JPH0121490B2 - - Google Patents
Info
- Publication number
- JPH0121490B2 JPH0121490B2 JP55052011A JP5201180A JPH0121490B2 JP H0121490 B2 JPH0121490 B2 JP H0121490B2 JP 55052011 A JP55052011 A JP 55052011A JP 5201180 A JP5201180 A JP 5201180A JP H0121490 B2 JPH0121490 B2 JP H0121490B2
- Authority
- JP
- Japan
- Prior art keywords
- heat
- group
- developable photosensitive
- silver
- photosensitive material
- 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
Links
- -1 silver halide Chemical class 0.000 claims description 59
- 239000000463 material Substances 0.000 claims description 50
- 229910052709 silver Inorganic materials 0.000 claims description 42
- 239000004332 silver Substances 0.000 claims description 42
- 150000001875 compounds Chemical class 0.000 claims description 27
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims description 23
- 239000011230 binding agent Substances 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- 239000002356 single layer Substances 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 125000000623 heterocyclic group Chemical group 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 230000033116 oxidation-reduction process Effects 0.000 claims description 2
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 30
- 238000000034 method Methods 0.000 description 26
- 230000035945 sensitivity Effects 0.000 description 25
- 238000011161 development Methods 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000006185 dispersion Substances 0.000 description 12
- 239000002904 solvent Substances 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 11
- 238000003756 stirring Methods 0.000 description 10
- 239000010410 layer Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 6
- 206010034972 Photosensitivity reaction Diseases 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000000975 dye Substances 0.000 description 6
- 229940100892 mercury compound Drugs 0.000 description 6
- 150000002731 mercury compounds Chemical class 0.000 description 6
- 230000036211 photosensitivity Effects 0.000 description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 6
- 229910052721 tungsten Inorganic materials 0.000 description 6
- 239000010937 tungsten Substances 0.000 description 6
- 206010070834 Sensitisation Diseases 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 5
- 230000008313 sensitization Effects 0.000 description 5
- AQRYNYUOKMNDDV-UHFFFAOYSA-M silver behenate Chemical compound [Ag+].CCCCCCCCCCCCCCCCCCCCCC([O-])=O AQRYNYUOKMNDDV-UHFFFAOYSA-M 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 230000005070 ripening Effects 0.000 description 4
- 239000008096 xylene Substances 0.000 description 4
- 235000021357 Behenic acid Nutrition 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 229940116226 behenic acid Drugs 0.000 description 3
- 229920002301 cellulose acetate Polymers 0.000 description 3
- 239000004815 dispersion polymer Substances 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- IJAPPYDYQCXOEF-UHFFFAOYSA-N phthalazin-1(2H)-one Chemical class C1=CC=C2C(=O)NN=CC2=C1 IJAPPYDYQCXOEF-UHFFFAOYSA-N 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 230000001235 sensitizing effect Effects 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 239000001856 Ethyl cellulose Substances 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- WRYNUJYAXVDTCB-UHFFFAOYSA-M acetyloxymercury Chemical class CC(=O)O[Hg] WRYNUJYAXVDTCB-UHFFFAOYSA-M 0.000 description 2
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 2
- 229920006217 cellulose acetate butyrate Polymers 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 238000000586 desensitisation Methods 0.000 description 2
- 229920001249 ethyl cellulose Polymers 0.000 description 2
- 235000019325 ethyl cellulose Nutrition 0.000 description 2
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 2
- 238000011066 ex-situ storage Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- 150000002730 mercury Chemical class 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 150000003378 silver Chemical class 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 2
- JWZZKOKVBUJMES-UHFFFAOYSA-N (+-)-Isoprenaline Chemical compound CC(C)NCC(O)C1=CC=C(O)C(O)=C1 JWZZKOKVBUJMES-UHFFFAOYSA-N 0.000 description 1
- QGKMIGUHVLGJBR-UHFFFAOYSA-M (4z)-1-(3-methylbutyl)-4-[[1-(3-methylbutyl)quinolin-1-ium-4-yl]methylidene]quinoline;iodide Chemical compound [I-].C12=CC=CC=C2N(CCC(C)C)C=CC1=CC1=CC=[N+](CCC(C)C)C2=CC=CC=C12 QGKMIGUHVLGJBR-UHFFFAOYSA-M 0.000 description 1
- PSBDWGZCVUAZQS-UHFFFAOYSA-N (dimethylsulfonio)acetate Chemical group C[S+](C)CC([O-])=O PSBDWGZCVUAZQS-UHFFFAOYSA-N 0.000 description 1
- OYWRDHBGMCXGFY-UHFFFAOYSA-N 1,2,3-triazinane Chemical group C1CNNNC1 OYWRDHBGMCXGFY-UHFFFAOYSA-N 0.000 description 1
- CSNIZNHTOVFARY-UHFFFAOYSA-N 1,2-benzothiazole Chemical group C1=CC=C2C=NSC2=C1 CSNIZNHTOVFARY-UHFFFAOYSA-N 0.000 description 1
- LQISTWAILIWIGP-UHFFFAOYSA-N 1,3,5-tris(chloromethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound ClCN1C(=O)N(CCl)C(=O)N(CCl)C1=O LQISTWAILIWIGP-UHFFFAOYSA-N 0.000 description 1
- WOXALUHCQWQCGY-UHFFFAOYSA-N 1-(bromomethyl)pyrrole-2,5-dione Chemical compound BrCN1C(=O)C=CC1=O WOXALUHCQWQCGY-UHFFFAOYSA-N 0.000 description 1
- KRODOTCDHSCOKN-UHFFFAOYSA-N 1-(bromomethyl)pyrrolidine-2,5-dione Chemical compound BrCN1C(=O)CCC1=O KRODOTCDHSCOKN-UHFFFAOYSA-N 0.000 description 1
- SMQIAQVRHOQLKW-UHFFFAOYSA-N 1-(chloromethyl)pyrrole-2,5-dione Chemical compound ClCN1C(=O)C=CC1=O SMQIAQVRHOQLKW-UHFFFAOYSA-N 0.000 description 1
- KEBMRNXDMRFGNV-UHFFFAOYSA-N 1-(chloromethyl)pyrrolidin-2-one Chemical compound ClCN1CCCC1=O KEBMRNXDMRFGNV-UHFFFAOYSA-N 0.000 description 1
- RUXXMOCJNFCADG-UHFFFAOYSA-N 1-(chloromethyl)pyrrolidine-2,5-dione Chemical compound ClCN1C(=O)CCC1=O RUXXMOCJNFCADG-UHFFFAOYSA-N 0.000 description 1
- MWPPTQBTKSTZCM-UHFFFAOYSA-N 1-(iodomethyl)pyrrolidine-2,5-dione Chemical compound ICN1C(=O)CCC1=O MWPPTQBTKSTZCM-UHFFFAOYSA-N 0.000 description 1
- ZEMODTUZIWTRPF-UHFFFAOYSA-N 1-n,4-n-diethylbenzene-1,4-diamine Chemical compound CCNC1=CC=C(NCC)C=C1 ZEMODTUZIWTRPF-UHFFFAOYSA-N 0.000 description 1
- PSMRKYCXNVSCHU-UHFFFAOYSA-N 2-(1-chloroethyl)isoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(C(Cl)C)C(=O)C2=C1 PSMRKYCXNVSCHU-UHFFFAOYSA-N 0.000 description 1
- RFAHYFCQZDZXLP-UHFFFAOYSA-N 2-(chloromethyl)-1,1-dioxo-1,2-benzothiazol-3-one Chemical compound C1=CC=C2S(=O)(=O)N(CCl)C(=O)C2=C1 RFAHYFCQZDZXLP-UHFFFAOYSA-N 0.000 description 1
- JKGLRGGCGUQNEX-UHFFFAOYSA-N 2-(chloromethyl)isoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(CCl)C(=O)C2=C1 JKGLRGGCGUQNEX-UHFFFAOYSA-N 0.000 description 1
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 1
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 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
- UGWULZWUXSCWPX-UHFFFAOYSA-N 2-sulfanylideneimidazolidin-4-one Chemical compound O=C1CNC(=S)N1 UGWULZWUXSCWPX-UHFFFAOYSA-N 0.000 description 1
- HXIQYSLFEXIOAV-UHFFFAOYSA-N 2-tert-butyl-4-(5-tert-butyl-4-hydroxy-2-methylphenyl)sulfanyl-5-methylphenol Chemical compound CC1=CC(O)=C(C(C)(C)C)C=C1SC1=CC(C(C)(C)C)=C(O)C=C1C HXIQYSLFEXIOAV-UHFFFAOYSA-N 0.000 description 1
- PFANXOISJYKQRP-UHFFFAOYSA-N 2-tert-butyl-4-[1-(5-tert-butyl-4-hydroxy-2-methylphenyl)butyl]-5-methylphenol Chemical compound C=1C(C(C)(C)C)=C(O)C=C(C)C=1C(CCC)C1=CC(C(C)(C)C)=C(O)C=C1C PFANXOISJYKQRP-UHFFFAOYSA-N 0.000 description 1
- BCHZICNRHXRCHY-UHFFFAOYSA-N 2h-oxazine Chemical group N1OC=CC=C1 BCHZICNRHXRCHY-UHFFFAOYSA-N 0.000 description 1
- AGIJRRREJXSQJR-UHFFFAOYSA-N 2h-thiazine Chemical group N1SC=CC=C1 AGIJRRREJXSQJR-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- KDCGOANMDULRCW-UHFFFAOYSA-N 7H-purine Chemical group N1=CNC2=NC=NC2=C1 KDCGOANMDULRCW-UHFFFAOYSA-N 0.000 description 1
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Natural products OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 1
- RAONXFAMPQBAOI-UHFFFAOYSA-N CCC(=O)NC(C)Br Chemical compound CCC(=O)NC(C)Br RAONXFAMPQBAOI-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- JRNVZBWKYDBUCA-UHFFFAOYSA-N N-chlorosuccinimide Chemical compound ClN1C(=O)CCC1=O JRNVZBWKYDBUCA-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical group C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 229910021612 Silver iodide Inorganic materials 0.000 description 1
