JPH01177029A - Thermal development photosensitive material - Google Patents
Thermal development photosensitive materialInfo
- Publication number
- JPH01177029A JPH01177029A JP33556987A JP33556987A JPH01177029A JP H01177029 A JPH01177029 A JP H01177029A JP 33556987 A JP33556987 A JP 33556987A JP 33556987 A JP33556987 A JP 33556987A JP H01177029 A JPH01177029 A JP H01177029A
- Authority
- JP
- Japan
- Prior art keywords
- group
- dye
- silver
- general formula
- hydrogen atom
- 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.)
- Pending
Links
- 239000000463 material Substances 0.000 title claims abstract description 75
- 238000011161 development Methods 0.000 title description 23
- -1 silver halide Chemical class 0.000 claims abstract description 68
- 229910052709 silver Inorganic materials 0.000 claims abstract description 51
- 239000004332 silver Substances 0.000 claims abstract description 51
- 239000000126 substance Substances 0.000 claims abstract description 39
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 35
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 27
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 22
- 125000003118 aryl group Chemical group 0.000 claims abstract description 19
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 11
- 125000000623 heterocyclic group Chemical group 0.000 claims abstract description 9
- 229910052717 sulfur Chemical group 0.000 claims abstract description 6
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 5
- 125000004430 oxygen atom Chemical group O* 0.000 claims abstract description 4
- 125000004434 sulfur atom Chemical group 0.000 claims abstract description 3
- 150000001875 compounds Chemical class 0.000 claims description 91
- 125000001424 substituent group Chemical group 0.000 claims description 14
- 125000003545 alkoxy group Chemical group 0.000 claims description 7
- 125000003277 amino group Chemical group 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 125000003342 alkenyl group Chemical group 0.000 claims description 4
- 125000001841 imino group Chemical group [H]N=* 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 abstract description 2
- 239000001301 oxygen Substances 0.000 abstract description 2
- 239000000975 dye Substances 0.000 description 103
- 239000010410 layer Substances 0.000 description 63
- 239000000839 emulsion Substances 0.000 description 42
- 238000000034 method Methods 0.000 description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 27
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 23
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 22
- 239000007864 aqueous solution Substances 0.000 description 21
- 239000002904 solvent Substances 0.000 description 21
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 18
- 108010010803 Gelatin Proteins 0.000 description 17
- 229920000159 gelatin Polymers 0.000 description 17
- 239000008273 gelatin Substances 0.000 description 17
- 235000019322 gelatine Nutrition 0.000 description 17
- 235000011852 gelatine desserts Nutrition 0.000 description 17
- 238000009835 boiling Methods 0.000 description 16
- 239000006185 dispersion Substances 0.000 description 16
- 239000000203 mixture Substances 0.000 description 15
- 230000001235 sensitizing effect Effects 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 13
- 239000002243 precursor Substances 0.000 description 13
- 238000003860 storage Methods 0.000 description 12
- 239000004094 surface-active agent Substances 0.000 description 12
- 206010070834 Sensitisation Diseases 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 11
- 230000008569 process Effects 0.000 description 11
- 230000008313 sensitization Effects 0.000 description 11
- 239000002585 base Substances 0.000 description 10
- 238000009792 diffusion process Methods 0.000 description 10
- 239000012992 electron transfer agent Substances 0.000 description 10
- 229910001961 silver nitrate Inorganic materials 0.000 description 10
- 238000012546 transfer Methods 0.000 description 10
- 239000003960 organic solvent Substances 0.000 description 9
- 150000003839 salts Chemical class 0.000 description 9
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 239000004848 polyfunctional curative Substances 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 239000011230 binding agent Substances 0.000 description 7
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 7
- 238000011282 treatment Methods 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000011241 protective layer Substances 0.000 description 6
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 6
- 235000019345 sodium thiosulphate Nutrition 0.000 description 6
- 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 6
- 238000003756 stirring Methods 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 125000006575 electron-withdrawing group Chemical group 0.000 description 5
- 239000007800 oxidant agent Substances 0.000 description 5
- 230000001603 reducing effect Effects 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 150000003378 silver Chemical class 0.000 description 5
