are suitable.
The suitable amount of the above-described binder dispersion to be coated on a support is about 0.2 to 3 g/m (calculated as silver), more preferably, 0.4 to 2 g/m. If the amount coated is less than 0.2 g/m sufficient image density cannot be obtained while if the amount coated is greater than 3 g/m the production cost is increased.
An anti-static layer or an electroconductive layer can be provided on the thermally developable lightsensitive material used for the practice of the invention. Also, an anti-halation substance and an anti-halation dye can be incorporated in the material.
In the thermally developable light-sensitive material used in the practice of the present invention can further be incorporated if desired, a matting agent such as starch, titanium dioxide zinc oxide, silica, etc. Also, flucrescent brightening agents such as the stilbenes, triazines, oxazoles, coumarines, etc. can be incorporated in the material.
Some of the optically sensitizing dyes which have heretofore been used for silver halide emulsions can advantageously be used so as to impart increased light sensitivity to the thermally developable light-sensitive material of the present invention. Suitable optical sensitizing dyes are disclosed for example, in U.S. Pat. No. 3,457,075. For example, optical sensitization can be effected by adding a sensitizing dye as an organic solvent solution or a dispersion. Suitable optical sensitizers are, e.g., cyanine dyes, merocyanine dyes, rhodacyanine dyes styryl dyes, Erythrosine, Eosine, tetrachloro tetrabromofluorescein, 2 ',7 dichlorofluorescein or like acidic dyes. The amount of these dyes can range from about 10 mol to about l0 mol per 1 mol of the silver laurate or silver caprate of component (a).
Furthermore various additives such as a toning agent (e.g., phthalazinone, etc.), a stabilizing agent (compound capable of preventing discoloration of images with the lapse of time after image formation (e.g., benzenesulfonic acid, p-toluenesulfonic acid, tetrabromophthalic acid, tetrabromophthalic acid anhydride, etc.) can be incorporated in the thermally developable light-sensitive layer.
Still further, in order to enhance transparency of the thermally developable light-sensitive layer to increase the image density and to improve the storage freshness (i.e., the retention upon storage of the photographic properties of the light-sensitive material immedately after production thereof), a top-coating polymer layer can be provided on the lightsensitive layer. The film thickness of the top-coating polymer layer can suitably range from about 1 p. to 20 t. Suitable polymers are, e.g., polyvinyl chloride, polyvinyl acetate, vinyl chloridevinyl acetate copolymers, polyvinyl butyral, polystyrene, polymethyl methacrylate, polyurethane rubber, xylene resins, benzyl cellulose, ethyl cellulose, cellulose acetate butyrate, cellulose diacetate, cellulose triacetate, polyvinylidene chloride, chlorinated polypropylene, polyvinyl pyrrolidone, cellulose propionate, polyvinyl formal, cellulose acetate phthalate, polycarbonate, cellulose acetate propionate, and the like.
The thermally developable light-sensitive layer and the top-coating layer to be used in the practice of the present invention can be applied to a support using various coating methods including a dip-coating method, an air knife-coating method, a curtain-coating method, and an extrusion coating method using a hopper as described in U.S. Pat. No. 2,681,294. If desired, two or more layers can be applied at the same time.
The above-described thermally developable lightsensitive material can be developed, after being exposed, e.g., for about 10 second to 10 seconds, to radiation from a xenon lamp, a tungsten lamp a mercury lamp or like light source by merely heating the light-sensitive material. Heating temperatures of about to 180 C, more preferably, C to C, are suitable for such development. Higher or lower temperatures can be selected within the above-described range by prolonging or shortening the heating time appropriately. The developing time is usually from 1 second to about 60 seconds.
Various means for heat-developing the light-sensitive material of the present invention can be used. For example, the light-sensitive material can be contacted with a simple heating plate or the like or with a heated drum, or, in some cases, the material can be passed through a heated space. Also, the material can be heated using high frequency induction heating or using a laser beam.
The thermally developable light-sensitive material in accordance with the present invention has less heat fog in the unexposed areas when development-processed after imagewise exposure.
The present invention will now be illustrated in greater detail by reference to the following non-limiting examples of preferred embodiments of the present invention. Unless otherwise indicated, all parts, percents ratios and the like are by weight.
EXAMPLE 1 A solution prepared by dissolving 8.6 g ofcapric acid in 100 ml of isoamyl acetate was maintained at 5C and while stirring with a stirrer 50 ml of an aqueous solution of a silver ammonium complex salt (cooled to 5C) containing 8.5 g of silver nitrate was added thereto over a 30 second period to react the capric acid with the silver ion. Thus, spindle-shaped silver caprate crystals of a length of about 3 uand a width of about 0.2 uwere obtained The resulting silver salt was washed successively with water and methanol. Thereafter, 3.0 g of polyvinyl butyral and ml of isopropyl alcohol were added to 2.1 g of the silver caprate and dispersed using a ball mill to prepare a polymer dispersion of the silver salt.