- SJOOOZPMQAWAOP-UHFFFAOYSA-N [Ag].BrCl Chemical compound [Ag].BrCl SJOOOZPMQAWAOP-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 1
- 229910001864 baryta Inorganic materials 0.000 description 1
- VQIZMFAABLAEJE-UHFFFAOYSA-N benzenesulfonamide;phenol Chemical compound OC1=CC=CC=C1.NS(=O)(=O)C1=CC=CC=C1 VQIZMFAABLAEJE-UHFFFAOYSA-N 0.000 description 1
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 description 1
- 150000001558 benzoic acid derivatives Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- SXDBWCPKPHAZSM-UHFFFAOYSA-M bromate Chemical class [O-]Br(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-M 0.000 description 1
- MBCFIGQQFXLXCB-UHFFFAOYSA-L butanedioate;mercury(2+) Chemical class [Hg+2].[O-]C(=O)CCC([O-])=O MBCFIGQQFXLXCB-UHFFFAOYSA-L 0.000 description 1
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229950005499 carbon tetrachloride Drugs 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- AJPXTSMULZANCB-UHFFFAOYSA-N chlorohydroquinone Chemical compound OC1=CC=C(O)C(Cl)=C1 AJPXTSMULZANCB-UHFFFAOYSA-N 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical class [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 150000001860 citric acid derivatives Chemical class 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000006081 fluorescent whitening agent Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229940093915 gynecological organic acid Drugs 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 230000002140 halogenating effect Effects 0.000 description 1
- WJRBRSLFGCUECM-UHFFFAOYSA-N hydantoin Chemical group O=C1CNC(=O)N1 WJRBRSLFGCUECM-UHFFFAOYSA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 125000004464 hydroxyphenyl group Chemical group 0.000 description 1
- 125000002632 imidazolidinyl group Chemical group 0.000 description 1
- 125000002636 imidazolinyl group Chemical group 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 125000003387 indolinyl group Chemical group N1(CCC2=CC=CC=C12)* 0.000 description 1
- 125000001041 indolyl group Chemical group 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 125000000904 isoindolyl group Chemical group C=1(NC=C2C=CC=CC12)* 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- TYQCGQRIZGCHNB-JLAZNSOCSA-N l-ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(O)=C(O)C1=O TYQCGQRIZGCHNB-JLAZNSOCSA-N 0.000 description 1
- 150000004668 long chain fatty acids Chemical class 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- NGYIMTKLQULBOO-UHFFFAOYSA-L mercury dibromide Chemical compound Br[Hg]Br NGYIMTKLQULBOO-UHFFFAOYSA-L 0.000 description 1
- DZVCFNFOPIZQKX-LTHRDKTGSA-M merocyanine Chemical compound [Na+].O=C1N(CCCC)C(=O)N(CCCC)C(=O)C1=C\C=C\C=C/1N(CCCS([O-])(=O)=O)C2=CC=CC=C2O\1 DZVCFNFOPIZQKX-LTHRDKTGSA-M 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- WIJVRJHQMZYHJI-UHFFFAOYSA-N n-(chloromethyl)-n-phenylacetamide Chemical compound CC(=O)N(CCl)C1=CC=CC=C1 WIJVRJHQMZYHJI-UHFFFAOYSA-N 0.000 description 1
- CIUJQWLLGXKZQD-UHFFFAOYSA-N n-(chloromethyl)benzamide Chemical compound ClCNC(=O)C1=CC=CC=C1 CIUJQWLLGXKZQD-UHFFFAOYSA-N 0.000 description 1
- XEUZNYLPUWEEQE-UHFFFAOYSA-N n-(chloromethyl)benzenesulfonamide Chemical compound ClCNS(=O)(=O)C1=CC=CC=C1 XEUZNYLPUWEEQE-UHFFFAOYSA-N 0.000 description 1
- KZZUBAQVMPHDHM-UHFFFAOYSA-N n-(chloromethyl)propanamide Chemical compound CCC(=O)NCCl KZZUBAQVMPHDHM-UHFFFAOYSA-N 0.000 description 1
- HSPSCWZIJWKZKD-UHFFFAOYSA-N n-chloroacetamide Chemical compound CC(=O)NCl HSPSCWZIJWKZKD-UHFFFAOYSA-N 0.000 description 1
- UPSNOKIUEULXHF-UHFFFAOYSA-N n-chloropropanamide Chemical compound CCC(=O)NCl UPSNOKIUEULXHF-UHFFFAOYSA-N 0.000 description 1
- 125000006501 nitrophenyl group Chemical group 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N o-dicarboxybenzene Natural products OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- CMCWWLVWPDLCRM-UHFFFAOYSA-N phenidone Chemical compound N1C(=O)CCN1C1=CC=CC=C1 CMCWWLVWPDLCRM-UHFFFAOYSA-N 0.000 description 1
- 125000001644 phenoxazinyl group Chemical group C1(=CC=CC=2OC3=CC=CC=C3NC12)* 0.000 description 1
- YSZIOXAEADAJLX-UHFFFAOYSA-N phthalazine-1,4-dione Chemical class C1=CC=C2C(=O)N=NC(=O)C2=C1 YSZIOXAEADAJLX-UHFFFAOYSA-N 0.000 description 1
- XKJCHHZQLQNZHY-UHFFFAOYSA-N phthalimide Chemical compound C1=CC=C2C(=O)NC(=O)C2=C1 XKJCHHZQLQNZHY-UHFFFAOYSA-N 0.000 description 1
- 125000004193 piperazinyl group Chemical group 0.000 description 1
- 125000003386 piperidinyl group Chemical group 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920003225 polyurethane elastomer Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002689 polyvinyl acetate 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
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000002755 pyrazolinyl group Chemical group 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 125000001422 pyrrolinyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- KIWUVOGUEXMXSV-UHFFFAOYSA-N rhodanine Chemical compound O=C1CSC(=S)N1 KIWUVOGUEXMXSV-UHFFFAOYSA-N 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000004904 shortening Methods 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
- 229940045105 silver iodide Drugs 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
- MNMYRUHURLPFQW-UHFFFAOYSA-M silver;dodecanoate Chemical compound [Ag+].CCCCCCCCCCCC([O-])=O MNMYRUHURLPFQW-UHFFFAOYSA-M 0.000 description 1
- LTYHQUJGIQUHMS-UHFFFAOYSA-M silver;hexadecanoate Chemical compound [Ag+].CCCCCCCCCCCCCCCC([O-])=O LTYHQUJGIQUHMS-UHFFFAOYSA-M 0.000 description 1
- ORYURPRSXLUCSS-UHFFFAOYSA-M silver;octadecanoate Chemical compound [Ag+].CCCCCCCCCCCCCCCCCC([O-])=O ORYURPRSXLUCSS-UHFFFAOYSA-M 0.000 description 1
- OHGHHPYRRURLHR-UHFFFAOYSA-M silver;tetradecanoate Chemical compound [Ag+].CCCCCCCCCCCCCC([O-])=O OHGHHPYRRURLHR-UHFFFAOYSA-M 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 1
- 150000003536 tetrazoles Chemical group 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 150000003852 triazoles Chemical group 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/494—Silver salt compositions other than silver halide emulsions; Photothermographic systems ; Thermographic systems using noble metal compounds
- G03C1/498—Photothermographic systems, e.g. dry silver
- G03C1/49836—Additives
- G03C1/49845—Active additives, e.g. toners, stabilisers, sensitisers
Description
本発明は、熱現像性感光材料に関し、更に詳し
くは加熱前処理を施こすことにより感光性が付与
される加熱前処理型熱現像性感光材料に関するも
のである。
従来、広範に使用されているハロゲン化銀写真
法は、ジアゾ写真、電子写真などの所謂非銀塩感
光材料を用いた写真法と比較して、感光性、階調
性などの写真特性に於いて極めて優れた写真法で
ある。しかしながら、この方法に用いられるハロ
ゲン化銀写真感光材料は安定画像を得るために現
像、停止、定着、水洗などの湿式処理工程を安全
光下あるいは暗室中でなさなければならないの
で、処理に時間と手間がかかり、また薬品の取扱
いによる人体に対する危険があつたり、処理室内
や作業者の手や衣服を汚染するといつた問題があ
つた。従つて、ハロゲン化銀を用いながら乾式処
理によつて安定画像を得ることができる写真法は
非常に望まれているもので、従つてこれまでにも
多くの研究がなされている。
例えば、特公昭43−4921号または特公昭43−
4924号公報などに記載されている有機銀塩、還元
剤および有機銀イオンに対し触媒的に接触してい
るハロゲン化銀の３成分の組合せから成る熱現像
性感光材料は最も成功した例である。
また、前記の例とは別に、特公昭53−2687号、
特開昭48−51626号または特開昭49−10039号公報
などに記載されている様な加熱前処理型熱現像性
感光材料が提案されている。この熱現像性感光材
料は、加熱前処理を施こすことにより感光性が付
与され、その後の像露光および熱現像によつて銀
画像が形成されるので、明室での取扱いが可能で
あり、しかも追加記録が行なえるなどの特長をも
つている。
本発明は、前記例のうち後者の加熱前処理型熱
現像性感光材料に関するものである。これまでの
この種の熱現像性感光材料は、感光性ハロゲン化
銀が加熱前処理の際に生成しうる様に感光層を設
計しておく必要があり、そのために製造条件を限
定したり、あるいは特定のハロゲン化剤を用いた
り、さらには溶剤雰囲気に曝露したりする手段が
採用されている。しかし、これらの方法によつて
製造されたこの種の熱現像性感光材料は、生保存
性、感度、階調性または地色濃度などの写真特性
上、未だ十分に満足できるものとは言えないもの
である。これまでにも、これらの欠点を改良する
ために数多くの発明がなされている。例えば、特
開昭52−73022号や特開昭53−25420号公報などに
記載されている族、族、族元素を含有する
有機ハライドやハロゲン分子錯体の使用が試みら
れている。しかしながら、これらの方法は生保存
性や地色のカブリ濃度を改善するものの、感度や
階調性の点での改善がなされていない。
その要因としては、第１に感光性ハロゲン化銀
が加熱前処理の際に生成することから、物理熟
成、化学熟成などの増感手段の適用や計算された
た調子コントロールをすることが難しいこと、第
２に熱現像性感光材料の保存中や加熱前処理の際
に生じる遊離ハロゲンが増感色素を破壊するため
に分光増感がなされないことである。
本発明は、下述する特定の化合物を用いること
により加熱前処理型熱現像性感光材料（以下単に
「熱現像性感光材料」という）を調整でき、しか
もこの種の熱現像性感光材料が固有する前記の如
き欠点を有効に解消しうるものである。
従つて、本発明の第１の目的は、高感度で高ガ
ンマな画像を与える熱現像性感光材料を提供する
ことにある。
本発明の第２の目的は、生保存性に優れた熱現
像性感光材料を提供することにある。
本発明の第３の目的は、熱現像時の熱カブリの
少ない熱現像性感光材料を提供することにある。
本発明の第４の目的は、画像形成後の光変色の
少ない熱現像性感光材料を提供することにある。
本発明にかかる目的は、支持体上に少なくとも
(a)被還元性有機銀塩および還元剤から成る酸化一
還元画像形成成分、(b)感光性ハロゲン化銀および
(c)バインダーから成る熱現像性感光要素を単層若
しくは多層に形成した加熱前処理型熱現像性感光
材料において、前記熱現像性感光要素が(d)下記一
般式〔〕若しくは〔〕で示される化合物の少
なくとも１種を含有する加熱前処理型熱現像性感
光材料によつて達成される。
一般式〔〕
式中、X1およびX2は、それぞれハロゲン原子
（例えば、塩素原子、臭素原子、沃素原子）表わ
す。R1、R2、R3、R4、R5およびR6は、それぞれ
水素原子、置換若しくは非置換アルキル基（例え
ば、メチル基、エチル基、プロピル基、ブチル
基、ｔ−ブチル基、ペンチル基、ヘキシル基、２
−エチルヘキシル基、ｎ−オクチル基、２−ヒド