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 238000011033 desalting Methods 0.000 description 4
- 230000006870 function Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- 238000006467 substitution reaction Methods 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- SJOOOZPMQAWAOP-UHFFFAOYSA-N [Ag].BrCl Chemical compound [Ag].BrCl SJOOOZPMQAWAOP-UHFFFAOYSA-N 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 125000003710 aryl alkyl group Chemical group 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 3
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 230000008707 rearrangement Effects 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 3
- 230000003595 spectral effect Effects 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- HBEDSQVIWPRPAY-UHFFFAOYSA-N 2,3-dihydrobenzofuran Chemical compound C1=CC=C2OCCC2=C1 HBEDSQVIWPRPAY-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 125000004414 alkyl thio group Chemical group 0.000 description 2
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 2
- 125000005110 aryl thio group Chemical group 0.000 description 2
- 239000013040 bath agent Substances 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 238000004061 bleaching Methods 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 2
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 2
- CHSBUVXZAGJOFK-UHFFFAOYSA-L disodium;dioxido-bis(sulfanylidene)-$l^{6}-sulfane Chemical compound [Na+].[Na+].[O-]S([O-])(=S)=S CHSBUVXZAGJOFK-UHFFFAOYSA-L 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000001804 emulsifying effect Effects 0.000 description 2
- NPERTKSDHFSDLC-UHFFFAOYSA-N ethenol;prop-2-enoic acid Chemical compound OC=C.OC(=O)C=C NPERTKSDHFSDLC-UHFFFAOYSA-N 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 229910052757 nitrogen Chemical group 0.000 description 2
- 239000002667 nucleating agent Substances 0.000 description 2
- 230000000269 nucleophilic effect Effects 0.000 description 2
- 150000007530 organic bases Chemical class 0.000 description 2
- 238000005691 oxidative coupling reaction Methods 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 2
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 2
- 229920000247 superabsorbent polymer Polymers 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 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
- 229920003169 water-soluble polymer Polymers 0.000 description 2
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 1
- MEKOFIRRDATTAG-UHFFFAOYSA-N 2,2,5,8-tetramethyl-3,4-dihydrochromen-6-ol Chemical compound C1CC(C)(C)OC2=C1C(C)=C(O)C=C2C MEKOFIRRDATTAG-UHFFFAOYSA-N 0.000 description 1
- IAONCYGNBVHNCT-UHFFFAOYSA-N 2-(4-chlorophenyl)sulfonylacetic acid Chemical compound OC(=O)CS(=O)(=O)C1=CC=C(Cl)C=C1 IAONCYGNBVHNCT-UHFFFAOYSA-N 0.000 description 1
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical class NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 125000004179 3-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(Cl)=C1[H] 0.000 description 1
- 125000004208 3-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C([H])C(*)=C1[H] 0.000 description 1
- 125000004207 3-methoxyphenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(OC([H])([H])[H])=C1[H] 0.000 description 1
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 description 1
- 241000238876 Acari Species 0.000 description 1
- 241000208140 Acer Species 0.000 description 1
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 229920002307 Dextran Polymers 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- 229920000084 Gum arabic Polymers 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
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 241000238413 Octopus Species 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 239000004373 Pullulan Substances 0.000 description 1
- 229920001218 Pullulan Polymers 0.000 description 1
- 241000978776 Senegalia senegal Species 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- WTFDOFUQLJOTJQ-UHFFFAOYSA-N [Ag].C#C Chemical compound [Ag].C#C WTFDOFUQLJOTJQ-UHFFFAOYSA-N 0.000 description 1
- HOLVRJRSWZOAJU-UHFFFAOYSA-N [Ag].ICl Chemical compound [Ag].ICl HOLVRJRSWZOAJU-UHFFFAOYSA-N 0.000 description 1
- 239000000205 acacia gum Substances 0.000 description 1
- 235000010489 acacia gum Nutrition 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 125000005336 allyloxy group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- DZGUJOWBVDZNNF-UHFFFAOYSA-N azanium;2-methylprop-2-enoate Chemical compound [NH4+].CC(=C)C([O-])=O DZGUJOWBVDZNNF-UHFFFAOYSA-N 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 description 1
- 125000001164 benzothiazolyl group Chemical group S1C(=NC2=C1C=CC=C2)* 0.000 description 1
- 150000001565 benzotriazoles Chemical class 0.000 description 1
- 235000013877 carbamide Nutrition 0.000 description 1
- STIAPHVBRDNOAJ-UHFFFAOYSA-N carbamimidoylazanium;carbonate Chemical compound NC(N)=N.NC(N)=N.OC(O)=O STIAPHVBRDNOAJ-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- VZWXIQHBIQLMPN-UHFFFAOYSA-N chromane Chemical group C1=CC=C2CCCOC2=C1 VZWXIQHBIQLMPN-UHFFFAOYSA-N 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000007771 core particle Substances 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 125000006222 dimethylaminomethyl group Chemical group [H]C([H])([H])N(C([H])([H])[H])C([H])([H])* 0.000 description 1
