US3751249A - Photothermic silver halide element containing a bis-beta-naphthol reducing agent and a 1, 3-dihydroxy-benzene reducing agent - Google Patents
Photothermic silver halide element containing a bis-beta-naphthol reducing agent and a 1, 3-dihydroxy-benzene reducing agent Download PDFInfo
- Publication number
- US3751249A US3751249A US00124464A US3751249DA US3751249A US 3751249 A US3751249 A US 3751249A US 00124464 A US00124464 A US 00124464A US 3751249D A US3751249D A US 3751249DA US 3751249 A US3751249 A US 3751249A
- Authority
- US
- United States
- Prior art keywords
- photothermographic
- photosensitive
- silver halide
- reducing agent
- bis
- 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
- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 60
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 title claims abstract description 25
- PPTXVXKCQZKFBN-UHFFFAOYSA-N (S)-(-)-1,1'-Bi-2-naphthol Chemical compound C1=CC=C2C(C3=C4C=CC=CC4=CC=C3O)=C(O)C=CC2=C1 PPTXVXKCQZKFBN-UHFFFAOYSA-N 0.000 title claims abstract description 19
- -1 silver halide Chemical class 0.000 title claims description 103
- 229910052709 silver Inorganic materials 0.000 title claims description 58
- 239000004332 silver Substances 0.000 title claims description 58
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 33
- IUNJCFABHJZSKB-UHFFFAOYSA-N 2,4-dihydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C(O)=C1 IUNJCFABHJZSKB-UHFFFAOYSA-N 0.000 claims abstract description 28
- ZXDDPOHVAMWLBH-UHFFFAOYSA-N 2,4-Dihydroxybenzophenone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 ZXDDPOHVAMWLBH-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003381 stabilizer Substances 0.000 claims abstract description 16
- 230000001235 sensitizing effect Effects 0.000 claims abstract description 15
- 239000002243 precursor Substances 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims description 53
- 150000003839 salts Chemical class 0.000 claims description 35
- 239000007800 oxidant agent Substances 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 29
- SULYEHHGGXARJS-UHFFFAOYSA-N 2',4'-dihydroxyacetophenone Chemical compound CC(=O)C1=CC=C(O)C=C1O SULYEHHGGXARJS-UHFFFAOYSA-N 0.000 claims description 22
- 229910001385 heavy metal Inorganic materials 0.000 claims description 22
- AQRYNYUOKMNDDV-UHFFFAOYSA-M silver behenate Chemical compound [Ag+].CCCCCCCCCCCCCCCCCCCCCC([O-])=O AQRYNYUOKMNDDV-UHFFFAOYSA-M 0.000 claims description 21
- XKJCHHZQLQNZHY-UHFFFAOYSA-N phthalimide Chemical compound C1=CC=C2C(=O)NC(=O)C2=C1 XKJCHHZQLQNZHY-UHFFFAOYSA-N 0.000 claims description 16
- 125000000654 isopropylidene group Chemical group C(C)(C)=* 0.000 claims description 14
- 230000033116 oxidation-reduction process Effects 0.000 claims description 14
- KLAKIAVEMQMVBT-UHFFFAOYSA-N p-hydroxy-phenacyl alcohol Natural products OCC(=O)C1=CC=C(O)C=C1 KLAKIAVEMQMVBT-UHFFFAOYSA-N 0.000 claims description 14
- KIWUVOGUEXMXSV-UHFFFAOYSA-N rhodanine Chemical compound O=C1CSC(=S)N1 KIWUVOGUEXMXSV-UHFFFAOYSA-N 0.000 claims description 13
- GSCHNMOIVICJQS-UHFFFAOYSA-N benzyl (5-acetyl-4-methyl-1,3-thiazol-2-yl)sulfanylformate Chemical compound CC1=C(C(=O)C)SC(SC(=O)OCC=2C=CC=CC=2)=N1 GSCHNMOIVICJQS-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 8
- IJAPPYDYQCXOEF-UHFFFAOYSA-N phthalazin-1(2H)-one Chemical compound C1=CC=C2C(=O)NN=CC2=C1 IJAPPYDYQCXOEF-UHFFFAOYSA-N 0.000 claims description 5
- 230000000087 stabilizing effect Effects 0.000 claims description 2
- 239000000975 dye Substances 0.000 abstract description 25
- 239000000463 material Substances 0.000 abstract description 21
- 238000012545 processing Methods 0.000 abstract description 14
- 125000004432 carbon atom Chemical group C* 0.000 description 19
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 16
- 239000000839 emulsion Substances 0.000 description 15
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- 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 description 10
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 230000003595 spectral effect Effects 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 125000000217 alkyl group Chemical group 0.000 description 7
- 125000002947 alkylene group Chemical group 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 7
- 125000000623 heterocyclic group Chemical group 0.000 description 7
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 6
- 150000005207 1,3-dihydroxybenzenes Chemical class 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 150000003378 silver Chemical class 0.000 description 5
- 229910052717 sulfur Chemical group 0.000 description 5
- 239000011593 sulfur Chemical group 0.000 description 5
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 125000000732 arylene group Chemical group 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 125000005243 carbonyl alkyl group Chemical group 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 4
- 150000007524 organic acids Chemical class 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Chemical group 0.000 description 4
- 239000000123 paper Substances 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 230000035945 sensitivity Effects 0.000 description 4
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 3
- 108010010803 Gelatin Proteins 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 229960005070 ascorbic acid Drugs 0.000 description 3
- 235000010323 ascorbic acid Nutrition 0.000 description 3
- 239000011668 ascorbic acid Substances 0.000 description 3
- 238000005282 brightening Methods 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 229920000159 gelatin Polymers 0.000 description 3
- 239000008273 gelatin Substances 0.000 description 3
- 235000019322 gelatine Nutrition 0.000 description 3
- 235000011852 gelatine desserts Nutrition 0.000 description 3
- 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 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 3
- 239000004848 polyfunctional curative Substances 0.000 description 3
- XYKIUTSFQGXHOW-UHFFFAOYSA-N propan-2-one;toluene Chemical compound CC(C)=O.CC1=CC=CC=C1 XYKIUTSFQGXHOW-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical class O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 3
- RYGGXWHCWARUBH-UHFFFAOYSA-N 1-naphthalen-1-yl-3h-naphthalene-2,2-diol Chemical group C1=CC=C2C(C3=C4C=CC=CC4=CCC3(O)O)=CC=CC2=C1 RYGGXWHCWARUBH-UHFFFAOYSA-N 0.000 description 2
- SGWZVZZVXOJRAQ-UHFFFAOYSA-N 2,6-Dimethyl-1,4-benzenediol Chemical compound CC1=CC(O)=CC(C)=C1O SGWZVZZVXOJRAQ-UHFFFAOYSA-N 0.000 description 2
- LAQYHRQFABOIFD-UHFFFAOYSA-N 2-methoxyhydroquinone Chemical compound COC1=CC(O)=CC=C1O LAQYHRQFABOIFD-UHFFFAOYSA-N 0.000 description 2
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 2
- QMHIMXFNBOYPND-UHFFFAOYSA-N 4-methylthiazole Chemical compound CC1=CSC=N1 QMHIMXFNBOYPND-UHFFFAOYSA-N 0.000 description 2
- NVXLIZQNSVLKPO-UHFFFAOYSA-N Glucosereductone Chemical compound O=CC(O)C=O NVXLIZQNSVLKPO-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 125000003282 alkyl amino group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 229940116224 behenate Drugs 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-M behenate Chemical compound CCCCCCCCCCCCCCCCCCCCCC([O-])=O UKMSUNONTOPOIO-UHFFFAOYSA-M 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 125000004181 carboxyalkyl group Chemical group 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 2
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- 150000002081 enamines Chemical class 0.000 description 2
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 2
- 150000004676 glycans Chemical class 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229940093915 gynecological organic acid Drugs 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 150000004668 long chain fatty acids Chemical class 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 2
- FBSFWRHWHYMIOG-UHFFFAOYSA-N methyl 3,4,5-trihydroxybenzoate Chemical compound COC(=O)C1=CC(O)=C(O)C(O)=C1 FBSFWRHWHYMIOG-UHFFFAOYSA-N 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 150000002916 oxazoles Chemical class 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920001282 polysaccharide Polymers 0.000 description 2
- 239000005017 polysaccharide Substances 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- ORYURPRSXLUCSS-UHFFFAOYSA-M silver;octadecanoate Chemical compound [Ag+].CCCCCCCCCCCCCCCCCC([O-])=O ORYURPRSXLUCSS-UHFFFAOYSA-M 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 125000004964 sulfoalkyl group Chemical group 0.000 description 2
- 229920001059 synthetic polymer Polymers 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- CWGBFIRHYJNILV-UHFFFAOYSA-N (1,4-diphenyl-1,2,4-triazol-4-ium-3-yl)-phenylazanide Chemical compound C=1C=CC=CC=1[N-]C1=NN(C=2C=CC=CC=2)C=[N+]1C1=CC=CC=C1 CWGBFIRHYJNILV-UHFFFAOYSA-N 0.000 description 1
- PSBDWGZCVUAZQS-UHFFFAOYSA-N (dimethylsulfonio)acetate Chemical group C[S+](C)CC([O-])=O PSBDWGZCVUAZQS-UHFFFAOYSA-N 0.000 description 1
- 150000005206 1,2-dihydroxybenzenes Chemical class 0.000 description 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 1
- DBCKMJVEAUXWJJ-UHFFFAOYSA-N 2,3-dichlorobenzene-1,4-diol Chemical compound OC1=CC=C(O)C(Cl)=C1Cl DBCKMJVEAUXWJJ-UHFFFAOYSA-N 0.000 description 1
- VZYDKJOUEPFKMW-UHFFFAOYSA-N 2,3-dihydroxybenzenesulfonic acid Chemical class OC1=CC=CC(S(O)(=O)=O)=C1O VZYDKJOUEPFKMW-UHFFFAOYSA-N 0.000 description 1
- GPASWZHHWPVSRG-UHFFFAOYSA-N 2,5-dimethylbenzene-1,4-diol Chemical compound CC1=CC(O)=C(C)C=C1O GPASWZHHWPVSRG-UHFFFAOYSA-N 0.000 description 1
- PVUWVZFMRJUSBN-UHFFFAOYSA-N 2,6-ditert-butyl-4-(1-phenyltetrazol-5-yl)benzenethiol Chemical compound C(C)(C)(C)C1=C(C(=CC(=C1)C1=NN=NN1C1=CC=CC=C1)C(C)(C)C)S PVUWVZFMRJUSBN-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JHKKTXXMAQLGJB-UHFFFAOYSA-N 2-(methylamino)phenol Chemical class CNC1=CC=CC=C1O JHKKTXXMAQLGJB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- PZTWFIMBPRYBOD-UHFFFAOYSA-N 2-acetylphthalazin-1-one Chemical compound C1=CC=C2C(=O)N(C(=O)C)N=CC2=C1 PZTWFIMBPRYBOD-UHFFFAOYSA-N 0.000 description 1
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 1
- CFMZSMGAMPBRBE-UHFFFAOYSA-N 2-hydroxyisoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(O)C(=O)C2=C1 CFMZSMGAMPBRBE-UHFFFAOYSA-N 0.000 description 1
- DFZVZKUDBIJAHK-UHFFFAOYSA-N 2-hydroxyoctadecanoic acid silver Chemical compound [Ag].OC(C(=O)O)CCCCCCCCCCCCCCCC DFZVZKUDBIJAHK-UHFFFAOYSA-N 0.000 description 1
- SRJCJJKWVSSELL-UHFFFAOYSA-N 2-methylnaphthalen-1-ol Chemical compound C1=CC=CC2=C(O)C(C)=CC=C21 SRJCJJKWVSSELL-UHFFFAOYSA-N 0.000 description 1
- UIQPERPLCCTBGX-UHFFFAOYSA-N 2-phenylacetic acid;silver Chemical compound [Ag].OC(=O)CC1=CC=CC=C1 UIQPERPLCCTBGX-UHFFFAOYSA-N 0.000 description 1
- UGWULZWUXSCWPX-UHFFFAOYSA-N 2-sulfanylideneimidazolidin-4-one Chemical compound O=C1CNC(=S)N1 UGWULZWUXSCWPX-UHFFFAOYSA-N 0.000 description 1
- IBWXIFXUDGADCV-UHFFFAOYSA-N 2h-benzotriazole;silver Chemical compound [Ag].C1=CC=C2NN=NC2=C1 IBWXIFXUDGADCV-UHFFFAOYSA-N 0.000 description 1
- XOHUESSDMRKYEV-UHFFFAOYSA-N 2h-phthalazin-1-one;silver Chemical compound [Ag].C1=CC=C2C(=O)NN=CC2=C1 XOHUESSDMRKYEV-UHFFFAOYSA-N 0.000 description 1
- OWIRCRREDNEXTA-UHFFFAOYSA-N 3-nitro-1h-indazole Chemical class C1=CC=C2C([N+](=O)[O-])=NNC2=C1 OWIRCRREDNEXTA-UHFFFAOYSA-N 0.000 description 1
- AGCMQUPIAYSTIL-UHFFFAOYSA-N 4-(5-acetyl-4-methyl-2-sulfanylidene-1,3-thiazol-3-yl)butan-2-one Chemical compound CC(=O)CCN1C(C)=C(C(C)=O)SC1=S AGCMQUPIAYSTIL-UHFFFAOYSA-N 0.000 description 1
- DSVIHYOAKPVFEH-UHFFFAOYSA-N 4-(hydroxymethyl)-4-methyl-1-phenylpyrazolidin-3-one Chemical compound N1C(=O)C(C)(CO)CN1C1=CC=CC=C1 DSVIHYOAKPVFEH-UHFFFAOYSA-N 0.000 description 1
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 1
- OORIFUHRGQKYEV-UHFFFAOYSA-N 6-bromo-1-(6-bromo-2-hydroxynaphthalen-1-yl)naphthalen-2-ol Chemical group BrC1=CC=C2C(C3=C4C=CC(Br)=CC4=CC=C3O)=C(O)C=CC2=C1 OORIFUHRGQKYEV-UHFFFAOYSA-N 0.000 description 1
- 235000021357 Behenic acid Nutrition 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- BKGOEKOJWMSNRX-UHFFFAOYSA-L C(C1(C)C(C)(C)C(C(=O)[O-])CC1)(=O)[O-].[Ag+2] Chemical compound C(C1(C)C(C)(C)C(C(=O)[O-])CC1)(=O)[O-].[Ag+2] BKGOEKOJWMSNRX-UHFFFAOYSA-L 0.000 description 1
- SOPOWMHJZSPMBC-UHFFFAOYSA-L C(C1=CC=C(C(=O)[O-])C=C1)(=O)[O-].[Ag+2] Chemical compound C(C1=CC=C(C(=O)[O-])C=C1)(=O)[O-].[Ag+2] SOPOWMHJZSPMBC-UHFFFAOYSA-L 0.000 description 1
- AXVCDCGTJGNMKM-UHFFFAOYSA-L C(C=1C(C(=O)[O-])=CC=CC1)(=O)[O-].[Ag+2] Chemical compound C(C=1C(C(=O)[O-])=CC=CC1)(=O)[O-].[Ag+2] AXVCDCGTJGNMKM-UHFFFAOYSA-L 0.000 description 1
- 229920002307 Dextran Polymers 0.000 description 1