ロキシエチル基、３−ヒドロキシプロピル基など
で、特にR1、R2、R4、R5およびR6は炭素原子数
１〜４個のアルキル基が好ましく、R3は炭素原
子数１〜８個のアルキル基が好ましい）または置
換若しくは非置換のアリール基（例えば、フエニ
ル基、トリル基、ナフチル基、ニトロフエニル
基、ヒドロキシフエニル基など）を表わし、互い
に同一であつてもよく或いは異なつていてもよ
い。Ｚは、５員または６員の複素環（例えば、ピ
ロール環、ピロリン環、ピロリジン環、イミダゾ
ール環、イミダゾリン環、イミダゾリジン環、ピ
ラゾール環、ピラゾリン環、ビラゾリジン環、ト
リアゾール環、テトラゾール環、ピペリジン環、
オキサジン環、チアジン環、ピペラジン環、ヒダ
ントイン環、シアヌル環、チオヒタントイン環、
ヘキサヒドロトリアジン環、インドール環、イン
ドリン環、イソインドール環、ベンゾイミダゾー
ル環、ベンゾイソチアゾール環、カルバゾール
環、フエノキサジン環、プリン環）を完成するに
必要な非金属原子群を表わす。また、この環には
アルキル基、アリール基、アルコキシ基、ハロゲ
ン原子、酸素（＝Ｏ）、硫黄（＝Ｓ）などの置換
基を有していても差支えない。上記アルキル基
は、例えばメチル基、エチル基、プロピル基、
iso−プロピル基、ブチル基、ｔ−ブチル基、iso
−ブチル基、ペンチル基、ヘキシル基、２−エチ
ルヘキシル基、オクチル基、ノニル基、デシル
基、ドデシル基などの炭素原子数１〜12個のアル
キル基が好ましい。アリール基としては置換基
（例えば、メチル基、エチル基、プロピル基、iso
−プロピル基、ブチル基、ｔ−ブチル基、塩素原
子、臭素原子など）を有するフエニル基、ナフチ
ル基などが好ましい。アルコキシ基としては、例
えば、メトキシ基、エトキシ基、プロポキシ基、
iso−プロポキシ基、ブトキシ基、ｔ−ブトキシ
基、オクトキシ基、ドデシルオキシ基などの炭素
原子数１〜12個のアルコキシ基が好ましい。A1
およびA2は、それぞれカルボニル基またはスル
ホニル基を表わす。
前記一般式〔〕若しくは〔〕で示される化
合物の代表例を下記に列挙する。
〔〕−(1)：Ｎ−クロルメチルサクシンイミド
〔〕−(2)：Ｎ−ブロムメチルサクシンイミド
〔〕−(3)：Ｎ−ヨードメチルサクシンイミド
〔〕−(4)：Ｎ−クロルメチルマレインイミド
〔〕−(5)：Ｎ−ブロムメチルマレインイミド
〔〕−(6)：Ｎ−クロルメチルフタルイミド
〔〕−(7)：Ｎ−（１−ブロムエチル）マレインイ
ミド
〔〕−(8)：Ｎ−（１−クロルエチル）フタルイミ
ド
〔〕−(9)：Ｎ−（フエニルブロムメチル）マレイ
ンイミド
〔〕−(10)：Ｎ−（フエニルクロムメチル）フタル
イミド
〔〕−(11)：Ｎ−クロルメチル−１，８−ナフタル
イミド
〔〕−(12)：Ｎ−（１−クロル−１−メチルエチル）
マレインイミド
〔〕−(13)：Ｎ−（１−ブロム−１−メチルエチ
ル）マレインイミド
〔〕−(14)：Ｎ−（１−クロル−１−メチルエチ
ル）フタルイミド
〔〕−(15)：Ｎ−（１−クロル−１−メチルエチ
ル）−１，８−ナフタルイミド
〔〕−(16)：Ｎ−（１−クロルエチル）−１，８−
ナフタルイミド
〔〕−(17)：Ｎ−クロルメチル−２−ピロリドン
〔〕−(18)：Ｎ−クロルメチル−α−ピペリドン
〔〕−(19)：Ｎ−クロルメチル−２−オキサゾリ
ノン
〔〕−(20)：Ｎ−ブロムメチルフタラジノン
〔〕−(21)：Ｎ，N′−ジ（クロルメチル）−５，
５−ジメチルバルビツール酸
〔〕−(22)：Ｎ，N′−ジ（ブロムメチル）−５，
５−ジメチルバルビツール酸
〔〕−(23)：Ｎ，N′−ジ（クロルメチル）−４，
４−ジメチルヒダントイン
〔〕−(24)：Ｎ，N′，N″−トリ（クロルメチル）
シアヌル酸
〔〕−(25)：Ｎ−クロルメチル−２，３−ヒドロ
−１，２−ベンゾイソスルホナゾール
〔〕−(26)：Ｎ−クロルメチルサツカリン
〔〕−(1)：Ｎ−クロルメチルアセトアミド
〔〕−(2)：Ｎ−（１−ブロムエチル）アセトアミ
ド
〔〕−(3)：Ｎ−クロルメチルプロピオアミド
〔〕−(4)：Ｎ−（１−ブロムエチル）プロピオア
ミド
〔〕−(5)：Ｎ−クロルメチルアセトアニリド
〔〕−(6)：Ｎ−クロルメチルベンツアミド
〔〕−(7)：Ｎ−クロルメチル−α−ナフトアミド
〔〕−(8)：Ｎ−ブロムメチル−β−ナフトアミド
〔〕−(9)：Ｎ−クロルメチルメタンスルホンアミ
ド
〔〕−(10)：Ｎ−クロルメチルベンゼンスルホンア
ミド
〔〕−(11)：Ｎ−ブロムメチルエタンスルホンアミ
ド
これらの化合物の添加時期は、熱現像性感光材
料の製造工程中の何れの時期でよいが、一般に前
記成分(b)の感光性ハロゲン化銀の生成形態によつ
てその添加時期は異なる。例えば、感光性ハロゲ
ン化銀が加熱熟成によつて有機銀塩の一部を置換
して形成される場合は、反応が完全に終了した後
に添加されることが望ましい。これは、熟成時に
おける加熱が前記化合物(a)の一部が分解されるこ
とにより、その化合物により奏される効果が減少
してしまうか、若しくは感光性ハロゲン化銀の形
成に阻害を及ぼすためである。また感光性ハロゲ
ン化銀が常温に近い緩かな条件下で形成される場
合や予め系外で生成された感光性ハロゲン化銀が
有機銀塩に別個に加えられる場合には、前記化合
物(a)の添加時期は、特に限定されるものではな
い。しかし、最も好ましい添加時期は、有効な量
の感光性ハロゲン化銀、有機銀塩およびバインダ
ーから成る分散液に添加するか、或いはこの分散
液を支持体上に塗布乾燥後、その被覆層とは別個
の層を形成し得る塗布液に添加する。
本発明で用いる化合物の添加量は、一般に使用
する化合物の種類によつて異なるが、概ね総銀量
に対して約0.1モル％〜50モル％で、好ましくは
0.5モル％〜25モル％の範囲である。0.1モル％以
下の場合では、熱現像性感光材料の非感光化が十
分になされず、しかも生保存性熱現像の際のカブ
リ抑制および画像形成後の光変色の改良がなされ
ない。また、50モル％以上の量で使用した場合で
は、感度の低下を惹き起こし、しかも逆に生保存
性を阻害してしまう。
本発明で用いる化合物は、それぞれ異なる２種
以上の化合物を併用することによつて使用するこ
ともできる。
本発明の熱現像性感光材料は、微量の水銀化合
物を含有することにより、一層効果的に熱現像時
のカブリ発生を抑制することができる。水銀化合
物の代表例としては、水銀のハロゲン塩、臭酸
塩、クロム酸塩、硝酸塩の如き無機水銀塩または
水銀の酢酸塩、安息香酸塩、クエン酸塩の如き有
機酸水銀塩或いは水銀のコハク酸イミド塩、フタ
ル酸イミド塩、フタラジノン塩の如き窒素酸塩な
どを挙げることができる。かかる水銀化合物の添
加量は、前記した本発明で用いる化合物を含有し
ていない場合では総銀量に対して数モル％以上で
あるのに対し、本発明の熱現像性感光材料の場合
では総銀量に対して約0.005モル％〜約1.0モル％
の範囲で十分である。水銀化合物の添加量が総銀
量に対して0.005モル％以下の場合には、水銀化
合物を含有させることにより奏される効果が十分
に得られず、また1.0モル％以上の添加量の場合
では感度の低下を惹き起こすので、望ましいもの
ではない。
本発明に用いる熱現像性感光材料は、(a)被還元
性有機銀塩および還元剤から成る酸化一還元画像
形成成分、(b)感光性ハロゲン化銀および(c)バイン
ダーを少なくとも含有しており、このものを単一
層に含有させることもできるし、或いは感光性ハ
ロゲン化銀を含む被還元性有機銀塩と還元剤を別
個の層に含有させた多層構造とすることもでき
る。さらには、これら単層若しくは多層で形成さ
れた熱現像性感光要素の上に上塗りポリマー層を
設けることもできる。適当なポリマー層として
は、例えば、ポリビニルブチラール、ポリスチレ
ン、ポリメチルメタアクリレート、ポリウレタン
ゴム、塩化ゴム、エチルセルロース、セルロース
アセテートブチレート、酢酸セルロース、ポリ塩
化ビニル、ポリ塩化ビニリデン、ポリカーボネー
ト、ポリビニルピロリドンなどを挙げることがで
きる。
本発明の熱現像性感光材料で用いる前記成分(a)
の被還元性有機銀塩は、特公昭43−4924号および
特開昭46−6074号各公報に記載の有機酸の銀塩、
或いはイミノ基又はメルカプト基を有する有機化
合物の銀塩であり、特に炭素数12個〜24個の長鎖
脂肪酸銀塩は室温、室内光下で暗着色化等の不都
合な変化を受け難いため好ましいものである。具
体的にはベヘン酸銀、ステアリン酸銀、パルミチ
ン酸銀、ミリスチン酸銀、ラウリン酸銀、オレイ
ン酸銀、又はヒドロキシステアリン酸銀等を挙げ
ることができ、そのうち特にベヘン酸銀が最も有
効である。
前述の酸化−還元画像形成成分に用いる還元剤
は種々のものを挙げることができる。一般的に
は、通常のハロゲン化銀感光材料に用いられる現
像薬、具体的にはハイドロキノン、メチルハイド
ロキノン、クロロハイドロキノン、メチルヒドロ
キシナフタレン、Ｎ，N′−ジエチル−Ｐ−フエ
ニレンジアミン、アミノフエノール、アスコルビ
ン酸、１−フエニル−３−ピラゾリドンなどを挙
げることができ、又これらの他に２，2′−メチレ
ンビス（６−ターシヤリーブチル−４−メチルフ
エノール）、４，4′−ブチリデンビス（６−ター
シヤリーブチル−３−メチルフエノール）、４，
4′−チオビス（６−ターシヤリーブチル−３−メ
チルフエノール）など、更には特開昭46−6074号
公報に記載のビスナフトール系還元性化合物、或
いはベルギー特許第802519号明細書に記載の４−
ベンゼンスルホンアミドフエノールなどのスルホ
ンアミドフエノール系化合物を挙げることができ
る。
本発明における前記成分(b)の感光性ハロゲン化
銀としては、例えば塩化銀、臭化銀、沃化銀、塩
臭化銀、沃臭化銀などがあげられる。この感光性
ハロゲン化銀は、特に微細な粒子状のものが好ま
しい。これを調製する方法としては、特公昭43−
4924号公報に記載された被還元性有機銀塩の一部
を例えば臭化アンモニウム、塩化ナトリウムなど
により感光性ハロゲン化銀に変換する方法や、特
公昭53−40484号公報に記載されている様にＮ−
ハロゲン化合物を加熱分解せしめて感光性ハロゲ
ン化銀を調製する方法が挙げられる。また、いわ
ゆる現場外ハロゲン化銀も使用することができ
る。この現場外ハロゲン化銀を含有する熱現像性
感光要素は、例えばベルギー特許第774436号明細
書に記載されている。すなわち、被還元性有機銀
塩とは別の場所で感光性ハロゲン化銀を調製し、
次いで被還元性有機銀塩に混合して調製するもの
である。また、かかる感光性ハロゲン化銀は、特
開昭53−28416号、特公昭53−2687号、特公昭54
−22296号公報などに記載されている様な増感処
理を施こした感光性ハロゲン化銀であつてもよ
く、或いは一般的なハロゲン化銀写真乳剤の技術
分野で利用されている硫黄増感、金増感、還元増
感などの様な増感処理された感光性ハロゲン化銀
であつてもよい。感光性ハロゲン化銀の含有量
は、被還元性有機銀塩に対して約0.1モル％〜約
30モル％が好ましく、特に約0.5モル％〜20モル
％の範囲が好適である。
本発明における前記成分(c)のバインダーは、単
独若しくは２種以上を組合せて層中に含有するこ
とができる。バインダーの適当な材料は疎水性あ
るいは親水性であることができ、又透明若しくは
半透明であることができる。具体的には、ポリビ
ニルブチラール、セルロースアセテートブチレー
ト、ポリメチルメタアクリレート、ポリビニルピ
ロリドン、エチルセルロース、酢酸セルローズ、
ポリ酢酸ビニル、ポリビニルアルコール、ゼラチ
ン、カナダ特許第774054号明細書に記載のスルホ
ベタイン繰り返し単位を有するもの等を挙げるこ
とができる。バインダーの使用量は、被還元性有
機銀塩に対して、重量比で約10対１〜１対10が好
ましく、さらに好ましくは約２対１〜１対４の範
囲である。
本発明の熱現像性感光材料は、適当な色調剤を
含有することが好ましい。この目的のための色調
剤は、米国特許第3080254号公報に記載のフタラ
ジノンまたはその誘導体、特開昭46−6074号公報
に記載の環式アミド類、特開昭50−32927号公報
に記載のフタラジンジオン化合物などを包含す
る。
本発明の熱現像性感光材料は、特開昭48−
97523号公報に記載されている様に、被還元性有
機銀塩として有機脂肪酸銀塩を用いて調製される
場合に、好ましくは炭素数が該有機脂肪酸銀塩の
ものと同一か若しくはその近傍の脂肪酸を約25モ
ル％以上で単独若しくは組合せて含有せしめるこ
とも望ましい。
本発明の熱現像性感光材料には、適当な分光増
感剤を含有することができる。有用な増感色素
は、シアニン色素、メロシアニン色素、キサテン
色素、特に「プロダクトライセシングインデツク
ス」Vol92、第107〜110頁（1971年12月発行）あ
るいはベルギー特許第772371号明細書、特開昭47
−6329号、特開昭50−105127号、特開昭51−
127719号、特開昭52−80829号公報などに記載さ
れたものが有用である。また、その他の適当な添
加剤、例えば現像促進剤、硬化剤、帯電防止剤
（層）、紫外線吸収剤、螢光増白剤、フイルター染
料（層）なども用いることができる。
本発明で用いる支持体は、広範なものから選択
して使用することができる。代表的な支持体とし
ては、ポリエチレン、ポリプロピレン、ポリエチ
レンテレフタレート、ポリカーボネート、酢酸セ
ルロースなどの合成樹脂フイルム、合成紙、ポリ
エチレンなどの樹脂フイルムで被覆された紙、ア
ート紙などの紙類または写真用バライタ紙、アル
ミニウムなどの金属板（箔）類、通常の方法によ
り金属蒸着膜を有する合成樹脂フイルム、ガラス
板などを挙げることができる。
本発明の熱現像性感光材料を製造する方法とし
ては、下述の方法を単独若しくは組合せて実施す
ることが好ましい。その１つの方法としては、安
全光下で調製された熱現像性感光要素を支持体に
単層若しくは多層にして塗布し、乾燥することか
ら成る製造工程の少なくとも最終工程、すなわち
最終塗布層を塗布形成する際の乾燥工程を低温、
例えば65℃以下の温度、好ましくは55℃以下の温
度で実施する方法である。この時の乾燥時間は、
10分以内、好ましくは５分以内が望ましい。
第２の方法としては、支持体上に塗布され、乾
燥された熱現像性感光要素（この時の乾燥温度は
65℃以上の高温であつてもよい）の表面を瞬間的
に溶媒によつて浸漬処理し、その後上述の如き低
温乾燥する方法、或いは熱現像性感光材料を溶媒
雰囲気中に低温で10秒から24時間程度曝露保持す
る方法である。この際に用いる適当な溶媒として
は、メタノール、エタノールなどの１価のアルコ
ール類、塩化メチレン、トリクレン、パークレン
などのハロゲン化炭化水素類、アセトン、メチル
エチルケトンなどのケトン類、酢酸メチル、酢酸
エチル、酢酸ブチルなどのエステル類、トルエ
ン、キシレンなどの芳香族炭化水素類、その他飽
和炭化水素類、多価アルコール類など特に多大な
反応性を有さない限り、多くの有機溶媒が使用で
きる。また、水も有効である。これらの溶媒のう
ち、メタノール、エタノール、アセトンなどの低
沸点極性溶媒が、その処理性からみて特に好まし
いものである。
第３の方法としては、高温乾燥処理された熱現
像性感光材料であつて、この熱現像性感光材料を
画像形成に供する前に単に約55℃の温度以下極端
な場合で５℃程度の冷蔵庫に24時間程度保持する
ことにより非感光化する方法である。この方法
は、前述の２種の方法と比較して、分散用溶媒、
塗布手段などに限定されないことおよび溶媒によ
る追加処理を必要としないので、単に熱現像性感
光材料をバルク状態で冷暗所に保持するだけで非
感光化されることからみて、好ましいものであ
る。
本発明の熱現像性感光材料は、露光前に60℃〜
120℃の温度範囲で２秒〜30秒の加熱処理（いわ
ゆる加熱前処理）を施こすことにより、光活性化
される。その後、キセノンランプ、水銀灯、タン
グステンランプ、CRTレーザ光などの光源で露
光され、次いで80℃〜180℃、好ましくは110℃〜
150℃の加熱温度範囲で現像される。上述の温度
範囲外でも加熱時間を延長若しくは短縮すること
によつて現像することもできるが、現像時間は通
常約１秒〜60秒の範囲にするのが好ましい。加熱
現像する手段は、加熱プレートまたは加熱ドラム
とに接触させることが通常の手段であるが、その
他に加熱された雰囲気内に一時保持する手段を採
用してもよく、或いは高周波加熱や赤外光による
加熱の手段を採用することもできる。
本発明の熱現像性感光材料は、安全光下で前述
の溶媒処理或いは一定時間放置することにより非
感光化（再非感光化）すること、および加熱前処
理によつて光活性化（再光活性化）することがで
きることから、追加記録を必要とするマイクロフ
イルムシステムなどに有利に利用することができ
る。例えば、本発明の熱現像性感光材料に加熱前
処理を施こし、次いで映像露光および加熱現像を
順に施こすことにより銀画像を形成せしめ、その
後当該熱現像性感光材料に溶媒処理或いは一定時
間放置することにより再非感光化し、そして再び
必要に応じて加熱前処理を施こすことによつて再
光活性化せしめて追加の画像を記録することがで
きる。
また、本発明の熱現像性感光材料は、形成画像
に特公昭54−5687号公報に記載されている様な溶
媒処理或いは一定時間放置することにより、形成
画像の熱に対する安定性を一層増大させることも
できる。
以下、本発明を実施例に基づいてさらに詳細に
説明する。
実施例 １
ベヘン酸銀25ｇ、ベヘン酸20ｇをキシレン325
ml及びｎ−ブタノール325mlからなる分散溶媒に
入れたホモミキサーを用いて分散した。この分散
液にバインダーとしてポリビニルブチラール60ｇ
を加え撹拌溶解して銀塩のポリマー分散液を作つ
た。この分散液を赤色安全光下で50℃に加熱調温
し、メタノール50mlに溶解させた臭化リチウム
0.24ｇを撹拌しつつ１時間かけて滴下した。さら
に２時間温度を保ち撹拌を続けた後、分散液を再
び室温まで下げて感光性スラリー（Ａ液）を調製
した。
Ａ液100ｇに化合物（）−(5)の2.0重量％のア
セトン溶液５mlを加え10分間撹拌した。これを写
真用原紙上に１m2当り銀量として0.5ｇになるよ
う75℃で塗布した。さらに塗布物上に下記の成分
からなる組成物（）を１m2当り乾燥時5.0ｇに
なるよう75℃で上塗りし試料(a)を作成した。
組成物（）
２，2′−メチレンビス（６−ｔ−ブチル−４−メ
チルフエノール） 25.0ｇ
フラタジノン 7.5ｇ
ポリビニルブチラール 20.0ｇ
３−エチル−５−〔（３−メチル−２−チアゾニリ
デン）エチリデン〕ローダニン 0.005ｇ
酢酸水銀 0.04ｇ
キシレン 250ml
ｎ−ブタノール 250ml
比較のためにＡ液100ｇに化合物（）−(5)の代
りとしてＮ−ブロムサクシンイミドの1.8重量％
アセトン溶液５mlを添加する以外は上記の方法に
準じて試料(b)を作成した。
さらに比較のためＡ液100ｇに全くモノハロゲ