To 20 g of this polymer dispersion of the silver salt were added the following components to prepare a thermally developable light-sensitive coating solution. This solution was applied to a paper support in a silver amount of 1.0 g per 1 m of the support to prepare Thermally Developable Light-Sensitive Material (A).
Separately for the purposes of comparison Thermally Developable Light-Sensitive Material (8) not containing lithium laurate and Thermally Developable Light- Sensitive Material (C) containing conventionally known mercuric acetate in place of the lithium laurate of the present invention were prepared in the similar manner.
Ammonium Bromide (2.5% by weight methanol solution) 1 ml Tetrachlorotetrabromofluorescein (sensitizing dye; 0.025% by weight methanol solution) 3 ml Phthalazinone (2.5% by weight methyl cellosolve solution) 1 ml Bisphenol A (70% by weight methyl cellosolve solution) 3 ml Lithium Lauratc l g low.
Light-Sensitive Material Image Density (Maximum Density Area) 1.30 1.45 1.20 Non-image Density (Heatfogged Area) 025 1.00 .18
From the results in above table it can be clearly seen that lithium laurate of the present invention reduces the heat fog and provides sufficient image density, i.e., images with good contrast are obtained.
EXAMPLE 2 The procedures described in Example 1 were repeated except for using 2 g oflithium laurate. When the resulting sample was exposed and heat-developed under the same conditions as described in Example 1, an image of an image density of 1.18 (maximum density area) and a non-image density of 0.17 (heat-fogged area) (reflection density) was obtained.
EXAMPLE 3 11 grams of lauric acid was dissolved in 100 ml of butyl acetate and while maintaining the solution at 10C, 100 ml of a dilute nitric acid aqueous solution (pH at 25C: 2.0) was added thereto under stirring with a stirrer. Then, while continuing the stirring, 50 ml of an aqueous solution (cooled to 0C) of a silver ammonium complex salt containing 8.5 g of silver nitrate was added thereto over a 1 minute period to react the lauric acid with the silver ion. Thus, spindle-shaped silver laurate crystals of a length of about 1 u and a width of 0.05 p. were obtained. The resulting silver salt was washed successively, with water and methanol. Thereafter, 3.0 g of polyvinyl butyral and 20ml of isopropyl alcohol were added to 2.7 g of the silver laurate and dispersed using a ball mill to prepare a polymer dispersion of the silver salt.
To 20 g of this polymer dispersion of the silver salt were added the following components to prepare a thermally developable light-sensitive omposition. The resulting composition was applied to a polyethylene terephthalate film support in a silver amount of 1.7 g per 1 m of the support to prepare Thermally Developable Light-Sensitive Material (A).
Separately, for the purposes of comparison, there Thermally Developable Light-Sensitive Material (B) not containing lithium laurate which is the anti-heat foggant of the present invention was prepared in a similar manner.
Ammonium Bromide (2.5% by weight methanol solution) 1 ml Benzoxazolylidene Rhodanine Sensitizing Dye (0.025 by weight chloroform solution) 1 ml pJhenylphenol by weight methyl cellosolve solution) 3 ml Phthalazinone (25% by weight methyl cellosolve solution) 1 ml Lithium Laurate 2 g Also, Thermally Developable Light-Sensitive Material (C) was prepared in the same manner using mercuric bromide, conventionally known as an anti-heat foggant, in the same molar amount in lieu of the lithium laurate.
On the light-sensitive layer of each of the thus prepared Light-Sensitive Materials (A), (B) and (C) was top-coated a 5 percent acetone solution of cellulose diacetate in a dry thickness of 10 1.1..
Each of these Light-Sensitive Materials (A), (B) and (C) was exposed to a radiation from a tungsten light source (using a step wedge) to impart an exposure of 500,000 lx' sec. Thereafter, the materials were heated at 120C for 20 seconds for development. Thus stepwise images were obtained.
Transmission densities at the image areas and the non-image areas were measured in the same manner as described in Example 1 to obtain the results tabulated below.
Light-Sensitive Materials (A) (B) lmage Density (Maximum Density Area) 1.41 1.61 1.12 Non-image Density (Heatfogged Area) 0.15 0.70 0.13
From the results in the above table, it can be clearly seen that lithium laurate of the present invention reduces heat fog and provides sufficient image density, i.e., images having good contrast were obtained.
EXAMPLE 4 EXAMPLE 5 grams of lauric acid and 2 g of sodium hydroxide were dissolved in 200 ml of water. Then, 100 ml of toluene containing dissolved therein 3 g of lauric acid was added thereto and stirred with a-stirrer to emulsify (800 rpm, 5 minutes). While continuing the stirring, a silver aqueous solution (8.5 g of silver nitrate plus 50 cc of water) was added thereto over a 60 second period to produce silver laurate.