- 229920002085 Dialdehyde starch Polymers 0.000 description 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Chemical class 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- 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 1
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 150000000996 L-ascorbic acids Chemical class 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
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- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-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
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 229920002433 Vinyl chloride-vinyl acetate copolymer Polymers 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
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- 229910021645 metal ion Chemical group 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
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- IBKQQKPQRYUGBJ-UHFFFAOYSA-N methyl gallate Natural products CC(=O)C1=CC(O)=C(O)C(O)=C1 IBKQQKPQRYUGBJ-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 230000007935 neutral effect Effects 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 150000002918 oxazolines Chemical class 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- 150000002941 palladium compounds Chemical class 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920006289 polycarbonate film Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- FYRHIOVKTDQVFC-UHFFFAOYSA-M potassium phthalimide Chemical compound [K+].C1=CC=C2C(=O)[N-]C(=O)C2=C1 FYRHIOVKTDQVFC-UHFFFAOYSA-M 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 1
- CWMRFSSMSXQUJC-UHFFFAOYSA-N pyrrole-2-thione Chemical compound S=C1C=CC=N1 CWMRFSSMSXQUJC-UHFFFAOYSA-N 0.000 description 1
- 150000003236 pyrrolines Chemical class 0.000 description 1
- 239000001397 quillaja saponaria molina bark Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000012260 resinous material Substances 0.000 description 1
- CVHZOJJKTDOEJC-UHFFFAOYSA-N saccharin Chemical compound C1=CC=C2C(=O)NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-N 0.000 description 1
- 229940081974 saccharin Drugs 0.000 description 1
- 235000019204 saccharin Nutrition 0.000 description 1
- 239000000901 saccharin and its Na,K and Ca salt Substances 0.000 description 1
- 229930182490 saponin Natural products 0.000 description 1
- 150000007949 saponins Chemical class 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- NBYLLBXLDOPANK-UHFFFAOYSA-M silver 2-carboxyphenolate hydrate Chemical compound C1=CC=C(C(=C1)C(=O)O)[O-].O.[Ag+] NBYLLBXLDOPANK-UHFFFAOYSA-M 0.000 description 1
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 description 1
- 229940071536 silver acetate Drugs 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- YRSQDSCQMOUOKO-KVVVOXFISA-M silver;(z)-octadec-9-enoate Chemical compound [Ag+].CCCCCCCC\C=C/CCCCCCCC([O-])=O YRSQDSCQMOUOKO-KVVVOXFISA-M 0.000 description 1
- OEVSPXPUUSCCIH-UHFFFAOYSA-M silver;2-acetamidobenzoate Chemical compound [Ag+].CC(=O)NC1=CC=CC=C1C([O-])=O OEVSPXPUUSCCIH-UHFFFAOYSA-M 0.000 description 1
- RDZTZLBPUKUEIM-UHFFFAOYSA-M silver;4-phenylbenzoate Chemical compound [Ag+].C1=CC(C(=O)[O-])=CC=C1C1=CC=CC=C1 RDZTZLBPUKUEIM-UHFFFAOYSA-M 0.000 description 1
- CLDWGXZGFUNWKB-UHFFFAOYSA-M silver;benzoate Chemical compound [Ag+].[O-]C(=O)C1=CC=CC=C1 CLDWGXZGFUNWKB-UHFFFAOYSA-M 0.000 description 1
- JKOCEVIXVMBKJA-UHFFFAOYSA-M silver;butanoate Chemical compound [Ag+].CCCC([O-])=O JKOCEVIXVMBKJA-UHFFFAOYSA-M 0.000 description 1
- OIZSSBDNMBMYFL-UHFFFAOYSA-M silver;decanoate Chemical compound [Ag+].CCCCCCCCCC([O-])=O OIZSSBDNMBMYFL-UHFFFAOYSA-M 0.000 description 1
- MNMYRUHURLPFQW-UHFFFAOYSA-M silver;dodecanoate Chemical compound [Ag+].CCCCCCCCCCCC([O-])=O MNMYRUHURLPFQW-UHFFFAOYSA-M 0.000 description 1
- GXBIBRDOPVAJRX-UHFFFAOYSA-M silver;furan-2-carboxylate Chemical compound [Ag+].[O-]C(=O)C1=CC=CO1 GXBIBRDOPVAJRX-UHFFFAOYSA-M 0.000 description 1
- LTYHQUJGIQUHMS-UHFFFAOYSA-M silver;hexadecanoate Chemical compound [Ag+].CCCCCCCCCCCCCCCC([O-])=O LTYHQUJGIQUHMS-UHFFFAOYSA-M 0.000 description 1
- OHGHHPYRRURLHR-UHFFFAOYSA-M silver;tetradecanoate Chemical compound [Ag+].CCCCCCCCCCCCCC([O-])=O OHGHHPYRRURLHR-UHFFFAOYSA-M 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 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
- 239000000758 substrate Substances 0.000 description 1
- 229960002317 succinimide Drugs 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 150000003461 sulfonyl halides Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 150000003498 tellurium compounds Chemical class 0.000 description 1
- 239000004250 tert-Butylhydroquinone Substances 0.000 description 1
- 235000019281 tert-butylhydroquinone Nutrition 0.000 description 1
- 150000003557 thiazoles Chemical class 0.000 description 1
- 150000003549 thiazolines Chemical class 0.000 description 1
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 229920003176 water-insoluble polymer Polymers 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
- 125000006839 xylylene group Chemical group 0.000 description 1
- 239000004246 zinc acetate Substances 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
- G03C1/49827—Reducing agents
-
- 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
- G03C2200/00—Details
- G03C2200/42—Mixtures in general
Definitions
- ABSTRACT In photosensitive materials for processing with heat, a combination of a bis-beta-naphthol reducing agent with a 1,3-dihydroxybenzene reducing agent, such as 2,4-dihydroxybenzaldehyde or 2,4-dihydroxybenzophenone, provides surprisingly increased relative speed, maximum density and exposure latitude.
- This combination of reducing agents can be used in photosensitive and thermosensitive materials for processing with heat.
- These materials can contain addenda commonly employed in photosensitive materials such as activator-toning agents, stabilizers or stabilizer precursors, sensitizing dyes and the like.
- This invention relates to photosensitive elements, compositions and processes for developing a latent image with heat. In one of its aspects it relates to photosensitive elements for processing with heat containing certain combinations of reducing agents which provide increased relative speed, increased maximum density and greater exposure latitude. In another of its aspects it relates to a photosensitive composition for processing with heat containing the described combination of reducing agents. A further aspect relates to photosensitive and thermosensitive compositions containing the described combination of reducing agents. Another aspect' relates to a thermographic combination comprising an oxidation-reduction image-forming combination containing a heavy metal salt oxidizing agent, such as silver behenate, with a described reducing agent combination. A further aspect relates to a process of developing a latent image in an exposed photosensitive and thermosensitive element employing the described combination of reducing agents.
- thermographic materials it has been known to employ a reducing agent which is inactivated by image wise exposure to U.V. radiation.
- a reducing agent which is inactivated by image wise exposure to U.V. radiation.
- One of the reducing agents employed in this thermographic element can be 1,1 dihydroxy-2,2'-binaphthol.
- a similar element employing, for example, an alpha or beta naphthol as a reducing agent and l-(2H)phthalazinone, as a toning agent, is described, for example, in U.S. Pat. No. 3,080,254 of Grant issued Mar. 5, 1963.
- 1,3-Dihydroxybenzene compounds have been employed in photosensitive materials in the past.
- U.S. Pat. No. 2,165,421 of Sheppard et al. issued July 11, 1939 indicates that a combination of an aliphatic aldehyde hardening agent with a 1,3- dihydroxybenzene compound can be employed for hardening gelatin.
- a 1,3- dihydroxybenzene compound such as 2,4-dihydroxybenzaldehyde
- this reducing agent does not provide the desired increased relative speed or increased maximum density. This is demonstrated in the following comparative Example 2 as well as in comparative Examples 4 and 5.
- a combination of a bisnaphthol reducing agent especially a bis-beta-naphthol reducing agent, with a 1,3-dihydroxybenzene compound, as described herein in a photosensitive element, composition or process for developing a latent image with heat provides surprising increased relative speed as well as increased maximum density as well as wider exposure latitude without increased minimum density.
- This combination of reducing agents provides especially useful results in a photothermographic composition, also described herein as a photosensitive and thermosensitive composition employing photosensitive silver halide with an oxidation-reduction image-forming combination comprising a heavy metal salt oxidizing agent with a described combination of reducing agents.
- the described combination of reducing agents provide the described results even in a combination with stabilizer precursors, activatontoning agents, sensitizing dyes and other addenda employed in photosensitive and thermosensitive elements, compositions and processes.
- R and/or R is hydrogen, alkyl with one to three carbon atoms, alkoxy, e.g., alkoxy containing one to two carbon atoms, such as methoxy or ethoxy; halogen, nitro, amino, or a dia zonium halide salt and n is 0 or 1.
- photosensitive composition employing the described reducing agent combination typically comprises photosensitive silver halide, a bis-naphthol reducing agent with a 1,3-dihydroxybenzene compound.
- a bis-naphthol reducing agent with a 1,3-dihydroxybenzene compound typically comprises photosensitive silver halide, a bis-naphthol reducing agent with a 1,3-dihydroxybenzene compound.
- preferred photosensitive and thermosensitive composition comprises a. photosensitive silver halide, with b. an oxidation-reduction image-forming combination comprising i. a heavy metal salt oxidizing agent with ii. a bis-naphthol reducing agent and c; a l,3dihydroxybenzene compound, asdescribed.
- the described combination of reducing agents can be employed in a range of concentrations in a photosensitive and thermosensitive element or composition.
- An especially suitable range of concentration is about 0.4 to about 2.0 moles of reducing agent combination per mole of photosensitive component employed.
- a preferred concentration range of components comprises 0.01 to 0.50 moles of photosensitive silver halide per mole of heavy metal salt oxidizing agent;
- Example 1 as a typical example, various desired concentrations can be determined by balancing the concentrations of components in the composition and/or element.
- reducing agents can be used in combination with the described bis-naphthol reducing agents and 1,3-dihydroxybenzene reducing agents.
- These are typically silver halide developing agents and include, for example, polyhydroxybenzenes such as hydroquinone developing agents, e.g., hydroquinone, alkylsubstituted hydroquinones as exemplified by tertiary butylhydroquinone, methylhydroquinone, 2,5-dimethylhydroquinone and 2,6-dimethylhydroquinone; catechols and pyrogallol; halo-substituted hydroquinones such as chlorohydroquinone or dichlorohydroquinone; alkoxy-substituted hydroquinones such as methoxyhydroquinone or ethoxyhyrdoquinone; methylhydroxynaphthalene; phenylenediamine developing agents; methylgallate; aminophenol developing agents, such as 2,4
- the described photosensitive element and/or composition contains a photosensitive component, preferably a photosensitive silver salt.
- a typical concentration range of photosensitive silver salt is from about 0.005 to about 0.50 mole of silver salt per mole of heavy metal salt oxidizing agent, such as per mole of silver salt of organic acid, e.g., per mole of silver behenate.
- a preferred photosensitive component is photosensitive silver halide, e.g., silver chloride, silver bromide, silver bromoiodide, silver chlorobromoiodide, or mixtures thereof.
- the photosensitive silver halide can be coarse or fine-grain, very fine-grain emulsions being especially useful.
- the silver halide emulsion can be a regular grain emulsion such as described in Klein and Moisar, Journal of Photographic Science, Volume l2, No. 5, September- October (1964) pages 242-251.
- the silver halide employed'in the practice of the in vention can be unwashed or washed to remove, soluble salts.
- the soluble salts can be removed by chill setting and leaching or the emulsion can be co agulation washed.
- the described photosensitive and thermosensitive elements or compositions comprise an oxidizing agent, especially a heavy metal salt oxidizing agent, such as a heavy metal salt of an organic acid.