ン化合物を添加せずに上記の方法に準じて試料(c)
を作成した。
これらの試料(a)、(b)及び(c)は作成後、２時間赤
色安全光下で室温に放置され、次いで光学楔（コ
ダツクステツプタブレツトNo.２）を通してタング
ステン光による4000ルツクス秒の露光が与えられ
後に、125℃の温度で10秒間の加熱現像が施こさ
れた。この結果得られたそれぞれの画像から感
度、反射最大濃度および熱カブリ濃度を測定し
た。これらの結果を下記の表に示す。尚、表中
の感度は熱カブリ濃度＋0.15の濃度を与えるに必
要な露光量の逆数とし、試料(c)の感度を「100」
とした相対感度で表示した。
The present invention relates to a heat-developable photosensitive material, and more particularly to a pre-heat-treated heat-developable photosensitive material that is imparted with photosensitivity by subjecting it to heat pretreatment. Conventionally, silver halide photography, which has been widely used, has improved photographic properties such as photosensitivity and gradation compared to photography methods using so-called non-silver salt photosensitive materials, such as diazo photography and electrophotography. This is an extremely excellent method of photography. However, the silver halide photographic materials used in this method require wet processing steps such as development, stopping, fixing, and washing under safe light or in a dark room in order to obtain stable images, which requires time and processing time. There were problems in that it was time-consuming, posed a danger to the human body due to the handling of chemicals, and contaminated the inside of the processing room and the hands and clothes of workers. Therefore, a photographic method that allows stable images to be obtained by dry processing while using silver halide is highly desired, and a great deal of research has been carried out to date. For example, Special Publication No. 43-4921 or Special Publication No. 43-4921
The most successful example is the heat-developable photosensitive material described in Publication No. 4924, which is made of a combination of three components: an organic silver salt, a reducing agent, and a silver halide in catalytic contact with organic silver ions. . In addition to the above-mentioned examples, there are also
Heat-pretreated heat-developable photosensitive materials such as those described in JP-A-48-51626 and JP-A-49-10039 have been proposed. This heat-developable photosensitive material is given photosensitivity through preheating treatment, and a silver image is formed through subsequent image exposure and heat development, so it can be handled in a bright room. Moreover, it has features such as the ability to perform additional recording. The present invention relates to the latter type of heat-pretreated heat-developable photosensitive material of the above-mentioned examples. In conventional heat-developable photosensitive materials of this type, it is necessary to design the photosensitive layer so that photosensitive silver halide can be generated during pre-heating treatment, which requires limiting the manufacturing conditions and Alternatively, methods have been adopted such as using a specific halogenating agent or exposing the material to a solvent atmosphere. However, these types of heat-developable photosensitive materials produced by these methods are still not fully satisfactory in terms of photographic properties such as shelf life, sensitivity, gradation, and background color density. It is something. Up to now, many inventions have been made to improve these drawbacks. For example, attempts have been made to use organic halides and halogen molecular complexes containing group, group, and group elements described in JP-A-52-73022 and JP-A-53-25420. However, although these methods improve storage stability and background color fog density, they do not improve sensitivity or gradation. The reasons for this are, firstly, that photosensitive silver halide is generated during heat pretreatment, making it difficult to apply sensitizing means such as physical ripening or chemical ripening, or to perform calculated tone control. Second, spectral sensitization cannot be achieved because free halogens generated during storage or heat pretreatment of heat-developable photosensitive materials destroy sensitizing dyes. The present invention makes it possible to prepare heat-pretreated heat-developable photosensitive materials (hereinafter simply referred to as "heat-developable photosensitive materials") by using the specific compounds described below. This can effectively eliminate the above-mentioned drawbacks. Therefore, a first object of the present invention is to provide a heat-developable photosensitive material that provides images with high sensitivity and high gamma. A second object of the present invention is to provide a heat-developable photosensitive material that has excellent shelf life. A third object of the present invention is to provide a heat-developable photosensitive material that exhibits less thermal fog during heat development. A fourth object of the present invention is to provide a heat-developable photosensitive material that exhibits less photodiscoloration after image formation. The object of the present invention is to provide at least
(a) an oxidation monoreduction image forming component consisting of a reducible organic silver salt and a reducing agent, (b) a photosensitive silver halide and
(c) In a heat-pretreated heat-developable photosensitive material in which a heat-developable photosensitive element comprising a binder is formed in a single layer or in multiple layers, the heat-developable photosensitive element (d) is represented by the following general formula [] or []. This can be achieved by using a heat-pretreated heat-developable photosensitive material containing at least one kind of compound. General formula [] In the formula, X 1 and X 2 each represent a halogen atom (eg, a chlorine atom, a bromine atom, an iodine atom). R 1 , R 2 , R 3 , R 4 , R 5 and R 6 each represent a hydrogen atom, a substituted or unsubstituted alkyl group (e.g. methyl group, ethyl group, propyl group, butyl group, t-butyl group, pentyl group) group, hexyl group, 2
- Ethylhexyl group, n-octyl group, 2-hydroxyethyl group, 3-hydroxypropyl group, etc., especially R 1 , R 2 , R 4 , R 5 and R 6 are alkyl groups having 1 to 4 carbon atoms. Preferably, R 3 represents an alkyl group having 1 to 8 carbon atoms) or a substituted or unsubstituted aryl group (e.g., phenyl group, tolyl group, naphthyl group, nitrophenyl group, hydroxyphenyl group, etc.), They may be the same or different. Z is a 5- or 6-membered heterocycle (e.g., pyrrole ring, pyrroline ring, pyrrolidine ring, imidazole ring, imidazoline ring, imidazolidine ring, pyrazole ring, pyrazoline ring, virazolidine ring, triazole ring, tetrazole ring, piperidine ring) ,
Oxazine ring, thiazine ring, piperazine ring, hydantoin ring, cyanuric ring, thiohytantoin ring,
Represents a group of nonmetallic atoms necessary to complete a hexahydrotriazine ring, indole ring, indoline ring, isoindole ring, benzimidazole ring, benzisothiazole ring, carbazole ring, phenoxazine ring, purine ring). Further, this ring may have a substituent such as an alkyl group, an aryl group, an alkoxy group, a halogen atom, oxygen (=O), or sulfur (=S). The above alkyl group is, for example, a methyl group, an ethyl group, a propyl group,
iso-propyl group, butyl group, t-butyl group, iso
- Alkyl groups having 1 to 12 carbon atoms such as butyl group, pentyl group, hexyl group, 2-ethylhexyl group, octyl group, nonyl group, decyl group, and dodecyl group are preferred. Aryl groups include substituents (for example, methyl, ethyl, propyl, iso
-propyl group, butyl group, t-butyl group, chlorine atom, bromine atom, etc.), phenyl group, naphthyl group, etc. are preferred. Examples of the alkoxy group include methoxy group, ethoxy group, propoxy group,
Preferred are alkoxy groups having 1 to 12 carbon atoms, such as iso-propoxy, butoxy, t-butoxy, octoxy, and dodecyloxy. A 1
and A 2 each represent a carbonyl group or a sulfonyl group. Representative examples of the compounds represented by the general formula [] or [] are listed below. []-(1): N-chloromethylsuccinimide []-(2): N-bromomethylsuccinimide []-(3): N-iodomethylsuccinimide []-(4): N-chloromethyl Maleimide []-(5): N-bromomethylmaleimide []-(6): N-chloromethylphthalimide []-(7): N-(1-bromoethyl)maleimide []-(8): N-(1-chloroethyl)phthalimide []-(9): N-(phenylbromomethyl)maleimide []-(10): N-(phenylchromemethyl)phthalimide []-(11): N- Chlormethyl-1,8-naphthalimide []-(12):N-(1-chloro-1-methylethyl)