The silver laurate thus precipitated was collected. 30 grams of polyvinyl butyral and 200 ml of isopropyl alcohol were added thereto and dispersed in a ball mill to prepare a silver laurate polymer dispersion. To this silver laurate polymer dispersion were added the following components to prepare a thermally developable light-sensitive composition. This was then coated on a paper support in a silver amount of 0.7 g per 1 m of the support to prepare a thermally developable lightsensitive material.
Ammonium Bromide (2.5% by weight methanol solution) 1 ml Tctrachlorotctrabromofluorescein (sensitizing dye; 0.025% by weight methanol solution) 5 ml p-Phenylphcnol (70% by weight methyl cellosolve solution 3 ml Phthalazinone (2.57: by weight methyl cellosolve solution) 1 ml Lithium Laurate 2 g When the resulting sample was exposed and heatdeveloped under the same conditions as described in Example 3, an image of an image density of 1.43 (at maximum density area) and a non-image density of 0.05 (at heat-fogged area) (reflection density) was obtained.
On the otherhand, a. thermally developable lightsensitive material containing no lithium laurate was prepared for the purposes of comparison. When this material was processed under the same conditions, an image of an imagedensity of 1.45 and an non-image density of 0.15 was obtained. 7
It can be clearly seen that heat fog is prevented with lithium laurate.
' EXAMPLE 6 The same procedures as described in Example 5 were repeated except that neither the sensitizing dye nor the phthalazinone was not used.
The same result as described in Example 5 was obtained except that the sensitivity was less than l/50th that in Example 5, and the color of the image was brown.
The above results demonstrate that lithium laurate has anti-heat fogging effect whether the sensitizing dye and the phthalazinone are present or not.
While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from spirit and scope thereof.
What is claimed is:
l. A thermally developable light-sensitive material comprising a support having thereon at least one layer containing: (a) silver laurate or silver caprate; (b) a catalytic amount of a light-sensitive silver halide or a compound capable of forming a light-sensitive silver halide by the reaction thereof with said organic silver salt (a); (c) a reducing agent; (d) a binder; and (e) lithium laurate.
2. The light-sensitive material according to claim 1, wherein said photosensitive silver halide is silver chloride, silver bromoiodide, silver chlorobromoiodide, silver chlorobromide or silver iodide.
3. The light-sensitive material according to claim 1, wherein the compound which reacts with said silver laurate or silver caprate of component (a) to form a photosensitive silver halide is selected from the group consisting of an inorganic compound represented by the formula:
wherein M is a hydrogen atom, an ammonium group or a metal atom, X is a halogen atom, and n is 1 when M is a hydrogen atom or an ammonium group and when M is a metal atom, n is equal to the valence of the metal, and an organic compound.
4. The light-sensitive material according to claim 3, wherein the organic halogen compound is triphenylmethyl chloride, triphenylmethyl bromide, 2-bromo-2- methylpropane, 2-bromo-butyric acid, 2- bromoethanol, dichlorobenzophenone, iodoform, bromoform, carbon tetrabromide, an N-haloacetamide, 1,3-dibromo-5 ,S-dimethylthiohydantoin, or 1,3- dichloro-5,5-dimethyl thiohydantoin 5. The light-sensitive material according to claim 1, wherein the amount of the photosensitive silver halide component (b) ranges from about 0.01 to 0.5 mole per mole of said silver laurate or silver caprate of component (a).
6. The light-sensitive material according to claim 1, where the reducing agent is a substituted phenol, a
naphthol, a substituted naphthol, a substituted or unsubstituted bisphenol or a hydroquinone monoether.
7. The light-sensitive material according to claim 1, where the amount of the reducing agent component (c) ranges from about 0.1 to moles per mole of said silver laurate or silver caprate of component (a).
8. The light-sensitive material according to claim 1, wherein the weight ratio of the binder component (d) to said silver laurate or silver caprate of component (a) ranges from about 4:l to 1:4.
9. The light-sensitive material according to claim 1, wherein said layer additionally contains at least one of or silver caprate of component (a).
l l l
Claims (12)
1. A THERMALLY DEVELOPABLE LIGHT-SENSITIVE MATERIAL COMPRISING A SUPPORT HAVING THEREON AT LEAST ONE LAYER CONTAINING: (A) SILVER LAURATE OR SILVER CAPRATE; (B) A CATALYTIC AMOUNT OF A LIGHT-SENSITIVE SILVER HALIDE OR A COMPOUND CAPABLE OF FROMING A LIGHT-SENSITIVE SILVER HALIDE BY THE REACTION THEREOF WITH SAID ORGANIC SILVER SALT (A); (C) A REDUCING AGENT; (D) A BINDER; AND (E) LITHIUM LAURATE.