- a heavy metal salt oxidizing agent such as a heavy metal salt of an organic acid.
- the heavy metal salts of the organic acids should be resistant to darkening under illumination to prevent undesired deterioration of a developed image.
- An especially suitable class of heavy metal salts of organic acids is repre sented by the water insoluble silver salts of long-chain fatty acids which are stable to light.
- Compounds which are suitable silver salts include silver behenate, silver stearate, silver oleate, silver laurate, silver hydroxystearate, silver caprate, silver myristate and silver palmitate.
- activator-toning agent is a heterocyclic activator-toning agent containing at least one nitrogen atom and of the formula:
- an especially suitable activatortoning agent is a heterocyclic activator-toning'agent containing at least one nitrogen atom which is'prefera bly a cyclicimide of the formula:
- R is hydrogen, hydroxyl, or a metal ion such as potassium, sodium, lithium, silver, gold or mercury
- Z represents carbon atoms of a series completing a cyclic imide nucleus, typically consisting of from five to six carbon atoms, e.g. a phthalimide or succinimide nucleus.
- the atoms of the cyclic imide nucleus can contain various substituent groups, especially amino, alkyl, such as alkyl containing one to five carbon atoms, such as methyl, ethyl, propyl, butyl or pentyl or aryl, such as aryl containing six to carbon atoms, such as phenyl, tolyl and xylyl.
- Suitable activator-toning agents which can be employed in the practice of the invention include:
- activator-toning agents can be employed in combination with or in place of the described cyclic imide activator-toning agents.
- a heterocyclic organic toning agent containing at least two hetero atoms in the heterocyclic ring of which at least one is a nitrogen atom is empoloyed.
- Suitable toners include, for example, phthalazinone, phthalic anhydride, 2- acetylphthalazinone and 2-phthalylphthalazinone.
- Other suitable toners are described, for example, in U.S. Pat. No. 3,446,648 of Workman issued May 27, 1969.
- activator-toning agents are suitable in a range of concentration however, they are especially employed at concentration of about 0.10 mole to about 1.05 moles of activator-toning agent per mole of oxidizing agent, e.g., per mole of silver behenate.
- a photosensitive element and composition described and used in the practice of the invention can contain various colloids alone or in combination as vehicles, binding agents and in various layers.
- Suitable materials are typically hydrophobic but hydrophilic materials can also be employed. They are transparent or translucent and include both naturally-occurring substances such as proteins, for example, gelatin, gelatin derivatives, cellulose derivatives, polysaccharides such as dextran, gum' arabic and the like; and synthetic polymeric substances such as water-soluble polyvinyl compounds like poly(vinyl pyrrolidone), acrylamide polymers and the like.
- Other synthetic polymeric compounds which can be employed include dispersed vinyl compounds such as in latex form and particularly those which increase dimensional stability of photographic materials. Suitable synthetic polymers include those described in U.S. Pat. No.
- Effective polymers include water insoluble polymers of alkyl acrylates and methacrylates, acrylic acid, sulfoalkyl acrylates or methacrylates, and those which have cross-linking sites which facilitate hardening or curing as well as those having recurring sulfobetaine units as described in Canadian Pat. No. 774,054.
- Preferred high molecular weight materials and resins'in include polyvinyl butyral, cellulose acetate butyrate, polymethyl methacrylate, poly(vinyl pyrrolidone), ethyl cellulose, polystyrene, polyvinyl chloride, chlorinated rubber, polyisobutylene, butadiene-styrene copolymers, vinyl chloridevinyl acetate copolymers, copolymers of vinyl acetate, vinyl chloride and maleic acid and polyvinyl alcohol.
- Typical supports include cellulose nitrate film, cellulose ester film, poly(vinylacetal) film, polystyrene film, poly(ethylene terephthalate) film, polycarbonate film and related films or resinous materials as well as glass, paper, metal and the like.
- a flexible support is employed, especially a paper support which can be partially acetylated or a coated with baryta and/or an alpha olefin polymer, particularly a polymer of an alpha olefin containing two to 10 carbon atoms such as polyethylene, polypropylene, ethylenebutene copolymers and the like.
- the photosensitive and thermosensitive elements used in the practice of the invention can contain antistatic or conducting layers.
- Such layers can comprise soluble salts such as chlorides, nitrates and the like, evaporated metal layers, ionic polymers such as those described in U.S. Pat. No. 2,861,056 of Minsk issued Nov. 18, 1958 and U.S. Pat. No. 3,206,312 of Sterrnan et al. issued Sept. 14, 1965 or insoluble inorganic salts such as those described in U.S. Pat. No. 3,428,451 of Trevoy issued Feb. 18, 1969.
- the photosensitive and thermosensitive elements can also contain antihalation materials and antihalation dyes.
- the photosensitive and thermosensitive layers or other layers employed in the practice of the invention can contain plasticizers and lubricants.
- plasticizers and lubricants include, for example, polyalcohols such as glycerin and diols described, for example, in U.S. Pat. No. 2,960,404 of Milton et al. issued Nov. 1, 1966; fatty acids or esters such as those described in U.S. Pat. No. 2,588,765 of Robijns issued Mar. 11, 1952; U.S. Pat. No. 3,121,060 ofDuane issued Feb. 11, 1964; and silicone resins such as those described in British Pat. No. 955,061.
- the photosensitive and thermosensitive layers or other layers employed in the practice of the invention can contain surfactants such as saponin; anionic compounds such as alkyl aryl sulfonates described, for example, in U.S. Pat. No. 2,600,831 of Baldsiefen issued June 17, 1962; amphoteric compounds such as those described in U.S. Pat. No. 3,133,816 of Ben-Ezra issued May 19, 1964; and adducts of glycidol and an alkyl phenol such as those described in British Pat. No. 1,022,878.
- surfactants such as saponin
- anionic compounds such as alkyl aryl sulfonates described, for example, in U.S. Pat. No. 2,600,831 of Baldsiefen issued June 17, 1962
- amphoteric compounds such as those described in U.S. Pat. No. 3,133,816 of Ben-Ezra issued May 19, 1964
- the photosensitive and thermosensitive elements employed in the practice of the invention can contain matting agents such as starch, titanium dioxide, zinc oxide, silica, polymeric beads including beads de scribed, for example, in U.S. Pat. No. 2,922,101 of Jelley et al. issued July 11, 1961 and U.S. Pat. No. 2,761,245 of Lynn issued Feb. 1, 1955.
- matting agents such as starch, titanium dioxide, zinc oxide, silica, polymeric beads including beads de scribed, for example, in U.S. Pat. No. 2,922,101 of Jelley et al. issued July 11, 1961 and U.S. Pat. No. 2,761,245 of Lynn issued Feb. 1, 1955.
- the photosensitive and thermosensitive elements and compositions employed in the practice of the invention can contain brightening agents including stilbenes, triazines, oxazoles, and coumarin brightening agents.
- Brightening agents including stilbenes, triazines, oxazoles, and coumarin brightening agents.
- Water-soluble brightening agents can be used such as those described in German Pat. No. 972,067 and U.S. Pat. No. 2,933,390 of McFall et al. issued Apr. 19, 1960 or dispersions of brighteners can be used such as those described in German Pat. No. 1,150,274; U.S. Pat. No. 3,406,070 of Oetiker et al. issued Oct. 15, 1968 and French Pat. No. 1,530,244.
- the photosensitive and thermosensitive layers used in the practice of the invention can be coated by various coating procedures including dip coa'ting, airknife coating, curtain coating or extrusion coating using hoppers such as described in U.S. Pat. No. 2,681,294 of Beguin issued June 15, 1954. If desired, two or more layers can be coated simultaneously such as by the procedures described in U.S. Pat. No. 2,761,791 of Russell issued Sept. 4, 1956 and British Pat. No. 837,095.
- a range of colorless onium halides can be employed in the described elements or compositions to provide an additional increase in photosensitivity, i.e., speed, and in some cases to obtain a reduction in background moiety, in a described photosensitive and thermosensitive element or composition suitable for processing with heat can in many cases also provide improved maximum image densities.
- Suitable nomaqueous solvents include, for example, tetrahydrothiophene-l,ldioxide, 4-hydroxybutanoic acid lactone and methylsulfinylmethane.
- a divalent metal salt which has the property of amplifying the developed image can be employed in the practice of the invention to further cause an increase in maximum image density.
- a suitable divalent metal salt image amplifier is zinc acetate, cadmium acetate or cupric acetate.
- the described image-amplifying compounds are suitable in a range of concentration of about 0.005 to about 0.20 mole of divalent metal salt image amplifier per mole of silver salt oxidizing agent; however, they are especially suitable at a concentration from about 0.010 mole to about 0.10 mole of divalent metal salt image amplifier per mole of silver salt oxidizing agent according to the invention in an element as described.
- the photosensitive silver halide can be prepared in situ, in the photosensitive and thermosensitive coatings of an element employed in the practice of the invention.
- a method is described, for example, in U.S. Pat. No. 3,457,075 of Morgan et al. issued July 22, 1969.
- a dilute solution of a halogen acid such as hydrochloric acid
- an organic silver salt such as silver behenate
- Silver halide is thus formed in situ throughout the surface of the coating of the organic silver salt.
- the photosensitive silver halide can be prepared on the oxidizing agent, such as silver behenate or silver stearate, or other organic silver salt, prior to application of the silver halide on the support employed.
- the oxidizing agent such as silver behenate or silver stearate, or other organic silver salt
- Spectral sensitizing dyes can be used conveniently to confer additional sensitivity to the elements and compositions of the invention.
- additional spectral sensitization can be obtained by treating the silver halide with a solution ofa sensitizing dye in an organic solvent or the dye can be added in the form of a dispersion as described in British Pat. No. 1,154,781.
- the dye can either be added to the emulsion as a final step or at some earlier stage.
- Sensitizing dyes useful in sensitizing silver halide emulsions are described, for example, in U.S. Pat. No. 2,526,632 of Brooker et al. issued Oct. 24, 1950; U.S. Pat. No. 2,503,776 of Sprague issued Apr. 11, 1950; U.S. Pat. No. 2,493,748 of Brooker et al. issued Jan. 10, 1950 and U.S. Pat. No. 3,384,486 of Taber et al. issued May 21, 1968.
- Spectral sensitizers which can be used, include the cyanines, merocyanines, complex (trinuclear or tetranuclear) cyanines, holopolar cyanines, styryls, hemicyanines such as enamine, hemicyanines, oxonols and hemioxonols.
- Dyes of the cyanine classes can contain such basic nuclei as the thiazolines, oxazolines, pyrrolines, pyridines, oxazoles, thiazoles, selenazoles, and imidazoles.
- Such nuclei can contain alkyl, alkylene, hydroxyalkyl, sulfoalkyl, carboxyalkyl, aminoalkyl, and enamine groups that can be fused to carbocyclic or heterocyclic ring systems either unsubstituted or substituted with halogen, phenyl, alkyl, haloalkyl, cyano, or alkoxy groups.
- the dyes can be symmetrical or unsymmetrical and can contain alkyl, phe nyl, enamine or heterocyclic substituents on the methine or polymethine chain.
- the merocyanine dyes can contain the basic nuclei described as well as acid nuclei such as thiohydantoins, rhodanines, oxazolidenediones, thiazolidenediones, barbituric acids, thiazolineones, and malononitrile.
- acid nuclei can be substituted with alkyl, alkylene, phenyl, carboxyalkyl, sulfoalkyl, hydroxyalkyl, alkoxyalkyl, alkylamine groups or heterocyclic nuclei. Combinations of these dyes can be used if desired.
- supersensitizing addenda which do not absorb visible light may be included such as, for instance, ascorbic acid derivatives, azaindenes, cadmium salts, and organic sulfonic acid as described in U.S. Pat. No. 2,933,390 of McFall et al. issued Apr. 19, 1960 and U.S. Pat. No. 2,937,089 of Jones et al. issued May 17, 1960.
- An especially suitable merocyanine dye is 3-carboxymethyl-5-[3-methyl-2(3H)- thiazolinylidene)isopropylidene] rhodanine of the formula:
- Suitable merocyanine dyes which can be employed in the practice of the invention include:
- a range of concentration of spectral sensitizing dye can be employed in the practice of the invention to provide spectral sensitivity.
- the desired concentration will be influenced by the desired spectral sensitivity, other components in the system, the desired image, processing conditions and the like.
- a concentration of the described spectral sensitizing dye is typically about 50 mg. to about 2 grams of spectral sensitizing dye per mole catalyst, e.g., per mole of photosensitive silver halide.
- the sensitizing dyes and other addenda used in the practice of the invention can be added from water solutions or suitable organic solvent solutions can be used.
- the compounds can be added using various procedures including, for example, those described in U.S. Pat. No. 2,912,343 of Collins et al. issued Nov. 10, 1959; U.S. Pat. No. 3,342,605 of McCrossen et al. issued Sept. 19, 1967; U.S. Pat. No. 2,996,287 of Audran issued Aug. 15, 1961; and U.S. Pat. No. 3,425,835 ofJohnson et al. issued Feb. 4, 1969.
- a preferred photosensitive ane thermosensitive element and composition according to the invention comprises a. photosensitive silver halide
- another embodiment of the invention is a process of developing a latent image in an exposed photosensitive and thermosensitive element comprising a support,
- an oxidation-reduction image-forming combination comprising i. a heavy metal salt oxidizing agent as described with ii. a bis-naphthol reducing agent, and
- a temperature range of about 80C. to about 250C. is suitable, usually a temperature range of about 120C. to about 180C. is employed for developing a desired image. By increasing or decreasing the length of time of heating, a higher or lower temperature within the described range can be employed.