Maleimide []-(13): N-(1-bromo-1-methylethyl)maleimide []-(14): N-(1-chloro-1-methylethyl)phthalimide []-(15): N-(1-chloro-1-methylethyl)-1,8-naphthalimide []-(16): N-(1-chloroethyl)-1,8-
Naphthalimide []-(17): N-chloromethyl-2-pyrrolidone []-(18): N-chloromethyl-α-piperidone []-(19): N-chloromethyl-2-oxazolinone []-(20) :N-bromomethylphthalazinone[]-(21):N,N'-di(chloromethyl)-5,
5-Dimethylbarbituric acid []-(22): N,N'-di(bromomethyl)-5,
5-dimethylbarbituric acid []-(23): N,N'-di(chloromethyl)-4,
4-Dimethylhydantoin []-(24): N,N',N''-tri(chloromethyl)
Cyanuric acid []-(25): N-chloromethyl-2,3-hydro-1,2-benziisosulfonazole []-(26): N-chloromethylsaccharin []-(1): N-chlor Methylacetamide []-(2): N-(1-bromoethyl)acetamide []-(3): N-chloromethylpropioamide []-(4): N-(1-bromoethyl)propioamide []-( 5): N-chloromethylacetanilide []-(6): N-chloromethylbenzamide []-(7): N-chloromethyl-α-naphthamide []-(8): N-bromomethyl-β-naphthamide [ ]-(9): N-chloromethylmethanesulfonamide []-(10): N-chloromethylbenzenesulfonamide []-(11): N-bromomethylethanesulfonamide The timing of addition of these compounds is It may be added at any time during the manufacturing process of the developable light-sensitive material, but generally the time of addition differs depending on the formation form of the photosensitive silver halide of component (b). For example, when a photosensitive silver halide is formed by partially replacing an organic silver salt by heat ripening, it is desirable to add it after the reaction is completely completed. This is because heating during ripening partially decomposes the compound (a), reducing the effect produced by the compound, or inhibiting the formation of photosensitive silver halide. It is. In addition, when the photosensitive silver halide is formed under mild conditions close to room temperature or when the photosensitive silver halide previously formed outside the system is added separately to the organic silver salt, the compound (a) The timing of addition is not particularly limited. However, the most preferable addition time is to add it to a dispersion consisting of an effective amount of photosensitive silver halide, an organic silver salt, and a binder, or to apply this dispersion onto a support and dry it, then form a coating layer. Added to coating solution capable of forming separate layers. The amount of the compound used in the present invention generally varies depending on the type of compound used, but is generally about 0.1 mol% to 50 mol% based on the total amount of silver, preferably
It ranges from 0.5 mol% to 25 mol%. If the amount is less than 0.1 mol %, the heat-developable photosensitive material will not be sufficiently desensitized, and furthermore, fogging during storage heat development will not be suppressed and photodiscoloration after image formation will not be improved. Moreover, when used in an amount of 50 mol% or more, it causes a decrease in sensitivity and conversely impairs raw storage stability. The compounds used in the present invention can also be used in combination of two or more different compounds. By containing a trace amount of a mercury compound, the heat-developable photosensitive material of the present invention can more effectively suppress the occurrence of fog during heat development. Typical examples of mercury compounds include inorganic mercury salts such as mercury halides, bromates, chromates, and nitrates; organic mercury salts such as mercury acetates, benzoates, and citrates; and mercury succinates. Examples include nitrates such as acid imide salts, phthalic acid imide salts, and phthalazinone salts. The amount of the mercury compound added is several mol% or more based on the total amount of silver in the case where the above-mentioned compound used in the present invention is not contained, whereas in the case of the heat-developable photosensitive material of the present invention, the amount of the mercury compound added is several mol% or more based on the total amount of silver. Approximately 0.005 mol% to approximately 1.0 mol% based on the amount of silver
is sufficient. If the amount of mercury compound added is less than 0.005 mol% based on the total amount of silver, the effect of containing the mercury compound will not be sufficiently obtained, and if the amount added is 1.0 mol% or more, This is not desirable because it causes a decrease in sensitivity. The heat-developable photosensitive material used in the present invention contains at least (a) an oxidation monoreduction image forming component consisting of a reducible organic silver salt and a reducing agent, (b) a photosensitive silver halide, and (c) a binder. This material can be contained in a single layer, or it can have a multilayer structure in which a reducible organic silver salt containing photosensitive silver halide and a reducing agent are contained in separate layers. Furthermore, an overcoat polymer layer can be provided on the heat-developable photosensitive element formed of a single layer or multiple layers. Suitable polymer layers include, for example, polyvinyl butyral, polystyrene, polymethyl methacrylate, polyurethane rubber, chlorinated rubber, ethyl cellulose, cellulose acetate butyrate, cellulose acetate, polyvinyl chloride, polyvinylidene chloride, polycarbonate, polyvinylpyrrolidone, and the like. be able to. The above component (a) used in the heat-developable photosensitive material of the present invention
The reducible organic silver salts include silver salts of organic acids described in Japanese Patent Publication No. 43-4924 and Japanese Patent Application Laid-open No. 46-6074,
Alternatively, it is a silver salt of an organic compound having an imino group or a mercapto group, and in particular, a silver salt of a long chain fatty acid having 12 to 24 carbon atoms is preferable because it is less susceptible to undesirable changes such as darkening at room temperature and under room light. It is something. Specific examples include silver behenate, silver stearate, silver palmitate, silver myristate, silver laurate, silver oleate, and silver hydroxystearate, among which silver behenate is particularly effective. . Various reducing agents can be used in the above-mentioned oxidation-reduction image forming component. In general, developers used in conventional silver halide photosensitive materials, specifically hydroquinone, methylhydroquinone, chlorohydroquinone, methylhydroxynaphthalene, N,N'-diethyl-P-phenylenediamine, aminophenol, Examples include ascorbic acid, 1-phenyl-3-pyrazolidone, etc. In addition to these, 2,2'-methylenebis(6-tertiarybutyl-4-methylphenol), 4,4'-butylidenebis(6- tert-butyl-3-methylphenol), 4,
4'-thiobis(6-tertiarybutyl-3-methylphenol), etc., as well as bisnaphthol reducing compounds described in JP-A-46-6074, or 4 as described in Belgian Patent No. 802519. −
Examples include sulfonamide phenol compounds such as benzenesulfonamide phenol. Examples of the photosensitive silver halide of component (b) in the present invention include silver chloride, silver bromide, silver iodide, silver chlorobromide, and silver iodobromide. This photosensitive silver halide is particularly preferably in the form of fine particles. The method for preparing this is
The method of converting a part of a reducible organic silver salt into a photosensitive silver halide using ammonium bromide, sodium chloride, etc., described in Japanese Patent Publication No. 4924, and the method described in Japanese Patent Publication No. 53-40484. N-
Examples include a method of preparing photosensitive silver halide by thermally decomposing a halide compound. It is also possible to use so-called ex-situ silver halides. A heat-developable photosensitive element containing this ex-situ silver halide is described, for example, in Belgian Patent No. 774,436. That is, photosensitive silver halide is prepared in a separate location from the reducible organic silver salt,
Next, it is prepared by mixing it with a reducible organic silver salt. In addition, such photosensitive silver halide is disclosed in JP-A No. 53-28416, JP-A No. 53-2687, JP-A-54