2. The light-sensitive material according to claim 1, wherein said photosensitive silver halide is silver chloride, silver bromoiodide, silver chlorobromoiodide, silver chlorobromide or silver iodide.
3. The light-sensitive material according to claim 1, wherein the compound which reacts with said silver laurate or silver caprate of component (a) to form a photosensitive silver halide is selected from the group consisting of an inorganic compound represented by the formula: MXn wherein M is a hydrogen atom, an ammonium group or a metal atom, X is a halogen atom, and n is 1 when M is a hydrogen atom or an ammonium group and when M is a metal atom, n is equal to the valence of the metal, and an organic compound.
4. The light-sensitive material according to claim 3, wherein the organic halogen compound is triphenylmethyl chloride, triphenylmethyl bromide, 2-bromo-2-methylpropane, 2-bromo-butyric acid, 2-bromoethanol, dichlorobenzophenone, iodoform, bromoform, carbon tetrabromide, an N-haloacetamide, 1,3-dibromo-5,5-dimethylthiohydantoin, or 1,3-dichloro-5,5-dimethyl thiohydantoin
5. The light-sensitive material according to claim 1, wherein the amount of the photosensitive silver halide component (b) ranges from about 0.01 to 0.5 mole per mole of said silver laurate or silver caprate of component (a).
6. The light-sensitive material according to claim 1, where the reducing agent is a substituted phenol, a naphthol, a substituted naphthol, a substituted or unsubstituted bisphenol or a hydroquinone monoether.
7. The light-sensitive material according to claim 1, where the amount of the reducing agent component (c) ranges from about 0.1 to 5 moles per mole of said silver laurate or silver caprate of component (a).
8. The light-sensitive material according to claim 1, wherein the weight ratio of the binder component (d) to said silver laurate or silver caprate of component (a) ranges from about 4:1 to 1:4.
9. The light-sensitive material according to claim 1, wherein said layer additionally contains at least one of an optical sensitizer and a toning agent.
10. The light-sensitive material according to claim 1, wherein said layer additionally contains at least one of a stabilizing agent and a matting agent.
11. The light-sensitive material according to claim 1, including a protective layer over said light-sensitive material.
12. The light-sensitive material according to claim 1, where said lithium laurate is present in an amount of about 0.01 mol to 5 moles per mol of said silver laurate or silver caprate of component (a).
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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US474635A US3885968A (en) | 1974-05-30 | 1974-05-30 | Thermally developable light-sensitive material |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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US474635A US3885968A (en) | 1974-05-30 | 1974-05-30 | Thermally developable light-sensitive material |
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US3885968A true US3885968A (en) | 1975-05-27 |
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4030931A (en) * | 1974-05-17 | 1977-06-21 | Fuji Photo Film Co., Ltd. | Heat developable light-sensitive material |
DE2657080A1 (en) * | 1975-12-16 | 1977-06-30 | Asahi Chemical Ind | DRY IMAGE RECORDING MATERIAL |
WO1981000921A1 (en) * | 1979-09-28 | 1981-04-02 | Tonec Sa | Material for obtaining photographic prints by dry process |
EP1431813A1 (en) * | 2002-12-19 | 2004-06-23 | Fuji Photo Film Co., Ltd. | Photothermographic material and image forming method using same |
US20070020566A1 (en) * | 2002-12-19 | 2007-01-25 | Fuji Photo Film., Ltd. | Photothermographic material and image forming method |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3782941A (en) * | 1972-07-18 | 1974-01-01 | Eastman Kodak Co | Photothermographic element,composition and process |
-
1974
- 1974-05-30 US US474635A patent/US3885968A/en not_active Expired - Lifetime
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3782941A (en) * | 1972-07-18 | 1974-01-01 | Eastman Kodak Co | Photothermographic element,composition and process |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4030931A (en) * | 1974-05-17 | 1977-06-21 | Fuji Photo Film Co., Ltd. | Heat developable light-sensitive material |
DE2657080A1 (en) * | 1975-12-16 | 1977-06-30 | Asahi Chemical Ind | DRY IMAGE RECORDING MATERIAL |
WO1981000921A1 (en) * | 1979-09-28 | 1981-04-02 | Tonec Sa | Material for obtaining photographic prints by dry process |
EP1431813A1 (en) * | 2002-12-19 | 2004-06-23 | Fuji Photo Film Co., Ltd. | Photothermographic material and image forming method using same |
US20040131983A1 (en) * | 2002-12-19 | 2004-07-08 | Tomoyuki Ohzeki | Photothermographic material and image forming method using same |
US20070020566A1 (en) * | 2002-12-19 | 2007-01-25 | Fuji Photo Film., Ltd. | Photothermographic material and image forming method |
US7410745B2 (en) | 2002-12-19 | 2008-08-12 | Fujifilm Corporation | Photothermographic material and image forming method using same |
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