- a developed image is typically produced within a few seconds, such as about 0.5 seconds to about 60 seconds but preferably within about 0.5 seconds to about seconds.
- Processing is usually carried out under ambient conditions of pressure and humidity. Temperatures, pressures and humidity outside normal atmospheric conditions can be employed if desired; however, normal atmospheric conditions are preferred.
- the heating means can be a simple hot plate, iron, roller or the like.
- an element can be prepared wherein the described silver halide can be in one layer and other components in other layers.
- an element according to the invention can comprise a support, a layer containing photographic silver halide and a layer comprising a so-called thermographic combina' tion or composition comprising a. a heavy metal salt oxidizing agent, as described,
- a reducing agent combination as described, preferably with c. an activator-toning agent, as described.
- composition and/or silver halide layer can contain other addenda, as described, also.
- thermographic combination is a composition comprising a. silver behenate, with b. 2,2-dihydroxy-1,l'-binaphthyl and a 1,3- dihydroxybenzene compound which is 2,4-dihydroxybenzaldehyde, 2,4-dihydroxybenzophenone and/or 2 ',4'-dihydroxyacetophenone.
- a polyvinylbutyral binder is employed with this composition.
- a photosensitive silver halide-silver behenate dispersion is prepared by ball-milling the following components together for about 72 hours:
- 150 milliliters of an acetone solution of lithium bromide 1.0 percent by weight lithium bromide in acetone
- the resulting silver photosensitive silver halide-silver behenate dispersion is designated as Dispersion I.
- Dispersion I 2.0 Milliliters of Dispersion I is mixed with the following components acetone-toluene (1:1 parts'by volume) to a total volume about Dye 1 is 3-Carboxymethyl-5-l3-methyl-2(3H)-thiazolinylidene) isopropylidene lrhodanine
- the resulting photosensitive composition is coated on a suitable photographic paper support at a wet thickness of 0.004 inches. Samples of the resulting photosensitive element are exposed .for 1 second to tungsten light at a contact printer. The exposed photosensitive element is heated by contacting the side opposite the photosensitive coating with a curved hot metal block for 4 seconds while the metal block is at a temperature of 145C.
- the resulting developed image has a maximum reflection density of 1.40, a minimum reflection density of 0.02, a relative speed, compared to a control which contains no bis-naphthol reducing agent, of 468, and on an exposure scale provides 11 visible steps.
- EXAMPLE 2 This is a comparative example.
- Example 1 The procedure set out in Example 1 is repeated with the exception that the described benzaldehyde compound is omitted from the photosensitive element.
- the resulting developed image has a maximum reflection density of 0.21 and a minimum reflection density of 0.02 with a relative speed of 100.On an exposure scale the developed image provides 8 visible steps.
- Example 1 The procedure set out in Example 1 is repeated with the exception that the described bis-naphthol reducing agent is omitted from the photosensitive element.
- the resulting developed image provides a maximum reflection density of 1.24 with a minimum reflection density of 0.02 and a relative speed of 100.
- the developed image provides 11 visible steps.
- Example 3 The procedure set out in Example 3 is repeated with the exception that the photosensitive element is heated for 7 seconds at l35C.
- the resulting developed image provides a maximum reflection density of 0.04 with a minimum reflection density of 0.02. Four visible steps are developed.
- EXAMPLE 7 This is a comparative example.
- EXAMPLE 8 EXAMPLE 9 This illustrates the invention.
- a photosensitive and thermosensitive element is prepared by mixing the following components Dispersion 1 (from Example 1) 2.0 ml Dye l (0.0l% by weight acetone) 1.0 ml l,l'-Bi-2-naphthol (5.0% by weight 1.0 ml acetone) 2,4'-Dihydroxyacetophenone 0.3 ml (5.0% b weight acetone) 4 S-Acety -2-benzyloxycarbonylthio- 0.5 ml 4-methylthiazole (1.0% by weight acetone) Acetone-toluene (lzl pans by volume) 8.0 ml
- Example 10 The procedure set out in Example 9 is repeated with the exception that 0.5 ml of an acetone solution of 2,4-dihydroxy-benzophenone (5.0 percent by weight in acetone) is employed in place of the described 2',4'- dihydroxyacetophenone.
- a visible line, black image on a beige background is produced upon heating the photosensitive element for 4 seconds on a hot metal block at a temperature of C.
- the developed image provides 9 visible dev'e1 oped steps.
- a photothennographic element comprising a support having thereon a. photosensitive silver halide
- an oxidation-reduction image forming combination comprising i. a heavy metal salt oxidizing agent with ii. a bis-betamaphthol reducing agent, and c. a 1,3-dihydroxybenzene compound of the formula:
- R is alkylene containing one to six carbon atoms, arylene containing six to 10 carbon atoms, carbonylalkyl containing two to three carbon atoms or carbonylphenyl, and Y is hydrogen, oxygen or sulfur.
- a photothermographic element as in claim 1 comprising a support having thereon a. photosensitive silver halide,
- an oxidation-reduction image forming combination comprising i. silver behenate with ii. 2,2'-dihydroxy-l ,l '-binaphthyl, and
- a photothermographic element as in claim 1 also comprising an activator-toning agent.
- a photothermographic element as in claim 1 also comprising phthalimide or phthalazinone.
- a photothermographic element as in claim 1 also comprising a stabilizer precursor.
- a photothermographic element as in claim 1 also comprising 5-acetyl-2-benzyloxycarbonylthio-4- methylthiazole.
- a photothermographic element as in claim 1 also comprising a sensitizing dye.
- a photothermographic element as in claim 1 also comprising 3-carboxymethyl5-[(3-methyl-2(3H)- thiazolinylidene)isopropylidene] rhodanine.
- a photothermographic element as in claim 1 comprising 0.01 to 0.50 moles of said photosensitive silver halide per mole of said heavy metal salt oxidizing agent; 0.4 to 2.0 moles of said bis-beta-naphthol reducing agent per mole of said heavy metal salt oxidizing agent; and wherein the ratio of said bis-beta-naphthol reducing agent to said 1,3-dihydroxybenzene compound is from 10:1 to 1:5.
- a photothermographic element comprising a support having thereon a. photosensitive silver halide, b. silver behenate, c. 2,2-dihydroxy-1,1-binaphthyl, d. 2,4-dihydroxybenzaldehyde, 2,4-dihydroxybenzophenone or 2,4-dihydroxyacetophenone, e. phthalimide, f. 5-acetyl-2-benzyloxycarbonylthio-4-methylthiazole, and 3-carboxymethyl-5-[(3-methyl-2(3H)- thiazolinylidene)isopropylidene]rhodanine.
- a photothermographic composition comprising a. photosensitive silver halide, with b.
- an oxidation-reduction image forming combination comprising i. a heavy metal salt oxidizing agent with ii. a bis-beta-naphthol reducing agent, and c. a 1,3-dihydroxybenzene compound of the formula:
- R is alkylene containing one to six carbon atoms, arylene containing six to carbon atoms, carbonylalkyl containing two to three carbon atoms or carbonylphenyl, and Y is hydrogen, oxygen or sulfur.
- a photothermographic composition as in claim 11 comprising a. photosensitive silver halide b. an oxidation-reduction image forming combination comprising i. silver behenate with ii. 2,2'-dihydroxy-1,1'-binaphthyl, and
- a photothermographic composition as in claim 11 also comprising an activator-toning agent.
- a photothermographic element as in claim 11 also comprising phthalimide or phthalazinone.
- a photothermographic composition as in claim 11 also comprising a sensitizing dye.
- a photothermographic composition as in claim 11 also comprising 3-carboxymethyl-5-[(3-methyl- 2(3H)-thiazolinylidene)isopropyl-idene]rhodanine.
- a photothermographic composition as in claim 11 comprising 0.01 to 0.50 moles of said photosensitive silver halide per mole of said heavy salt oxidizing agent; 0.4 to 2.0 moles of said bis-beta-naphthol reducing agent per mole of said heavy metal salt oxidizing agent; and wherein the ratio of said bis-beta-naphthol reducing agent to said 1,3-dihydroxybenzene compound is from 10:1 to 1:5.
- a photothermographic composition comprisng a. photosensitive silver halide,
- a process of developing a latent image in an exposed photothermographic element comprising a support having thereon a. photosensitive silver halide,
- an oxidation-reduction image forming combination comprising i. a heavy metal salt oxidizing agent with ii. a bis-beta-naphthol reducing agent, and
- a process of developing and stabilizing a latent image in an exposed photothermographic element comprising a support having thereon a. photosensitive silver halide,
Abstract
In photosensitive materials for processing with heat, a combination of a bis-beta-naphthol reducing agent with a 1,3dihydroxybenzene reducing agent, such as 2,4dihydroxybenzaldehyde or 2,4-dihydroxybenzophenone, provides surprisingly increased relative speed, maximum density and exposure latitude. This combination of reducing agents can be used in photosensitive and thermosensitive materials for processing with heat. These materials can contain addenda commonly employed in photosensitive materials such as activatortoning agents, stabilizers or stabilizer precursors, sensitizing dyes and the like.
Description
United States Patent Hiller PHOTOTHERMIC SILVER HALIDE ELEMENT CONTAINING A BIS-BETA-NAPHTHOL REDUCING AGENT AND A I, S-DII-IYDROXY-BENZENE REDUCING AGENT [75] Inventor: Gary Lynn Hillel, Hilton, NY.
[73] Assignee: Eastman Kodak Company,
Rochester, NY.
[22] Filed: Mar. 15, 1971 m1 Appi. No.: 124,464
[52] U.S. Cl. 96/50 R, 96/1 14.1, 117/368 [51] Int. Cl G03c 5/26, G03c 1/04 [58] Field of Search 96/l l4.l, 67
[56] References Cited UNITED STATES PATENTS 3,667,958 6/1972 Evans 96/1 l4.l FOREIGN PATENTS OR APPLICATIONS l,l78,800 l/l970 Great Britain 96/1 14.]
[ Aug. 7, 1973 Primary Examiner-Norman G. Torchin Assistant Examiner-Won H. Louie, Jr. Att0rneyR0bert W. Hampton, B. D. Wiese and R. E. Knapp [57] ABSTRACT In photosensitive materials for processing with heat, a combination ofa bis-beta-naphthol reducing agent with a 1,3-dihydroxybenzene reducing agent, such as 2,4-dihydroxybenzaldehyde or 2,4-dihydroxybenzophenone, provides surprisingly increased relative speed, maximum density and exposure latitude. This combination of reducing agents can be used in photosensitive and thermosensitive materials for processing with heat. These materials can contain addenda commonly employed in photosensitive materials such as activator-toning agents, stabilizers or stabilizer precursors, sensitizing dyes and the like.
24 Claims, No Drawings BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to photosensitive elements, compositions and processes for developing a latent image with heat. In one of its aspects it relates to photosensitive elements for processing with heat containing certain combinations of reducing agents which provide increased relative speed, increased maximum density and greater exposure latitude. In another of its aspects it relates to a photosensitive composition for processing with heat containing the described combination of reducing agents. A further aspect relates to photosensitive and thermosensitive compositions containing the described combination of reducing agents. Another aspect' relates to a thermographic combination comprising an oxidation-reduction image-forming combination containing a heavy metal salt oxidizing agent, such as silver behenate, with a described reducing agent combination. A further aspect relates to a process of developing a latent image in an exposed photosensitive and thermosensitive element employing the described combination of reducing agents.
2-. Description of the State of the Art It is known to provide a developed image in a photosensitive material employing so-called dry processing with heat. The photosensitive material can contain a reducing agent. Such photosensitive materials are described, for example, in U.S. Pat. No. 3,152,903 of Shepard et al. issued Oct. 13, 1964; U.S. Pat. No. 3,152,904 of Sorensen et al. issued Oct. 13, 1964; U.S. Pat. No. 3,392,020 of Yutzy and Yackel issued July 9, 1968; U.S. Pat. No. 3,457,075 of Morgan and Shely issued July 22, 1969; British Pat. No. 1,161,777 and Belgian Pat. No. 705,872. There has been a continuing need to provide combinations of reducing agents in photosensitive materials for processing with heat which provide increased relative speed and maximum density.
in thermographic materials it has been known to employ a reducing agent which is inactivated by image wise exposure to U.V. radiation. Such an element is described, for example, in U.S. Pat. No. 3,094,619 of Grant issued June 18, 1963. One of the reducing agents employed in this thermographic element can be 1,1 dihydroxy-2,2'-binaphthol. A similar element employing, for example, an alpha or beta naphthol as a reducing agent and l-(2H)phthalazinone, as a toning agent, is described, for example, in U.S. Pat. No. 3,080,254 of Grant issued Mar. 5, 1963.
Other bis-naphthol reducing agents which can be employed in photosensitive materials for processing with heat are described in copending U.S. Patent application Ser. No. 33,964 of DeMauriac filed May 1, 1970 now U.S. Pat. No. 3,672,904 issued June 27, 1972.
1,3-Dihydroxybenzene compounds have been employed in photosensitive materials in the past. For instance, U.S. Pat. No. 2,165,421 of Sheppard et al. issued July 11, 1939 indicates that a combination of an aliphatic aldehyde hardening agent with a 1,3- dihydroxybenzene compound can be employed for hardening gelatin. However, when a 1,3- dihydroxybenzene compound such as 2,4-dihydroxybenzaldehyde, is employed in a photosensitive material for processing with heat employing an oxidationreduction image-forming combination, this reducing agent does not provide the desired increased relative speed or increased maximum density. This is demonstrated in the following comparative Example 2 as well as in comparative Examples 4 and 5.