It may be a photosensitive silver halide that has been subjected to a sensitization treatment as described in Publication No. 22296, or a sulfur sensitized silver halide used in the technical field of general silver halide photographic emulsions. It may be a photosensitive silver halide that has been subjected to sensitization treatment such as gold sensitization, reduction sensitization, or the like. The content of photosensitive silver halide is approximately 0.1 mol% to approximately
30 mol% is preferred, particularly a range of about 0.5 mol% to 20 mol%. The binder as component (c) in the present invention may be contained in the layer alone or in combination of two or more. Suitable materials for the binder can be hydrophobic or hydrophilic, and transparent or translucent. Specifically, polyvinyl butyral, cellulose acetate butyrate, polymethyl methacrylate, polyvinyl pyrrolidone, ethyl cellulose, cellulose acetate,
Examples include polyvinyl acetate, polyvinyl alcohol, gelatin, and those having a sulfobetaine repeating unit as described in Canadian Patent No. 774054. The amount of the binder to be used is preferably about 10:1 to 1:10, more preferably about 2:1 to 1:4, based on the weight ratio of the reducible organic silver salt. The heat-developable photosensitive material of the present invention preferably contains a suitable color toning agent. Color toning agents for this purpose include phthalazinone or its derivatives as described in U.S. Pat. Includes phthalazinedione compounds, etc. The heat-developable photosensitive material of the present invention is disclosed in Japanese Patent Application Laid-Open No.
As described in Publication No. 97523, when an organic fatty acid silver salt is used as the reducible organic silver salt, it is preferable to use a silver salt having the same number of carbon atoms as that of the organic fatty acid silver salt, or a carbon number close to that of the organic fatty acid silver salt. It is also desirable to contain about 25 mole percent or more of fatty acids, alone or in combination. The heat-developable photosensitive material of the present invention may contain a suitable spectral sensitizer. Useful sensitizing dyes include cyanine dyes, merocyanine dyes, and xatene dyes, especially "Product Licensing Index" Vol. 92, pp. 107-110 (published December 1971) or Belgian Patent No. 772371, JP-A-Sho. 47
−6329, JP-A No. 105127, JP-A-51-
127719, JP-A-52-80829, etc. are useful. Other suitable additives such as development accelerators, curing agents, antistatic agents (layers), ultraviolet absorbers, fluorescent whitening agents, filter dyes (layers), etc. can also be used. The support used in the present invention can be selected from a wide variety of supports. Typical supports include synthetic resin films such as polyethylene, polypropylene, polyethylene terephthalate, polycarbonate, and cellulose acetate, synthetic papers, papers coated with resin films such as polyethylene, papers such as art paper, and photographic baryta paper. , metal plates (foils) such as aluminum, synthetic resin films having metal vapor-deposited films by ordinary methods, glass plates, and the like. As a method for producing the heat-developable photosensitive material of the present invention, it is preferable to carry out the following methods alone or in combination. One method involves at least the final step of the manufacturing process, which consists of coating a heat-developable photosensitive element prepared under safe light on a support in a single layer or in multiple layers and drying, i.e., applying the final coated layer. Low temperature drying process when forming
For example, the method is carried out at a temperature of 65°C or lower, preferably 55°C or lower. The drying time at this time is
It is desirable within 10 minutes, preferably within 5 minutes. In the second method, a heat-developable photosensitive element is coated on a support and dried (the drying temperature at this time is
The surface of the material (which may be at a high temperature of 65°C or higher) is momentarily immersed in a solvent and then dried at a low temperature as described above, or the heat-developable photosensitive material is placed in a solvent atmosphere at a low temperature for 10 seconds or more. This is a method of exposing and holding for about 24 hours. Suitable solvents to be used in this case include monohydric alcohols such as methanol and ethanol, halogenated hydrocarbons such as methylene chloride, trichlene, and perchloromethane, ketones such as acetone and methyl ethyl ketone, methyl acetate, ethyl acetate, and acetic acid. Many organic solvents can be used as long as they do not have particularly high reactivity, such as esters such as butyl, aromatic hydrocarbons such as toluene and xylene, other saturated hydrocarbons, and polyhydric alcohols. Water is also effective. Among these solvents, low-boiling polar solvents such as methanol, ethanol, and acetone are particularly preferred in view of their processability. The third method is to use a heat-developable photosensitive material that has been subjected to a high-temperature drying process, and simply store the heat-developable photosensitive material in a refrigerator at a temperature of about 55°C or less, or about 5°C in extreme cases, before using it for image formation. This method desensitizes the material by holding it for about 24 hours. This method, compared to the two methods mentioned above, uses a dispersing solvent,
This method is preferable because it is not limited to the coating means and does not require additional treatment with a solvent, so that the heat-developable photosensitive material can be made non-sensitized simply by keeping it in a bulk state in a cool, dark place. The heat-developable photosensitive material of the present invention can be heated at 60°C or more before exposure.
It is photoactivated by heat treatment (so-called heat pretreatment) in a temperature range of 120°C for 2 seconds to 30 seconds. After that, it is exposed with a light source such as xenon lamp, mercury lamp, tungsten lamp, CRT laser light, etc., and then 80℃~180℃, preferably 110℃~
Developed at a heating temperature range of 150℃. Although development can be carried out outside the above-mentioned temperature range by extending or shortening the heating time, it is preferable that the developing time is usually in the range of about 1 second to 60 seconds. The usual method for heat development is to bring the material into contact with a heating plate or heating drum, but other means for temporarily holding the material in a heated atmosphere may also be used, or high frequency heating or infrared light may be used. It is also possible to employ heating means such as The heat-developable photosensitive material of the present invention can be desensitized (re-desensitized) by the above-mentioned solvent treatment or left to stand for a certain period of time under safe light, and photoactivated (re-desensitized) by heat pretreatment. Activation), it can be advantageously used in microfilm systems that require additional recording. For example, a silver image is formed by subjecting the heat-developable photosensitive material of the present invention to a heat pretreatment, and then sequentially subjecting it to image exposure and heat development, and then subjecting the heat-developable photosensitive material to a solvent treatment or leaving it for a certain period of time. By doing so, it can be re-desensitized and, if necessary, can be re-photoactivated by subjecting it to a heating pretreatment to record additional images. Furthermore, the heat-developable photosensitive material of the present invention can further increase the stability of the formed image against heat by subjecting the formed image to a solvent treatment as described in Japanese Patent Publication No. 54-5687 or by leaving it for a certain period of time. You can also do that. Hereinafter, the present invention will be explained in more detail based on examples. Example 1 25 g of silver behenate and 20 g of behenic acid were mixed with 325 g of xylene.
ml and n-butanol using a homomixer in a dispersion solvent consisting of 325 ml. Add 60g of polyvinyl butyral as a binder to this dispersion.
was added and dissolved with stirring to prepare a polymer dispersion of silver salt. This dispersion was heated to 50℃ under red safety light, and lithium bromide was dissolved in 50ml of methanol.