Accordingly, there has been a continuing need to provide a combination of reducing agents in photosensitive elements, compositions and processes for developing a latent image with heat which provide increased relative speed and increased maximum density as well as increased exposure latitude without increased minimum density.
SUMMARY OF THE INVENTION According to the invention, a combination of a bisnaphthol reducing agent especially a bis-beta-naphthol reducing agent, with a 1,3-dihydroxybenzene compound, as described herein in a photosensitive element, composition or process for developing a latent image with heat provides surprising increased relative speed as well as increased maximum density as well as wider exposure latitude without increased minimum density. This combination of reducing agents provides especially useful results in a photothermographic composition, also described herein as a photosensitive and thermosensitive composition employing photosensitive silver halide with an oxidation-reduction image-forming combination comprising a heavy metal salt oxidizing agent with a described combination of reducing agents.
The described combination of reducing agents provide the described results even in a combination with stabilizer precursors, activatontoning agents, sensitizing dyes and other addenda employed in photosensitive and thermosensitive elements, compositions and processes.
DETAILED DESCRIPTION OF THE INVENTION wherein R and/or R, is hydrogen, alkyl with one to three carbon atoms, alkoxy, e.g., alkoxy containing one to two carbon atoms, such as methoxy or ethoxy; halogen, nitro, amino, or a dia zonium halide salt and n is 0 or 1.
An especially suitable bis-fi-naphthol is 2,2'-dihydroxy-1,1'-binaphthyl of the formula Other examples of suitable bis-B-naphthols which can be employed in the practice of the invention include:
6,6'-dibromo-2,2'-dihydroxy-1,1'-binaphthyl 6,6'-dinitro-2,2 '-dihydroxy-l ,1-binaphthyl bis(2-hydroxy-1-naphthyl)methane.
A range of 1,3-dihydroxybenzene compounds as described herein can also be employed in the described combination of reducing agents. A suitable l,3- dihydroxybenzene compound is one which provides the desired increase in maximum density, relative speed and exposure latitude without undesired increase in minimum density. A suitable test for determining an acceptable 1,3-dihydroxybenzene compound to be employed in the practice of the invention is set out in Example 1 following. A class of 1,3-dihydroxybenzene compounds which has been found to satisfy this test and provide the desired properties is represented by the formula:
wherein R is alkylene containing one to six carbon atoms, such as methylene, ethylene, propylene, butylene, pentylene and hexylene or arylene containing six to carbon atoms, such as phenylene, methylphenylene, and xylylene, and carbonylalkyl, such as and carbonylphenyl, Y is hydrogen, oxygen or sulfur. These 1,3-dihydroxybenzene compounds can contain substituent groups which do not adversely affect the described desired properties, such as hydroxyl groups. Examples of suitable 1,3-dihydroxybenzene compounds are 2,4-dihydroxy benzaldehyde,
2,4-dihydroxy benzophenone, and
2,4-dihydroxy acetophenone.
The described combination of reducing agents is typically employed as a component of a photosensitive element. Accordingly, one of the embodiments of the invention is a photosensitive element comprising a support, a photosensitive component, typically photosensitive silver halide, and a bisnaphthol reducing agent with a 1,3-dihydroxybenzene compound, as described. A
. photosensitive composition employing the described reducing agent combination typically comprises photosensitive silver halide, a bis-naphthol reducing agent with a 1,3-dihydroxybenzene compound. However, a
preferred photosensitive and thermosensitive composition comprises a. photosensitive silver halide, with b. an oxidation-reduction image-forming combination comprising i. a heavy metal salt oxidizing agent with ii. a bis-naphthol reducing agent and c; a l,3dihydroxybenzene compound, asdescribed. The described combination of reducing agents can be employed in a range of concentrations in a photosensitive and thermosensitive element or composition. An especially suitable range of concentration is about 0.4 to about 2.0 moles of reducing agent combination per mole of photosensitive component employed. In a photosensitive and thermosensitive element or composition a preferred concentration range of components comprises 0.01 to 0.50 moles of photosensitive silver halide per mole of heavy metal salt oxidizing agent;
of Example 1 as a typical example, various desired concentrations can be determined by balancing the concentrations of components in the composition and/or element.
The photosensitive and thermosensitive elements and compositions in which the described combination of reducing agents can be employed are described, for example, in U.S. Pat. No. 3,457,075 of Morgen et al. issued July 22, 1969; U.S. Pat. No. 3,152,904 of Sorensen et al. issued Oct. 13, 1964; as well as in copending U.S. patent applications Ser. No. 33,964 of DeMauriac filed May 1, 1970 now U.S. Pat. No. 3,672,904 is sued June 27, 1972; Ser. No. 43,171 of Hiller filed June 3, 1970 corresponding to Belgian Patent No. 768,071 issued July 30, 1971; Ser. No. 43,173 of Hiller filed June 3, 1970 corresponding to Belgian Patent No. 768,073 issued July 30, 1971; Ser. No. 33,966 of Bojara and DeMauriac filed May 1, 1970 now U.S. Pat. No. 3,667,959 issued June 6, 1972; and Ser. No. 70,466 of DeMauriac and Gaugh filed Sept. 8, 1970 corresponding to Belgian Patent No. 772,371 issued Oct. 15,1971.
Other reducing agents can be used in combination with the described bis-naphthol reducing agents and 1,3-dihydroxybenzene reducing agents. These are typically silver halide developing agents and include, for example, polyhydroxybenzenes such as hydroquinone developing agents, e.g., hydroquinone, alkylsubstituted hydroquinones as exemplified by tertiary butylhydroquinone, methylhydroquinone, 2,5-dimethylhydroquinone and 2,6-dimethylhydroquinone; catechols and pyrogallol; halo-substituted hydroquinones such as chlorohydroquinone or dichlorohydroquinone; alkoxy-substituted hydroquinones such as methoxyhydroquinone or ethoxyhyrdoquinone; methylhydroxynaphthalene; phenylenediamine developing agents; methylgallate; aminophenol developing agents, such as 2,4-diaminophenols and methylaminophenols; ascorbic acid developing agents such as ascorbic acid, ascorbic acid ketals and ascrobic acid derivatives such as those described in U.S. Pat. No. 3,337,342 of Green issued Aug. 22, 1967; hydroxylamine developing agents such as N ,N '-di(Z-ethoxy-ethyl)hydroxylamine; 3- pyraz'olidone' developing agents such as l-phenyl-3- pyrazolidone and 4-methyl-4-hydroxymethyl-l-phenyl- 3-pyrazolidone including those described in British Patent 930,572 published July 3, 1963; hydroxytetronic acid, and hydroxytetronimide developing agents; reductone developing agents such as anhydrodihydropyrrolidino hexose reductone; and the like.
The described photosensitive element and/or composition contains a photosensitive component, preferably a photosensitive silver salt. A typical concentration range of photosensitive silver salt is from about 0.005 to about 0.50 mole of silver salt per mole of heavy metal salt oxidizing agent, such as per mole of silver salt of organic acid, e.g., per mole of silver behenate. A preferred photosensitive component is photosensitive silver halide, e.g., silver chloride, silver bromide, silver bromoiodide, silver chlorobromoiodide, or mixtures thereof. The photosensitive silver halide can be coarse or fine-grain, very fine-grain emulsions being especially useful. An emulsion containing the photosensitive silver halide can be prepared by any of the well-known procedures in the photographic art, such as single-jet emulsion, double-jet emulsions, such as Lippman emulsions, ammoniacal emulsions, thiocyanate or thioether ripened emulsions, such as those described in U.S. Pat. No. 2,222,264 of Nietz et al. issued Nov. 14, 1940; U.S. Pat. No. 3,320,069 of Illingsworth issued May 15, 1967 and U.S. Pat. No. 3,271,157 of McBride issued Sept. 6, 1966. Surface image silver halide emulsions can be used if desired. Mixtures of surface and internal image silver halide emulsions can be used as described in U.S. Pat. No. 2,996,332 of Luckey et al. issued Apr. 15, 1961. Negative type emulsions can be used. The silver halide emulsion can be a regular grain emulsion such as described in Klein and Moisar, Journal of Photographic Science, Volume l2, No. 5, September- October (1964) pages 242-251.
The silver halide employed'in the practice of the in vention can be unwashed or washed to remove, soluble salts. In the latter case the soluble salts can be removed by chill setting and leaching or the emulsion can be co agulation washed.
The silver halide employed in the practice of the invention can be sensitized with chemical sensitizers, such as with reducing agents; sulfur, selenium, or tellurium compounds; gold, platinum, or palladium compounds, or combinations of these. Suitable procedures are described, for example, in U.S. Pat. No. 1,623,499 of Shepard issued Apr. 5, 1927; U.S. Pat. No. 2,399,083 of Waller et al. issued Apr. 23, 194.6; U.S. Pat. No. 3,297,447 of McVeigh issued; Jan. 10, 1967 and U.S. Pat. No. 3,297,446 of Dunn issued Jan. 10, 1967.
Photosensitive silver halide employed in the practice of the invention can be protected against the production of fog and can be stabilized againstloss of sensitivity during keeping. Suitable antifoggants and stabilizers, e.g., used alone or in combination include, for example, thiazolium salts; azaindenes; me,rcury salts as,
described, for example, in U.S. Pat. No. 2,728,66 3 of Allen et al. issued Dec. 27, 1955; urazoles; sulfocatechols; oximes described, for example, in British Pat. No. 623,448; nitron; nitroindazoles; polyvalent metal salts described, for example, in U.S. Pat. No. 2,839,405 of Jones issued June 17, 1958; platinum, palladiumand gold salts described, for example, in U.S. Pat. No.
2,566,263 of Trivelli et al. issued Aug. 28, 19 51 and U.S. Pat. No. 2,597,915 ofYutzy et-al. issued May 27, 1952.
The described photosensitive and thermosensitive elements or compositions comprise an oxidizing agent, especially a heavy metal salt oxidizing agent, such as a heavy metal salt of an organic acid. The heavy metal salts of the organic acids should be resistant to darkening under illumination to prevent undesired deterioration of a developed image. An especially suitable class of heavy metal salts of organic acids is repre sented by the water insoluble silver salts of long-chain fatty acids which are stable to light. Compounds which are suitable silver salts include silver behenate, silver stearate, silver oleate, silver laurate, silver hydroxystearate, silver caprate, silver myristate and silver palmitate.
Other suitable carboxylic acid silver salt oxidizing agents, which are not silver salts of long-chain fatty acids, include silver benzoate, silver 4'-noctadecyloxydiphenyl-4-carboxylate, silver 0- aminobenzoate, silver acetamidobenzoate, silver furoate, silver camphorate, silver p-phenylbenzoate, silver phenylacetate, silver salicylate, silver butyrate, silver terephthalate, silver phthalate, silver acetate and silver acid phthalate.
Oxidizing agents which are not-silver salts of a carboxylic acid can be employed, if desired, such as silver phthalazinone, silver benzotriazole and silver saccharin. Oxidizing agents which are not silver salts can be employed, if desired, such as zinc oxide, gold stearate, mercuric behenate, auric behenate and the like, but silver salts are preferred. 1 7
It is desirable to employ a so-called activator-toning agent in the elements, compositions and processes of the invention to obtain a more neutral (black) image, particularly when phenolic reducing agents are used. A suitable activator-toning agent is a heterocyclic activator-toning agent containing at least one nitrogen atom and of the formula:
or an alkylene group containing three or four carbon atoms. The atoms completing the heterocyclic nucleus can contain various substituent groups, such as amino, alkyl amino, e.g. methylamino or ethylamino, hydroxyl, carbamyl and the. like. An especially suitable activatortoning agent is a heterocyclic activator-toning'agent containing at least one nitrogen atom which is'prefera bly a cyclicimide of the formula:
wherein R is hydrogen, hydroxyl, or a metal ion such as potassium, sodium, lithium, silver, gold or mercury; Z represents carbon atoms of a series completing a cyclic imide nucleus, typically consisting of from five to six carbon atoms, e.g. a phthalimide or succinimide nucleus. The atoms of the cyclic imide nucleus can contain various substituent groups, especially amino, alkyl, such as alkyl containing one to five carbon atoms, such as methyl, ethyl, propyl, butyl or pentyl or aryl, such as aryl containing six to carbon atoms, such as phenyl, tolyl and xylyl. Suitable activator-toning agents which can be employed in the practice of the invention include:
Phthalimide,
N-Hydroxyphthalimide,
N-Potassium phthalimide,
N-Silver phthalimide,
N-Mercury phthalimide,
Succinimide, and/or N-l-lydroxysuccinimide.
Other so-called activator-toning agents can be employed in combination with or in place of the described cyclic imide activator-toning agents. Typically a heterocyclic organic toning agent containing at least two hetero atoms in the heterocyclic ring of which at least one is a nitrogen atom is empoloyed. These are described, for example, in U.S. Pat. No. 3,080,254 of Grant issued Mar. 5, 1963. Suitable toners include, for example, phthalazinone, phthalic anhydride, 2- acetylphthalazinone and 2-phthalylphthalazinone. Other suitable toners are described, for example, in U.S. Pat. No. 3,446,648 of Workman issued May 27, 1969. The described activator-toning agents are suitable in a range of concentration however, they are especially employed at concentration of about 0.10 mole to about 1.05 moles of activator-toning agent per mole of oxidizing agent, e.g., per mole of silver behenate.
It is desirable to employ an image stabilizer or stabilizer precursor in the described elements or compositions of the invention. These can be employed in the practice of the invention to reduce the amount of postprocessing print-out due to room light exposure and to reduce the background stain. Suitable stabilizer precursors include azole thioethers and blocked azole thione stabilizer precursors, e.g., 5-acetyl-4-methy1-2-(3- oxobutylthio )thiazole, 4-furoyl-3 -methylthio-l ,2,4- thiadiazole-S-thione, 5-acetyl-4-methyl-3-(3- oxobutyl)-thiazoline-2-thione and 2,6-di-tert-butyl-4- (1-phenyl-5-tetrazolyl)thiophenol. The described stabilizer precursors are suitable in a range of concentration; however, they are especiallysuitable at a concentration from about 0.002 mole to about 0.10 mole of stabilizer precursor per mole of oxidizing agent, e.g., per mole of silver behenate in an element or composition as described.
A photosensitive element and composition described and used in the practice of the invention can contain various colloids alone or in combination as vehicles, binding agents and in various layers. Suitable materials are typically hydrophobic but hydrophilic materials can also be employed. They are transparent or translucent and include both naturally-occurring substances such as proteins, for example, gelatin, gelatin derivatives, cellulose derivatives, polysaccharides such as dextran, gum' arabic and the like; and synthetic polymeric substances such as water-soluble polyvinyl compounds like poly(vinyl pyrrolidone), acrylamide polymers and the like. Other synthetic polymeric compounds which can be employed include dispersed vinyl compounds such as in latex form and particularly those which increase dimensional stability of photographic materials. Suitable synthetic polymers include those described in U.S. Pat. No. 3,142,586 of Nottorf issued July 28, 1964; U.S. Pat. No. 3,193,386 of White issued July 6, 1955; U.S. Pat. No. 3,062,674 of Houck et al. issued Nov. 6, 1962; U.S. Pat. No. 3,220,844 of Houck et al. issued Nov. 30, 1965; U.S. Pat. No. 3,287,289 of Ream et al. issued Nov. 22, 1966; and U.S. Pat. No. 3,411,911 of Dykstra issued Nov. 19, 1968. Effective polymers include water insoluble polymers of alkyl acrylates and methacrylates, acrylic acid, sulfoalkyl acrylates or methacrylates, and those which have cross-linking sites which facilitate hardening or curing as well as those having recurring sulfobetaine units as described in Canadian Pat. No. 774,054. Preferred high molecular weight materials and resins'include polyvinyl butyral, cellulose acetate butyrate, polymethyl methacrylate, poly(vinyl pyrrolidone), ethyl cellulose, polystyrene, polyvinyl chloride, chlorinated rubber, polyisobutylene, butadiene-styrene copolymers, vinyl chloridevinyl acetate copolymers, copolymers of vinyl acetate, vinyl chloride and maleic acid and polyvinyl alcohol.
The photosensitive and thermosensitive layers and other layers of an element employed in the practice of the invention and described herein can be coated on a wide variety of supports. Typical supports include cellulose nitrate film, cellulose ester film, poly(vinylacetal) film, polystyrene film, poly(ethylene terephthalate) film, polycarbonate film and related films or resinous materials as well as glass, paper, metal and the like. Typically a flexible support is employed, especially a paper support which can be partially acetylated or a coated with baryta and/or an alpha olefin polymer, particularly a polymer of an alpha olefin containing two to 10 carbon atoms such as polyethylene, polypropylene, ethylenebutene copolymers and the like.
The photosensitive and thermosensitive and other hardenable layers of an element used in the practice of this invention can be hardened by various organic or inorganic hardeners, alone or in combination, such as aldehydes, and blocked aldehydes, ketones, carboxylic and carbonic acid derivatives, sulfonate esters, sulfonyl halides and vinyl sulfonyl ethers, active halogen compounds, epoxy compounds, aziridines, active olefins, isocyanates, carbodiimides, mixed-function hardeners and polymeric hardeners such as oxidized polysaccharides like dialdehyde starch and oxyguargum and the like.
The photosensitive and thermosensitive elements used in the practice of the invention can contain antistatic or conducting layers. Such layers can comprise soluble salts such as chlorides, nitrates and the like, evaporated metal layers, ionic polymers such as those described in U.S. Pat. No. 2,861,056 of Minsk issued Nov. 18, 1958 and U.S. Pat. No. 3,206,312 of Sterrnan et al. issued Sept. 14, 1965 or insoluble inorganic salts such as those described in U.S. Pat. No. 3,428,451 of Trevoy issued Feb. 18, 1969. The photosensitive and thermosensitive elements can also contain antihalation materials and antihalation dyes.
The photosensitive and thermosensitive layers or other layers employed in the practice of the invention can contain plasticizers and lubricants. Suitable plasticizers and lubricants include, for example, polyalcohols such as glycerin and diols described, for example, in U.S. Pat. No. 2,960,404 of Milton et al. issued Nov. 1, 1966; fatty acids or esters such as those described in U.S. Pat. No. 2,588,765 of Robijns issued Mar. 11, 1952; U.S. Pat. No. 3,121,060 ofDuane issued Feb. 11, 1964; and silicone resins such as those described in British Pat. No. 955,061.
The photosensitive and thermosensitive layers or other layers employed in the practice of the invention can contain surfactants such as saponin; anionic compounds such as alkyl aryl sulfonates described, for example, in U.S. Pat. No. 2,600,831 of Baldsiefen issued June 17, 1962; amphoteric compounds such as those described in U.S. Pat. No. 3,133,816 of Ben-Ezra issued May 19, 1964; and adducts of glycidol and an alkyl phenol such as those described in British Pat. No. 1,022,878.
If desired, the photosensitive and thermosensitive elements employed in the practice of the invention can contain matting agents such as starch, titanium dioxide, zinc oxide, silica, polymeric beads including beads de scribed, for example, in U.S. Pat. No. 2,922,101 of Jelley et al. issued July 11, 1961 and U.S. Pat. No. 2,761,245 of Lynn issued Feb. 1, 1955.
The photosensitive and thermosensitive elements and compositions employed in the practice of the invention can contain brightening agents including stilbenes, triazines, oxazoles, and coumarin brightening agents. Water-soluble brightening agents can be used such as those described in German Pat. No. 972,067 and U.S. Pat. No. 2,933,390 of McFall et al. issued Apr. 19, 1960 or dispersions of brighteners can be used such as those described in German Pat. No. 1,150,274; U.S. Pat. No. 3,406,070 of Oetiker et al. issued Oct. 15, 1968 and French Pat. No. 1,530,244.
The various layers including the photosensitive and thermosensitive layers of an element employed in the practice of the invention can contain light-absorbing materials, filterdyes, antihalation dyes and absorbing dyes such as those described in U.S. Pat. No. 3,253,921 of Sawdey issued May 31, 1966; U.S. Pat. No. 2,274,782 of Gaspar issued Mar. 3, 1942; U.S. Pat. No. 2,527,583 of Silberstein et al. issued Oct. 31, 1950; and U.S. Pat. No. 2,956,879 of VanCampen issued Oct. 18, 1960. If desired, the dyes can be mordanted, for example, as described in U.S. Pat. No. 3,282,699 of Jones et al. issued Nov. 1, 1966.
The photosensitive and thermosensitive layers used in the practice of the invention can be coated by various coating procedures including dip coa'ting, airknife coating, curtain coating or extrusion coating using hoppers such as described in U.S. Pat. No. 2,681,294 of Beguin issued June 15, 1954. If desired, two or more layers can be coated simultaneously such as by the procedures described in U.S. Pat. No. 2,761,791 of Russell issued Sept. 4, 1956 and British Pat. No. 837,095.
A range of colorless onium halides can be employed in the described elements or compositions to provide an additional increase in photosensitivity, i.e., speed, and in some cases to obtain a reduction in background moiety, in a described photosensitive and thermosensitive element or composition suitable for processing with heat can in many cases also provide improved maximum image densities. Suitable nomaqueous solvents include, for example, tetrahydrothiophene-l,ldioxide, 4-hydroxybutanoic acid lactone and methylsulfinylmethane.
A divalent metal salt which has the property of amplifying the developed image can be employed in the practice of the invention to further cause an increase in maximum image density. A suitable divalent metal salt image amplifier is zinc acetate, cadmium acetate or cupric acetate. The described image-amplifying compounds are suitable in a range of concentration of about 0.005 to about 0.20 mole of divalent metal salt image amplifier per mole of silver salt oxidizing agent; however, they are especially suitable at a concentration from about 0.010 mole to about 0.10 mole of divalent metal salt image amplifier per mole of silver salt oxidizing agent according to the invention in an element as described.
If desired, the photosensitive silver halide can be prepared in situ, in the photosensitive and thermosensitive coatings of an element employed in the practice of the invention. Such a method is described, for example, in U.S. Pat. No. 3,457,075 of Morgan et al. issued July 22, 1969. For example, a dilute solution of a halogen acid such as hydrochloric acid, can be applied to the surface of a thin coating containing an organic silver salt, such as silver behenate, on a suitable substrate followed by removal of the solvent if desired. Silver halide is thus formed in situ throughout the surface of the coating of the organic silver salt.
The photosensitive silver halide can be prepared on the oxidizing agent, such as silver behenate or silver stearate, or other organic silver salt, prior to application of the silver halide on the support employed. This is also described in U.S. Pat. No. 3,457,075 of Morgan et al. issued July 22, 1969, for example, a halogen acid by employing highly purifiedrnaterials; for-example, I
freedom from halides and sulfides increase stability to light exposure. The use of highly purified silver behenate can, for example, reduce propensity to print out in background areas of an element prepared according to the invention.
Spectral sensitizing dyes can be used conveniently to confer additional sensitivity to the elements and compositions of the invention. For instance, additional spectral sensitization can be obtained by treating the silver halide with a solution ofa sensitizing dye in an organic solvent or the dye can be added in the form of a dispersion as described in British Pat. No. 1,154,781. For optimum results the dye can either be added to the emulsion as a final step or at some earlier stage.
Sensitizing dyes useful in sensitizing silver halide emulsions are described, for example, in U.S. Pat. No. 2,526,632 of Brooker et al. issued Oct. 24, 1950; U.S. Pat. No. 2,503,776 of Sprague issued Apr. 11, 1950; U.S. Pat. No. 2,493,748 of Brooker et al. issued Jan. 10, 1950 and U.S. Pat. No. 3,384,486 of Taber et al. issued May 21, 1968. Spectral sensitizers, which can be used, include the cyanines, merocyanines, complex (trinuclear or tetranuclear) cyanines, holopolar cyanines, styryls, hemicyanines such as enamine, hemicyanines, oxonols and hemioxonols. Dyes of the cyanine classes can contain such basic nuclei as the thiazolines, oxazolines, pyrrolines, pyridines, oxazoles, thiazoles, selenazoles, and imidazoles. Such nuclei can contain alkyl, alkylene, hydroxyalkyl, sulfoalkyl, carboxyalkyl, aminoalkyl, and enamine groups that can be fused to carbocyclic or heterocyclic ring systems either unsubstituted or substituted with halogen, phenyl, alkyl, haloalkyl, cyano, or alkoxy groups. The dyes can be symmetrical or unsymmetrical and can contain alkyl, phe nyl, enamine or heterocyclic substituents on the methine or polymethine chain.
The merocyanine dyes can contain the basic nuclei described as well as acid nuclei such as thiohydantoins, rhodanines, oxazolidenediones, thiazolidenediones, barbituric acids, thiazolineones, and malononitrile. These acid nuclei can be substituted with alkyl, alkylene, phenyl, carboxyalkyl, sulfoalkyl, hydroxyalkyl, alkoxyalkyl, alkylamine groups or heterocyclic nuclei. Combinations of these dyes can be used if desired. In addition, supersensitizing addenda which do not absorb visible light may be included such as, for instance, ascorbic acid derivatives, azaindenes, cadmium salts, and organic sulfonic acid as described in U.S. Pat. No. 2,933,390 of McFall et al. issued Apr. 19, 1960 and U.S. Pat. No. 2,937,089 of Jones et al. issued May 17, 1960.
An especially suitable merocyanine dye is 3-carboxymethyl-5-[3-methyl-2(3H)- thiazolinylidene)isopropylidene] rhodanine of the formula:
Other examples of suitable merocyanine dyes which can be employed in the practice of the invention include:
l. 3-p-Carboxyphenyl-5-[B-ethyl-2( 3 benzoxazolylidene) ethylidene]rhodanine, 2 5-[ (3-B-carboxyethyl-2( 3- thiazolinylidene)ethylidenel-3-ethylrhodanine,
3. 3-Carboxymethyl-5-[(S-methylthiazolinylidene)- a-ethyl-ethylidenel-rhodanine,
4. l-Carboxymethyl-5-[(3-ethyl-2-(3H)- benzoxazolylidene) ethylidene]-3-phenyl-2 thiohydantoin,
5. 5-[(3-ethyl-2-benzoxazolinylidene)-1-methylethylidene]-3-[3-pyrrolin-lyl)-propyl]rhodanine, and/or 6. 3-ethyl-5-[(3-ethyl-2(3H)-benzothiazolylidene) isopropylidene]-2-thio-2,4-oxazolidinedione.
A range of concentration of spectral sensitizing dye can be employed in the practice of the invention to provide spectral sensitivity. The desired concentration will be influenced by the desired spectral sensitivity, other components in the system, the desired image, processing conditions and the like. Typically a concentration of the described spectral sensitizing dye is typically about 50 mg. to about 2 grams of spectral sensitizing dye per mole catalyst, e.g., per mole of photosensitive silver halide.
The sensitizing dyes and other addenda used in the practice of the invention can be added from water solutions or suitable organic solvent solutions can be used. The compounds can be added using various procedures including, for example, those described in U.S. Pat. No. 2,912,343 of Collins et al. issued Nov. 10, 1959; U.S. Pat. No. 3,342,605 of McCrossen et al. issued Sept. 19, 1967; U.S. Pat. No. 2,996,287 of Audran issued Aug. 15, 1961; and U.S. Pat. No. 3,425,835 ofJohnson et al. issued Feb. 4, 1969.