0.24 g was added dropwise over 1 hour while stirring. After maintaining the temperature for another 2 hours and continuing stirring, the dispersion was cooled to room temperature again to prepare a photosensitive slurry (liquid A). 5 ml of a 2.0% by weight acetone solution of compound ()-(5) was added to 100 g of Solution A and stirred for 10 minutes. This was coated onto photographic base paper at 75° C. to give a silver amount of 0.5 g per 1 m 2 . Further, the coated material was overcoated with a composition () consisting of the following components at 75° C. at a dry weight of 5.0 g per 1 m 2 to prepare sample (a). Composition () 2,2'-methylenebis(6-t-butyl-4-methylphenol) 25.0g Fratadinone 7.5g Polyvinyl butyral 20.0g 3-ethyl-5-[(3-methyl-2-thiazonylidene)ethylidene]rhodanine 0.005g mercury acetate 0.04g xylene 250ml n-butanol 250ml For comparison, 1.8% by weight of N-bromsuccinimide was added to 100g of solution A in place of compound ()-(5).
Sample (b) was prepared according to the above method except that 5 ml of acetone solution was added. Furthermore, for comparison, sample (c) was prepared according to the above method without adding any monohalogen compound to 100 g of liquid A.
It was created. After preparation, these samples (a), (b) and (c) were left at room temperature under red safety light for 2 hours and then exposed to 4000 lux seconds with tungsten light through an optical wedge (Kodak Step Tablet No. 2). After exposure, heat development was performed at a temperature of 125° C. for 10 seconds. Sensitivity, maximum reflection density, and thermal fog density were measured from each of the resulting images. These results are shown in the table below. The sensitivity in the table is the reciprocal of the exposure amount required to give a density of thermal fog density + 0.15, and the sensitivity of sample (c) is "100".
It is expressed as a relative sensitivity.
【表】
さらに、試料(a)〜(c)をそれぞれ５℃の温度の冷
蔵庫に３日間保存した後に、それぞれについて
110℃の温度で５秒間の加熱前処理を施こし、次
いで前記と同様の方法により像露光および加熱現
像して銀画像を形成させた。得られた画像につい
て前記と同様のセンシトメトリーを行なつた。ま
た、加熱前処理を施こさない場合についても、上
記と同様のテストを行なつた。得られた画像につ
いて、前記と同様のセンシトメトリーを行なつ
た。これらの結果を下記の表２に示す。尚、表中
の感度は、前記テストNo.３で用いた試料(c)の感度
を「100」とした相対感度で表示した。[Table] In addition, after storing each sample (a) to (c) in a refrigerator at a temperature of 5℃ for 3 days,
A preheating treatment was carried out at a temperature of 110° C. for 5 seconds, followed by imagewise exposure and heat development in the same manner as described above to form a silver image. Sensitometry similar to that described above was performed on the obtained images. In addition, the same test as above was also conducted in the case where no preheating treatment was performed. Sensitometry similar to that described above was performed on the obtained images. These results are shown in Table 2 below. Note that the sensitivity in the table is expressed as a relative sensitivity, with the sensitivity of sample (c) used in Test No. 3 being "100".
【表】
（表中、※はほとんどタングステン感度を示さな
いことを表わす。以下の実施例においても同様）
また、前記テストNo.４〜９で実施した冷蔵庫に保
存された試料(a)〜(c)をさらに35℃の温度で相対湿
度80％の雰囲気下に１週間保存した後、前記テス
ト４〜９で採用したテスト法を用いて画像を形成
させた。得られた画像について前記と同様のセン
シトメトリーを行なつた。これらの結果を下記の
表３に示す。尚、表中の感度はテストNo.３で用い
た試料(c)の感度を「100」とした相対感度で表示
した。[Table] (In the table, * indicates almost no tungsten sensitivity. The same applies to the following examples)
In addition, the samples (a) to (c) stored in the refrigerator carried out in Tests Nos. 4 to 9 were further stored for one week in an atmosphere of 80% relative humidity at a temperature of 35°C. Images were formed using the test method adopted in 9. Sensitometry similar to that described above was performed on the obtained images. These results are shown in Table 3 below. Note that the sensitivity in the table is expressed as a relative sensitivity, with the sensitivity of sample (c) used in Test No. 3 being "100".
【表】
（表中、※※は全くタングステン感度を示さない
ことを表わす。以下の実施例においても同様）
これらの表から、本発明の試料(a)は塗布乾燥後
放置されることにより徐々に感光性を失い、かつ
加熱前処理によつて感光性を回復する特異な性質
を有することが明らかである。一方試料(b)ではこ
れらの性能が得られず、かつ感度が著るしく阻害
されることが判る。さらに、生保存性に於いて
も、試料(a)は試料(c)が著るしく熱カブリを増すの
に対し、全くその変化を認めなかつた。
実施例 ２
前記実施例１で使用した化合物（）−(5)の代
りにＡ液100ｇに対し化合物（）−(4)の1.5重量
％のアセトン溶液５mlを添加した以外は実施例１
の方法と同様の方法で試料(d)を作成した。
さらに、化合物（）−(4)に代えてＮ−クロル
サクシンイミドの1.3重量％のアセトン溶液５ml
を用いた以外は試料(d)を作成した方法と同様の方
法で試料(e)を作成した。
この試料(d)および(e)を前記実施例１で採用した
同様のセンシトメトリー法を用いて感光特性を測
定した。試料(d)は実施例１における試料(a)に比較
して、やゝ効果が弱いものゝ同様の性能を示し
た。一方、試料(e)は減感が著しいので、好ましく
なかつた。
実施例 ３
ベヘン酸銀25ｇ、ベヘン酸20ｇをトルエン130
ml、メチルエチルケトン195mlおよびエタノール
75mlから成る分散溶媒に入れ、これをホモミキサ
ーを用いて分散した。この分散液にバインダーと
しポリビニルブチラール60ｇを加え撹拌溶解して
銀塩のポリマー分散液を作つた。この分散液を赤
色安全光下で30℃に保ち、メタノール50mlに溶解
させた臭化アンモニウム0.14ｇを撹拌しつつ滴下
した。さらに２時間撹拌を続けて感光性スラリー
（Ｂ液）を調製した。
Ｂ液75ｇに化合物（）−(1)の0.6重量％アセト
ン溶液５mlを加え10分間撹拌した。さらに下記の
成分からなる組成物（）を加え撹拌混合した後
に、写真用原紙上に１m2当り銀量として0.5ｇに
なるよう55℃で塗布乾燥し、これを試料(f)とし
た。
組成物（）
ｄ，ｄ−ビス−（２−ヒドロキシ−３，５−ジメ
チルフエニル）−３，５，５−トリメチルヘキサ
ン 3.0ｇ
フタラジノン 0.9ｇ
１−アリル−３−カルボキシメチル−４−〔３−
エチル−２−ナフトオキサゾニリデン）エチリデ
ン〕チオヒダントイン 0.002ｇ
臭化水銀 0.027ｇ
エチルアルコール ２ml
比較のために、試料(g)として化合物（）−(1)
に代えてＮ−クロルアセトアミドの0.7重量％ア
セトン溶液５mlをＢ液に加えた以外は、試料(f)を
作成した方法と同様の方法で作成した。また、試
料(f)を作成する時に用いた化合物（）−(1)を含
有させなかつた以外は、試料(f)を作成した方法と
同様の方法で試料(h)を作成した。
試料(f)〜(h)をそれぞれ35℃の温度で相対湿度80
％の条件下に１週間保存し、次いでそれぞれにつ
いて110℃の温度で５秒間の加熱前処理を施こし
た後、前記実施例１と同様の方法で画像を形成さ
せ、そして得られた画像について実施例１と同様
のセンシトメトリーを行なつた。また、加熱前処
理を施こさない場合についても、同様のテストを
繰り返した。これらの結果を下記の表４に示す。
尚、表中の感度はテストNo.３で用いた試料(c)の感
度を「100」とした相対感度で表示した。[Table] (In the table, * indicates no tungsten sensitivity at all. The same applies to the following examples.) From these tables, it can be seen that sample (a) of the present invention gradually shows no tungsten sensitivity after coating and drying. It is clear that it has the unique property of losing photosensitivity when exposed to heat and recovering photosensitivity by pretreatment with heat. On the other hand, it can be seen that sample (b) does not provide these performances and the sensitivity is significantly impaired. Furthermore, in terms of raw storage stability, sample (a) showed no change at all, whereas sample (c) showed a marked increase in thermal fog. Example 2 Example 1 except that 5 ml of a 1.5% by weight acetone solution of compound ()-(4) was added to 100 g of solution A instead of compound ()-(5) used in Example 1.
Sample (d) was prepared in the same manner as in . Furthermore, in place of compound ()-(4), 5 ml of a 1.3% by weight acetone solution of N-chlorsuccinimide
Sample (e) was prepared in the same manner as sample (d) except that . The photosensitivity properties of these samples (d) and (e) were measured using the same sensitometric method employed in Example 1 above. Sample (d) showed similar performance as sample (a) in Example 1, although the effect was slightly weaker. On the other hand, sample (e) showed significant desensitization and was therefore not preferred. Example 3 25g of silver behenate, 20g of behenic acid and 130g of toluene
ml, methyl ethyl ketone 195 ml and ethanol
The mixture was placed in 75 ml of a dispersion solvent and dispersed using a homomixer. To this dispersion, 60 g of polyvinyl butyral as a binder was added and dissolved with stirring to prepare a polymer dispersion of silver salt. This dispersion was kept at 30° C. under a red safety light, and 0.14 g of ammonium bromide dissolved in 50 ml of methanol was added dropwise with stirring. Stirring was continued for an additional 2 hours to prepare a photosensitive slurry (liquid B). 5 ml of a 0.6% by weight acetone solution of compound ()-(1) was added to 75 g of Solution B and stirred for 10 minutes. Further, a composition (2) consisting of the following components was added and mixed by stirring, and then coated on photographic base paper at 55° C. to give a silver content of 0.5 g per 1 m 2 and dried, and this was used as sample (f). Composition () d,d-bis-(2-hydroxy-3,5-dimethylphenyl)-3,5,5-trimethylhexane 3.0g Phthalazinone 0.9g 1-allyl-3-carboxymethyl-4-[3 −
Ethyl-2-naphthoxazonylidene)ethylidene]thiohydantoin 0.002g Mercury bromide 0.027g Ethyl alcohol 2ml For comparison, compound ()-(1) was used as sample (g).