A preferred photosensitive ane thermosensitive element and composition according to the invention comprises a. photosensitive silver halide,
b. silver behenate,
c. 2,2-dihydroxy-l,l -binaphthyl,
d. 2,4-dihydroxybenzaldehyde, 2,4-dihydroxybenzophenone or 2,4-dihydroxyacetophenone,
e. phthalimide,
f. 5-acetyl-2-benzyloxycarbonyl methylthiazole, and
thio-4- 3-carboxymethyl-5-[ 3-methyl-2( 31-1)- thiazolinylidene) isopropylidene]rhodanine.
After exposure of the described photosensitive element, the resulting latent image can be developed merely by heating the element. Accordingly, another embodiment of the invention is a process of developing a latent image in an exposed photosensitive and thermosensitive element comprising a support,
a. photosensitive silver halide,
b. an oxidation-reduction image-forming combination comprising i. a heavy metal salt oxidizing agent as described with ii. a bis-naphthol reducing agent, and
c. a 1,3-dihydroxybenzene compound, as described, comprising heating said element to about C. to about 250C.
While a temperature range of about 80C. to about 250C. is suitable, usually a temperature range of about 120C. to about 180C. is employed for developing a desired image. By increasing or decreasing the length of time of heating, a higher or lower temperature within the described range can be employed. A developed image is typically produced within a few seconds, such as about 0.5 seconds to about 60 seconds but preferably within about 0.5 seconds to about seconds.
Processing is usually carried out under ambient conditions of pressure and humidity. Temperatures, pressures and humidity outside normal atmospheric conditions can be employed if desired; however, normal atmospheric conditions are preferred.
Any suitable means can be used for providing the desired processing temperature range. The heating means can be a simple hot plate, iron, roller or the like.
in some cases, if desired, an element can be prepared wherein the described silver halide can be in one layer and other components in other layers. For example, an element according to the invention can comprise a support, a layer containing photographic silver halide and a layer comprising a so-called thermographic combina' tion or composition comprising a. a heavy metal salt oxidizing agent, as described,
and
b. a reducing agent combination, as described, preferably with c. an activator-toning agent, as described.
This composition and/or silver halide layer can contain other addenda, as described, also.
A typical thermographic combination is a composition comprising a. silver behenate, with b. 2,2-dihydroxy-1,l'-binaphthyl and a 1,3- dihydroxybenzene compound which is 2,4-dihydroxybenzaldehyde, 2,4-dihydroxybenzophenone and/or 2 ',4'-dihydroxyacetophenone.
Typically, a polyvinylbutyral binder is employed with this composition.
Other addenda known to be useful in photosensitive and thermosensitive elements of this type, such as described in British Pat. No. 1,161,777 published Aug. 20, 1969; U.S. Pat. No. 3,152,904 of Sorensen and Shepard issued Oct. 13, 1964 and US. Pat. No. 3,457,075 of Morgan and Shely patented July 22, 1969 can be employed in the practice of the invention.
The'following examples are included for a further understanding of the invention.
EXAMPLE 1 This illustrates the invention.
A photosensitive silver halide-silver behenate dispersion is prepared by ball-milling the following components together for about 72 hours:
Silver behenate 84.0 g Behenic acid 64.0 g Polyvinyl butyral 30.0 g Phthalimide 17.0 g Acetone-toluene (1:1 pans 1000.0 ml by volume) When the ball-milling procedure is completed, 150 milliliters of an acetone solution of lithium bromide (1.0 percent by weight lithium bromide in acetone) is added to the resulting composition and the composition stirred for about 16 hours. The resulting silver photosensitive silver halide-silver behenate dispersion is designated as Dispersion I.
2.0 Milliliters of Dispersion I is mixed with the following components acetone-toluene (1:1 parts'by volume) to a total volume about Dye 1 is 3-Carboxymethyl-5-l3-methyl-2(3H)-thiazolinylidene) isopropylidene lrhodanine The resulting photosensitive composition is coated on a suitable photographic paper support at a wet thickness of 0.004 inches. Samples of the resulting photosensitive element are exposed .for 1 second to tungsten light at a contact printer. The exposed photosensitive element is heated by contacting the side opposite the photosensitive coating with a curved hot metal block for 4 seconds while the metal block is at a temperature of 145C.
The resulting developed image has a maximum reflection density of 1.40, a minimum reflection density of 0.02, a relative speed, compared to a control which contains no bis-naphthol reducing agent, of 468, and on an exposure scale provides 11 visible steps.
EXAMPLE 2 This is a comparative example.
The procedure set out in Example 1 is repeated with the exception that the described benzaldehyde compound is omitted from the photosensitive element.
The resulting developed image has a maximum reflection density of 0.21 and a minimum reflection density of 0.02 with a relative speed of 100.On an exposure scale the developed image provides 8 visible steps.
This illustrates the surprising increase in maximum density, relative speed and exposure latitude, demonstrated by the increased number of visible steps, provided by the combinations of reducing agents of the invention.
EXAMPLE 3 This is a comparative example.
The procedure set out in Example 1 is repeated with the exception that the described bis-naphthol reducing agent is omitted from the photosensitive element.
The resulting developed image provides a maximum reflection density of 0.14 and a minimum reflection density of 0.02 with a relative speed of 16 compared to the photosensitive element of Examples 1 and 2. On an exposure scale the developed image provides 7 visible steps.
EXAMPLE 4 This is a comparative example.
The procedure set out in Example 2 is repeated with the exception that the photosensitive element is heated for 7 seconds at C. I
The resulting developed image provides a maximum reflection density of 0.59, aminimum reflection density of 0.02 with a relative speed of 69 with 9 visible steps developed.
EXAMPLE This is a comparative example.
The procedure set out in Example 2 is repeated with the exception that the photosensitive element is heated for seconds at 135C.
The resulting developed image provides a maximum reflection density of 1.24 with a minimum reflection density of 0.02 and a relative speed of 100. The developed image provides 11 visible steps.
EXAMPLE 6 This is a comparative example.
The procedure set out in Example 3 is repeated with the exception that the photosensitive element is heated for 7 seconds at l35C.
The resulting developed image provides a maximum reflection density of 0.04 with a minimum reflection density of 0.02. Four visible steps are developed.
EXAMPLE 7 This is a comparative example.
The procedure set out in Example 3 is repeated with the exception that the photosensitive element is heated for 15 seconds at 135C.
The resulting developed image provides a maximum reflection density of 0.14 with a minimum reflection density of 0.02. Six visible steps are developed.
EXAMPLE 8 EXAMPLE 9 This illustrates the invention. A photosensitive and thermosensitive element is prepared by mixing the following components Dispersion 1 (from Example 1) 2.0 ml Dye l (0.0l% by weight acetone) 1.0 ml l,l'-Bi-2-naphthol (5.0% by weight 1.0 ml acetone) 2,4'-Dihydroxyacetophenone 0.3 ml (5.0% b weight acetone) 4 S-Acety -2-benzyloxycarbonylthio- 0.5 ml 4-methylthiazole (1.0% by weight acetone) Acetone-toluene (lzl pans by volume) 8.0 ml
to a total volume of about The resulting composition is coated on a photographic paper support at a wet thickness of 0.004 inches. A sample of the resulting photosensitive and thermosensitive element is exposed for one second to tungsten light in a contact printer. The exposed photosensitive element is heated by contacting the side opposite the photosensitive coating with a curved hot metal block for 4 seconds while the metal block is at a tem- EXAMPLE 10 The procedure set out in Example 9 is repeated with the exception that 0.5 ml of an acetone solution of 2,4-dihydroxy-benzophenone (5.0 percent by weight in acetone) is employed in place of the described 2',4'- dihydroxyacetophenone.
A visible line, black image on a beige background is produced upon heating the photosensitive element for 4 seconds on a hot metal block at a temperature of C. The developed image provides 9 visible dev'e1 oped steps.
The invention has been described in detail with particular reference to preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention.
What is claimed is:
1. A photothennographic element comprising a support having thereon a. photosensitive silver halide,
b. an oxidation-reduction image forming combination comprising i. a heavy metal salt oxidizing agent with ii. a bis-betamaphthol reducing agent, and c. a 1,3-dihydroxybenzene compound of the formula:
wherein R is alkylene containing one to six carbon atoms, arylene containing six to 10 carbon atoms, carbonylalkyl containing two to three carbon atoms or carbonylphenyl, and Y is hydrogen, oxygen or sulfur.
2. A photothermographic element as in claim 1 comprising a support having thereon a. photosensitive silver halide,
b. an oxidation-reduction image forming combination comprising i. silver behenate with ii. 2,2'-dihydroxy-l ,l '-binaphthyl, and
c. 2,4-dihydroxybenzaldehyde, 2,4-dihydroxybenzophenone, or 2,4'-dihydroxyacetophenone.
3. A photothermographic element as in claim 1 also comprising an activator-toning agent.
4. A photothermographic element as in claim 1 also comprising phthalimide or phthalazinone.
5. A photothermographic element as in claim 1 also comprising a stabilizer precursor.
6. A photothermographic element as in claim 1 also comprising 5-acetyl-2-benzyloxycarbonylthio-4- methylthiazole.
7. A photothermographic element as in claim 1 also comprising a sensitizing dye.
8. A photothermographic element as in claim 1 also comprising 3-carboxymethyl5-[(3-methyl-2(3H)- thiazolinylidene)isopropylidene] rhodanine.
9. A photothermographic element as in claim 1 comprising 0.01 to 0.50 moles of said photosensitive silver halide per mole of said heavy metal salt oxidizing agent; 0.4 to 2.0 moles of said bis-beta-naphthol reducing agent per mole of said heavy metal salt oxidizing agent; and wherein the ratio of said bis-beta-naphthol reducing agent to said 1,3-dihydroxybenzene compound is from 10:1 to 1:5.
10. A photothermographic element comprising a support having thereon a. photosensitive silver halide, b. silver behenate, c. 2,2-dihydroxy-1,1-binaphthyl, d. 2,4-dihydroxybenzaldehyde, 2,4-dihydroxybenzophenone or 2,4-dihydroxyacetophenone, e. phthalimide, f. 5-acetyl-2-benzyloxycarbonylthio-4-methylthiazole, and 3-carboxymethyl-5-[(3-methyl-2(3H)- thiazolinylidene)isopropylidene]rhodanine. 11. A photothermographic composition comprising a. photosensitive silver halide, with b. an oxidation-reduction image forming combination comprising i. a heavy metal salt oxidizing agent with ii. a bis-beta-naphthol reducing agent, and c. a 1,3-dihydroxybenzene compound of the formula:
wherein R is alkylene containing one to six carbon atoms, arylene containing six to carbon atoms, carbonylalkyl containing two to three carbon atoms or carbonylphenyl, and Y is hydrogen, oxygen or sulfur.
12. A photothermographic composition as in claim 11 comprising a. photosensitive silver halide b. an oxidation-reduction image forming combination comprising i. silver behenate with ii. 2,2'-dihydroxy-1,1'-binaphthyl, and
c. 2,4-dihydroxybenzaldehyde, 2,4-dihydroxybenzophenone, or 2,4'-dihydroxyacetophenone.
13. A photothermographic composition as in claim 11 also comprising an activator-toning agent.
14. A photothermographic element as in claim 11 also comprising phthalimide or phthalazinone.
15. A photothermographic composition as in claim 11 also comprising a stabilizer precursor.
16. A photothermographic composition as in claim 11 also comprising 5-acetyl-2-benzyloxycarbonylthio- 4-methylthiazole.
17. A photothermographic composition as in claim 11 also comprising a sensitizing dye.
18. A photothermographic composition as in claim 11 also comprising 3-carboxymethyl-5-[(3-methyl- 2(3H)-thiazolinylidene)isopropyl-idene]rhodanine.
19. A photothermographic composition as in claim 11 comprising 0.01 to 0.50 moles of said photosensitive silver halide per mole of said heavy salt oxidizing agent; 0.4 to 2.0 moles of said bis-beta-naphthol reducing agent per mole of said heavy metal salt oxidizing agent; and wherein the ratio of said bis-beta-naphthol reducing agent to said 1,3-dihydroxybenzene compound is from 10:1 to 1:5.
20. A photothermographic composition comprisng a. photosensitive silver halide,
b. silver behenate, I
c. 2,2-dihydroxy-l,1'-binaphthyl,
d. 2,4-dihydroxybenzyaldehyde, 2,4-dihydroxybenzophenone, or 2,4-dihydroxyacetophenone,
e. phthalimide,
f. 5-acetyl2-benzyloxycarbonylthio-4-methylthiazole, and 3-carboxymethyl-5-[(3-methyl-2(3H)- thiazolinylidene)isopropylidene]rhodanine.
21. A process of developing a latent image in an exposed photothermographic element comprising a support having thereon a. photosensitive silver halide,
b. an oxidation-reduction image forming combination comprising i. a heavy metal salt oxidizing agent with ii. a bis-beta-naphthol reducing agent, and
c. a 1,3-dihydroxybenzene compound represented by the formula:
wherein R, is alkylene containing one to six carbon atoms, arylene containing six to 10 carbon atoms, carbonylalkyl containing two.to three carbon atoms or carbonylphenyl, and Y'is hydrogen, oxygen or sulfur, comprising heating said element to about C. to about 250C.
22. The process of claim 28 wherein said element is heated to about 80C. to about 250C. for about 0.5 to
about 60 seconds.
23. A process of developing and stabilizing a latent image in an exposed photothermographic element comprising a support having thereon a. photosensitive silver halide,
b. silver behenate,
c. 2,2-dihydroxy-1,1-binaphthyl,
d. 2,4-dihydroxybenzaldehyde, 2,4-dihydroxybenzophenone or 2,4-dihydroxyacetophenone,
e. phthalimide,
f. 5-acetyl-2-benzyloxycarbonylthio-4- methylthiazole, and
g. 3-carboxymethyl-5-[(3-methyl-2(3H)- thiazolinylidene )isopropylidene lrhodanine, comprising heating said element to about 80C. to about 250C.
24. The process of claim 30 wherein saidelement is heated at about C. to about 180C. for about 0.5
to about 5 seconds.
i i t t PC4050 UNITED STATES PATENT OFFICE 9 CERTIFICATE OF CORRECTION Patent No.- I 3,75l, 9 Dated Augugt 7, 973
Inventor(s) Gary L Hillel" T v It is certified that err or appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:
- Column 12, line 1M, "3- rro1in-1 l" should read -+--"3 pyrrolin-l-yl---.
In the Claims: I
Column 18, line Y 59 "claim 30" should read ---claim 23- Signed and sealed this 27th day of Nbvember 1973.
(SEAL) Attest:
' ARD NLFLETCHER JR. RENE D. TEGTMEYER I EDW Acting Commissloner of Patents Attesting Officet
Claims (23)
- 2. A photothermographic element as in claim 1 comprising a support having thereon a. photosensitive silver halide, b. an oxidation-reduction image forming combination comprising i. silver behenate with ii. 2,2''-dihydroxy-1,1''-binaphthyl, and c. 2,4-dihydroxybenzaldehyde, 2,4-dihydroxybenzophenone, or 2'', 4''-dihydroxyacetophenone.
- 3. A photothermographic element as in claim 1 also comprising an activator-toning agent.
- 4. A photothermographic element as in claim 1 also comprising phthalimide or phthalazinone.
- 5. A photothermographic element as in claim 1 also comprising a stabilizer precursor.
- 6. A photothermographic element as in claim 1 also comprising 5-acetyl-2-benzyloxycarbonylthio-4-methylthiazole.
- 7. A photothermographic element as in claim 1 also comprising a sensitizing dye.
- 8. A photothermographic element as in claim 1 also comprising 3-carboxymethyl-5-((3-methyl-2(3H)-thiazolinylidene)isopropylidene) rhodanine.
- 9. A photothermographic element as in claim 1 comprising 0.01 to 0.50 moles of said photosensitive silver halide per mole of said heavy metal salt oxidizing agent; 0.4 to 2.0 moles of said bis-beta-naphthol reducing agent per mole of said heavy metal salt oxidizing agent; and wherein the ratio of said bis-beta-naphthol reducing agent to said 1,3-dihydroxybenzene compound is from 10:1 to 1:5.
- 10. A photothermographic element comprising a support having thereon a. photosensitive silver halide, b. silver behenate, c. 2,2''-dihydroxy-1,1''-binaphthyl, d. 2,4-dihydroxybenzaldehyde, 2,4-dihydroxybenzophenone or 2,4-dihydroxyacetophenone, e. phthalimide, f. 5-acetyl-2-benzyloxycarbonylthio-4-methyl-thiazole, and g. 3-carboxymethyl-5-((3-methyl-2(3H) -thiazolinylidene)isopropylidene)rhodanine.
- 11. A photothermographic composition comprising a. photosensitive silver halide, with b. an oxidation-reduction image forming combination comprising i. a heavy metal salt oxidizing agent with ii. a bis-beta-naphthol reducing agent, and c. a 1,3-dihydroxybenzene compound of the formula:
- 12. A photothermographic composition as in claim 11 comprising a. photosensitive silver halide b. an oxidation-reduction image forming combination comprising i. silver behenate with ii. 2,2''-dihydroxy-1,1''-binaphthyl, and c. 2,4-dihydroxybenzaldehyde, 2,4-dihydroxybenzophenone, or 2'', 4''-dihydroxyacetophenone.
- 13. A photothermographic composition as in claim 11 also comprising an activator-toning agent.
- 14. A photothermographic element as in claim 11 also comprising phthalimide or phthalazinone.
- 15. A photothermographic composition as in claim 11 also comprising a stabilizer precursor.
- 16. A photothermographic composition as in claim 11 also comprising 5-acetyl-2-benzyloxycarbonylthio-4-methylthiazole.
- 17. A photothermographic composition as in claim 11 also comprising a sensitizing dye.
- 18. A photothermographic composition as in claim 11 also comprising 3-carboxymethyl-5-((3-methyl-2(3H)-thiazolinylidene)isopropyl -idene)rhodanine.
- 19. A photothermographic composition as in claim 11 comprising 0.01 to 0.50 moles of said photosensitive silver halide per mole of said heavy salt oxidizing agent; 0.4 to 2.0 moles of said bis-beta-naphthol reducing agent per mole of said heavy metal salt oxidizing agent; and wherein the ratio of said bis-beta-naphthol reducing agent to said 1,3-dihydroxybenzene compound is from 10:1 to 1:5.
- 20. A photothermographic composition comprisng a. photosensitive silver halide, b. silver behenate, c. 2,2''-dihydroxy-1,1''-binaphthyl, d. 2,4-dihydroxybenzyaldehyde, 2,4-dihydroxybenzophenone, or 2, 4-dihydroxyacetophenone, e. phthalimide, f. 5-acetyl-2-benzyloxycarbonylthio-4-methyl-thiazole, and g. 3-carboxymethyl-5-((3-methyl-2(3H) -thiazolinylidene)isopropylidene)rhodanine.
- 21. A process of developing a latent image in an exposed photothermographic element comprising a support having thereon a. photosensitive silver halide, b. an oxidation-reduction image forming combination comprising i. a heavy metal salt oxidizing agent with ii. a bis-beta-naphthol reducing agent, and c. a 1,3-dihydroxybenzene compound represented by the formula:
- 22. The process of claim 28 wherein said element is heated to aboUt 80*C. to about 250*C. for about 0.5 to about 60 seconds.
- 23. A process of developing and stabilizing a latent image in an exposed photothermographic element comprising a support having thereon a. photosensitive silver halide, b. silver behenate, c. 2,2''-dihydroxy-1,1''-binaphthyl, d. 2,4-dihydroxybenzaldehyde, 2,4-dihydroxybenzo-phenone or 2,4-dihydroxyacetophenone, e. phthalimide, f. 5-acetyl-2-benzyloxycarbonylthio-4-methylthiazole, and g. 3-carboxymethyl-5-((3-methyl-2(3H) -thiazolinylidene)isopropylidene)rhodanine, comprising heating said element to about 80*C. to about 250*C.
- 24. The process of claim 30 wherein said element is heated at about 120*C. to about 180*C. for about 0.5 to about 5 seconds.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US12446471A | 1971-03-15 | 1971-03-15 |
Publications (1)
Publication Number | Publication Date |
---|---|
US3751249A true US3751249A (en) | 1973-08-07 |
Family
ID=22415053
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US00124464A Expired - Lifetime US3751249A (en) | 1971-03-15 | 1971-03-15 | Photothermic silver halide element containing a bis-beta-naphthol reducing agent and a 1, 3-dihydroxy-benzene reducing agent |
Country Status (5)
Country | Link |
---|---|
US (1) | US3751249A (en) |
JP (1) | JPS532323B1 (en) |
BE (1) | BE780624A (en) |
FR (1) | FR2130147B1 (en) |
GB (1) | GB1381007A (en) |
Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3839041A (en) * | 1970-06-03 | 1974-10-01 | Eastman Kodak Co | Stabilizer precursors in photothermographic elements and compositions |
US3852093A (en) * | 1972-12-13 | 1974-12-03 | Minnesota Mining & Mfg | Heat-sensitive copy-sheet |
US3936309A (en) * | 1972-08-05 | 1976-02-03 | Mitsubishi Paper Mills, Ltd. | Heat-sensitive recording composition and sheet |
US4021240A (en) * | 1975-12-22 | 1977-05-03 | Eastman Kodak Company | Photothermographic and thermographic compositions and uses therefor containing sulfonamidophenol reducing agents and four equivalent color couplers |
US4065312A (en) * | 1974-04-19 | 1977-12-27 | Agfa-Gevaert, A.G. | Process for the production of photographic vesicular images in photographic silver halide material |
US4260674A (en) * | 1974-04-19 | 1981-04-07 | Agfa-Gevaert Aktiengesellschaft | Silver salt photographic material for the production of silver and bubble photographic images with 80% transparency |
US5582953A (en) * | 1994-07-07 | 1996-12-10 | Agfa-Gevaert N.V. | Direct thermal recording process |
US5663032A (en) * | 1988-01-29 | 1997-09-02 | Canon Kabushiki Kaisha | Photosensitive composition containing photosensitive and heat developable element and polymer element and image-forming method utilizing the same |
US6280922B1 (en) | 1998-12-30 | 2001-08-28 | Eastman Kodak Company | High chloride silver halide elements containing activated precursors to thiolic stabilizers |
US20020048732A1 (en) * | 2000-03-17 | 2002-04-25 | Toyohisa Oya | Photothermographic material and method for forming images |
EP1245404A1 (en) * | 2001-03-29 | 2002-10-02 | Agfa-Gevaert | Thermographic recording material providing prints with good image density and tone having improved archivability |
US20030054958A1 (en) * | 2001-03-29 | 2003-03-20 | Agfa-Gevaert | Thermographic recording material with improved print archivability without loss in printability |
US20050123867A1 (en) * | 2003-12-04 | 2005-06-09 | Eastman Kodak Company | Silver halide elements containing activated precursors to thiocyanato stabilizers |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1178800A (en) * | 1966-03-01 | 1970-01-21 | Minnesota Mining & Mfg | Improvements in or relating to Copying Materials |
US3667958A (en) * | 1970-04-09 | 1972-06-06 | Eastman Kodak Co | Photosensitive and thermosensitive elements,compositions and processes |
-
1971
- 1971-03-15 US US00124464A patent/US3751249A/en not_active Expired - Lifetime
-
1972
- 1972-03-10 FR FR7208343A patent/FR2130147B1/fr not_active Expired
- 1972-03-13 BE BE780624A patent/BE780624A/en unknown
- 1972-03-15 JP JP2582272A patent/JPS532323B1/ja active Pending
- 1972-03-15 GB GB1216372A patent/GB1381007A/en not_active Expired
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1178800A (en) * | 1966-03-01 | 1970-01-21 | Minnesota Mining & Mfg | Improvements in or relating to Copying Materials |
US3667958A (en) * | 1970-04-09 | 1972-06-06 | Eastman Kodak Co | Photosensitive and thermosensitive elements,compositions and processes |
Cited By (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3839041A (en) * | 1970-06-03 | 1974-10-01 | Eastman Kodak Co | Stabilizer precursors in photothermographic elements and compositions |
US3936309A (en) * | 1972-08-05 | 1976-02-03 | Mitsubishi Paper Mills, Ltd. | Heat-sensitive recording composition and sheet |
US3852093A (en) * | 1972-12-13 | 1974-12-03 | Minnesota Mining & Mfg | Heat-sensitive copy-sheet |
US4065312A (en) * | 1974-04-19 | 1977-12-27 | Agfa-Gevaert, A.G. | Process for the production of photographic vesicular images in photographic silver halide material |
US4260674A (en) * | 1974-04-19 | 1981-04-07 | Agfa-Gevaert Aktiengesellschaft | Silver salt photographic material for the production of silver and bubble photographic images with 80% transparency |
US4021240A (en) * | 1975-12-22 | 1977-05-03 | Eastman Kodak Company | Photothermographic and thermographic compositions and uses therefor containing sulfonamidophenol reducing agents and four equivalent color couplers |
US5663032A (en) * | 1988-01-29 | 1997-09-02 | Canon Kabushiki Kaisha | Photosensitive composition containing photosensitive and heat developable element and polymer element and image-forming method utilizing the same |
US5582953A (en) * | 1994-07-07 | 1996-12-10 | Agfa-Gevaert N.V. | Direct thermal recording process |
US6280922B1 (en) | 1998-12-30 | 2001-08-28 | Eastman Kodak Company | High chloride silver halide elements containing activated precursors to thiolic stabilizers |
US20020048732A1 (en) * | 2000-03-17 | 2002-04-25 | Toyohisa Oya | Photothermographic material and method for forming images |
US7229753B2 (en) * | 2000-03-17 | 2007-06-12 | Fujifilm Corporation | Photothermographic material and method for forming images |
EP1245404A1 (en) * | 2001-03-29 | 2002-10-02 | Agfa-Gevaert | Thermographic recording material providing prints with good image density and tone having improved archivability |
US20030054958A1 (en) * | 2001-03-29 | 2003-03-20 | Agfa-Gevaert | Thermographic recording material with improved print archivability without loss in printability |
US6759367B2 (en) | 2001-03-29 | 2004-07-06 | Agfa-Gevaert | Thermographic recording material with improved print archivability without loss in printability |
US20050123867A1 (en) * | 2003-12-04 | 2005-06-09 | Eastman Kodak Company | Silver halide elements containing activated precursors to thiocyanato stabilizers |
Also Published As
Publication number | Publication date |
---|---|
DE2212302A1 (en) | 1972-09-28 |
BE780624A (en) | 1972-07-03 |
FR2130147A1 (en) | 1972-11-03 |
DE2212302B2 (en) | 1976-10-07 |
FR2130147B1 (en) | 1974-08-02 |
GB1381007A (en) | 1975-01-22 |
JPS532323B1 (en) | 1978-01-27 |
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