Sample (f) was prepared in the same manner as sample (f), except that 5 ml of a 0.7% by weight acetone solution of N-chloroacetamide was added to Solution B instead. In addition, sample (h) was prepared in the same manner as sample (f), except that the compound ()-(1) used in preparing sample (f) was not included. Samples (f) to (h) were each heated at a temperature of 35℃ and a relative humidity of 80℃.
% conditions for one week, and then each was subjected to preheating treatment at a temperature of 110°C for 5 seconds, and then an image was formed in the same manner as in Example 1, and the resulting image was Sensitometry similar to Example 1 was performed. In addition, the same test was repeated in the case where no preheating treatment was performed. These results are shown in Table 4 below.
Note that the sensitivity in the table is expressed as a relative sensitivity, with the sensitivity of sample (c) used in Test No. 3 being "100".
【表】
以上の実施例１〜３から明らかな様に、本発明
の熱現像性感光材料は、加熱前処理型のものとし
て非常に優れていることが判る。
実施例 ４
ベヘン酸銀25ｇ、ベヘン酸20ｇをキシレン325
mlおよびｎ−ブタノール325mlからなる分散溶媒
に入れ、これをホモミキサーを用いて分散した。
この分散液にバインダーとしてポリビニリブチラ
ール60ｇを加え撹拌溶解して、銀塩のポリマー分
散液を作つた。この分散液を赤色安全光下で50℃
に加熱調温し、これにアセトン50mlに溶解させた
Ｎ−ブロムサクシンイミド0.5ｇを撹拌しつゝ滴
下した。２時間温度を保ち撹拌を続けた後、分散
液を再び室温まで下げて感光性スラリー（Ｃ液）
を調製した。
Ｃ液50ｇを10個に分け取り、それぞれに下記の
表５に示す濃度の化合物のアセトン溶液2.5mlを
添加し10分間撹拌した。これを写真用原紙上に１
m2当り銀量として0.5ｇになるよう75℃で塗布し
た。さらに、これ等10種の塗布物上に前記実施例
１の組成物（）を１m2当り乾燥時5.0ｇになる
よう75℃で上塗して、それぞれ10種の試料(i)〜
（ｒ）を作成した。[Table] As is clear from Examples 1 to 3 above, the heat-developable photosensitive material of the present invention is extremely excellent as a heat-pretreated type. Example 4 25 g of silver behenate and 20 g of behenic acid were mixed with 325 g of xylene.
ml and 325 ml of n-butanol, and this was dispersed using a homomixer.
To this dispersion, 60 g of polyvinybutyral was added as a binder and dissolved with stirring to prepare a polymer dispersion of silver salt. This dispersion was heated at 50°C under red safety light.
0.5 g of N-bromsuccinimide dissolved in 50 ml of acetone was added dropwise to the mixture while stirring. After maintaining the temperature for 2 hours and continuing stirring, the dispersion was cooled to room temperature again to form a photosensitive slurry (liquid C).
was prepared. 50 g of Solution C was divided into 10 portions, and 2.5 ml of an acetone solution of a compound having a concentration shown in Table 5 below was added to each portion and stirred for 10 minutes. Place this on photographic paper 1
Coating was carried out at 75° C. so that the amount of silver was 0.5 g per m 2 . Furthermore, on top of these 10 types of coatings, the composition () of Example 1 was overcoated at 75°C at a dry weight of 5.0 g per 1 m 2 , and each of the 10 types of samples (i) to
(r) was created.
【表】
（尚、表中、試料(i)および(j)は、本発明品であ
り、他の試料は比較品である。）
試料(i)〜（ｒ）について、それぞれ前記実施例
３と同様の方法により画像を形成させ、次いで形
成された画像について前記実施例１と同様の方法
のセンシトメトリーを行なつた。これらの結果を
下記の表６に示す。但し、表中の感度はテストNo.
42で用いた試料（ｒ）の感度を「100」とした相
対感度で表示した。また、それぞれの画像の色調
についての観察結果も表６に併記した。[Table] (In the table, samples (i) and (j) are products of the present invention, and other samples are comparative products.) Regarding samples (i) to (r), each sample was obtained from Example 3 above. An image was formed in the same manner as in Example 1, and then the formed image was subjected to sensitometry in the same manner as in Example 1. These results are shown in Table 6 below. However, the sensitivity in the table is based on test No.
The sensitivity of the sample (r) used in 42 is expressed as a relative sensitivity of "100". Table 6 also lists the observation results regarding the color tone of each image.
【表】
（尚、表中の「fresh」は、冷暗所に保存した試
料（ｒ）を他のテストと同様の像露光および加熱
現像して形成された画像のセンシトメトリーを表
わす。）
上記表から明らかな様に、本発明に係る係合物
の他にも非感光化を促進する化合物が見い出され
たが、写真特性を考慮した場合その効果は弱く、
本発明に係る試料が最も優れていることが判る。
実施例 ５
前記実施例４で用いた試料(j)に含まれている化
合物（）−(6)の量を下記の表７に示す様に量変
化させた以外は、試料(j)を作成した方法と同様の
方法で試料（ｓ）〜（ｖ）を作成した。
試料（ｓ）〜（ｖ）をそれぞれ110℃の温度で
５秒間の加熱前処理し、次いで光学楔（コダツク
ステツプタブレツトNo.２）を通してタングステン
光による4000ルツクス・秒の露光を与えた後、
125℃の温度で10秒間加熱現像した。その後形成
された画像を室内光（螢光灯5000ルツクス）下に
144時間曝露した。この時、所定時間経過毎にカ
ブリ濃度の変化を測定した。この結果を表７に示
す。[Table] (In addition, "fresh" in the table represents the sensitometry of the image formed by imagewise exposure and heat development of the sample (r) stored in a cool and dark place in the same way as in other tests.) The above table As is clear from the above, compounds that promote desensitization were found in addition to the engaging compound according to the present invention, but their effects were weak when photographic properties were taken into consideration.
It can be seen that the sample according to the present invention is the best. Example 5 Sample (j) was prepared except that the amount of compound ()-(6) contained in sample (j) used in Example 4 was changed as shown in Table 7 below. Samples (s) to (v) were prepared in the same manner as described above. Samples (s) to (v) were each subjected to a heating pretreatment at a temperature of 110°C for 5 seconds, and then exposed to 4000 lux·sec of tungsten light through an optical wedge (Kodak Step Tablet No. 2). ,
Heat development was performed at a temperature of 125°C for 10 seconds. The formed image is then placed under room light (5000 lux of fluorescent light).
Exposure for 144 hours. At this time, changes in fog density were measured every predetermined time period. The results are shown in Table 7.
【表】
上記表から明らかな様に、本発明に係る試料は
形成された画像が光に対して極めて安定化されて
いることが判る。[Table] As is clear from the above table, it can be seen that the images formed by the samples according to the present invention are extremely stabilized against light.
Claims (1)
よび還元剤から成る酸化−還元画像形成成分、(b)
感光性ハロゲン化銀および(c)バインダーから成る
熱現像性感光要素を単層若しくは多層に形成した
加熱前処理型熱現像性感光材料において、前記熱
現像性感光要素が(d)下記一般式［］若しくは
［］で示される化合物の少なくとも１種を含有
することを特徴とする加熱前処理型熱現像性感光
材料。 一般式［］ 一般式［］ （式中、X1およびX2はハロゲン原子を表わす。
R1、R2、R3、R4、R5およびR6は水素原子、置換
若しくは非置換のアルキル基または置換若しくは
非置換のアリール基を表わし、互いに同一であつ
てもよくあるいは異なつていてもよい。Ｚは５員
または６員の複素環を形成するに必要な非金属原
子群を表わし、上記複素環には置換基を有しても
よい。A1およびA2は、カルボニル基またはスル
ホニル基を表わす。）[Scope of Claims] 1. At least (a) an oxidation-reduction image forming component comprising a reducible organic silver salt and a reducing agent, (b) on a support;
In a heat-pretreated heat-developable photosensitive material in which a heat-developable photosensitive element comprising a photosensitive silver halide and (c) a binder is formed in a single layer or in multiple layers, the heat-developable photosensitive element has (d) the following general formula [ ] or [ ] A heat-pretreated heat-developable photosensitive material, characterized in that it contains at least one compound represented by [ ] or [ ]. General formula [] General formula [] (In the formula, X 1 and X 2 represent halogen atoms.
R 1 , R 2 , R 3 , R 4 , R 5 and R 6 represent a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, and may be the same or different. It's okay. Z represents a nonmetallic atomic group necessary to form a 5- or 6-membered heterocycle, and the heterocycle may have a substituent. A 1 and A 2 represent a carbonyl group or a sulfonyl group. )
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5201180A JPS56147143A (en) | 1980-04-18 | 1980-04-18 | Heat developing photosensitive material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5201180A JPS56147143A (en) | 1980-04-18 | 1980-04-18 | Heat developing photosensitive material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS56147143A JPS56147143A (en) | 1981-11-14 |
| JPH0121490B2 true JPH0121490B2 (en) | 1989-04-21 |
Family
ID=12902867
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5201180A Granted JPS56147143A (en) | 1980-04-18 | 1980-04-18 | Heat developing photosensitive material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS56147143A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4671446A (en) * | 1982-12-02 | 1987-06-09 | Stanley Electric Company, Ltd. | Method and system for automatically bonding a leadwire on a semiconductor |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS53125014A (en) * | 1977-04-08 | 1978-11-01 | Fuji Photo Film Co Ltd | Preparation of heat developable photosensitive material |
| JPS53143310A (en) * | 1977-05-20 | 1978-12-13 | Asahi Chemical Ind | Dry type image forming material |
-
1980
- 1980-04-18 JP JP5201180A patent/JPS56147143A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS53125014A (en) * | 1977-04-08 | 1978-11-01 | Fuji Photo Film Co Ltd | Preparation of heat developable photosensitive material |
| JPS53143310A (en) * | 1977-05-20 | 1978-12-13 | Asahi Chemical Ind | Dry type image forming material |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS56147143A (en) | 1981-11-14 |
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