- AFOSIXZFDONLBT-UHFFFAOYSA-N divinyl sulfone Chemical compound C=CS(=O)(=O)C=C AFOSIXZFDONLBT-UHFFFAOYSA-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
- KWKXNDCHNDYVRT-UHFFFAOYSA-N dodecylbenzene Chemical compound CCCCCCCCCCCCC1=CC=CC=C1 KWKXNDCHNDYVRT-UHFFFAOYSA-N 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- ZMYGMDGWVGLYBL-UHFFFAOYSA-N ethane;2-ethenylsulfonyl-n-[2-[(2-ethenylsulfonylacetyl)amino]ethyl]acetamide Chemical compound CC.C=CS(=O)(=O)CC(=O)NCCNC(=O)CS(=O)(=O)C=C ZMYGMDGWVGLYBL-UHFFFAOYSA-N 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- 238000005259 measurement Methods 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
- 229910021645 metal ion Inorganic materials 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
- UMBBGOALZMAJSF-UHFFFAOYSA-N n-benzylethenamine;hydrochloride Chemical compound [Cl-].C=C[NH2+]CC1=CC=CC=C1 UMBBGOALZMAJSF-UHFFFAOYSA-N 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000005445 natural material Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000012038 nucleophile Substances 0.000 description 1
- 238000007344 nucleophilic reaction Methods 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- QUBQYFYWUJJAAK-UHFFFAOYSA-N oxymethurea Chemical compound OCNC(=O)NCO QUBQYFYWUJJAAK-UHFFFAOYSA-N 0.000 description 1
- 229950005308 oxymethurea Drugs 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 125000003356 phenylsulfanyl group Chemical group [*]SC1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000191 poly(N-vinyl pyrrolidone) Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 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
- 235000019423 pullulan Nutrition 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000005070 ripening Effects 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229940100890 silver compound Drugs 0.000 description 1
- 150000003379 silver compounds Chemical group 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- MGGIUSCEEFSDGT-UHFFFAOYSA-M silver;3-phenylprop-2-ynoate Chemical compound [Ag+].[O-]C(=O)C#CC1=CC=CC=C1 MGGIUSCEEFSDGT-UHFFFAOYSA-M 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229940047670 sodium acrylate Drugs 0.000 description 1
- SONHXMAHPHADTF-UHFFFAOYSA-M sodium;2-methylprop-2-enoate Chemical compound [Na+].CC(=C)C([O-])=O SONHXMAHPHADTF-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007962 solid dispersion Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 150000003456 sulfonamides Chemical class 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- IELLVVGAXDLVSW-UHFFFAOYSA-N tricyclohexyl phosphate Chemical compound C1CCCCC1OP(OC1CCCCC1)(=O)OC1CCCCC1 IELLVVGAXDLVSW-UHFFFAOYSA-N 0.000 description 1
- 125000002889 tridecyl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000003672 ureas Chemical class 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
- G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
- G03C8/40—Development by heat ; Photo-thermographic processes
- G03C8/4013—Development by heat ; Photo-thermographic processes using photothermographic silver salt systems, e.g. dry silver
- G03C8/408—Additives or processing agents not provided for in groups G03C8/402 - G03C8/4046
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
Abstract
Description
【発明の詳細な説明】
く従来技術とその問題点〉
ハロゲン化銀を用いる写真法は他の写真法たとえば電子
写真やジアゾ写真法に比べて、感度や階調調節などの写
真特性にすぐれているので、従来から最も広範に用いら
れてきた。近年になってハロゲン化銀を用いた感光材料
の画像形成処理法を従来の境像液等による湿式処理から
、加熱等による乾式処理にかえることにより簡易で迅速
に＋ｌ１３ｉ １＆を得ることのできる技術が開発され
てきた。[Detailed description of the invention] Prior art and its problems> Photography using silver halide has superior photographic properties such as sensitivity and gradation control compared to other photographic methods such as electrophotography and diazo photography. Because of this, it has traditionally been the most widely used. In recent years, a technology has been developed that allows +l13i 1& to be obtained simply and quickly by changing the image forming method for photosensitive materials using silver halide from the conventional wet processing using a developing liquid, etc. to a dry processing using heating, etc. has been developed.
熱現像感光材料は当該技術分野では公知であり熱塊＠感
光材料とそのプロセスについては、たとえは写真工学の
基礎（／り７Ｐ年コロナ社発行）の、ｔ３３員、３１６
貞、／り７♂年弘月発行映像情報弘Ｏ貝、「ネブレッッ
、フォトグラフィーとりプログラフイーのハンドブック
」第７版（Ｎｅｂｌｅｔｔｓ ）Ｊａｎｄｂｏｏｋ
ｏｆＰｈｏｔｏｇｒａｐｈｙ ａｎｄ １もｅｏ
ｒｏｇｒａｐｈｙ ７ｔｈＥｄ、）ジアゾ・ノストラ
ンド・ラインホールド・カンパ＝−（Ｖａｎ Ｎｏ５ｔ
ｒａｎｄ ＲｅｉｎｈｏｌｄＣｏｍｐａｎｙ）のＪｕ〜
Ｊｊｊｊ、米国特許第３．／ｊ２．りθμ号、第Ｊ、３
０／、６７１号、第３゜３タコ、０２０号、第ｚ、ｕ！
７．０７ｊ号、英国特許第１．／３／、ｉｏｒ号、第１
．／Ａ７゜７７７号および、リサーチ・ディスクロージ
ャー誌／り７ｇ年６月号７〜／！ベージ（ＲＤ−／７０
２り）に記載されている。Heat-developable photosensitive materials are well known in the art, and the thermal mass@photosensitive materials and their processes are described in, for example, Fundamentals of Photographic Engineering (Published by Corona Publishing, 7P), t33 member, 316.
Sada, / 7♂ Published by Hirotsuki Video information Hirokai, "Nebletts, Photography and Programming Handbook" 7th edition (Nebletts) Jandbook
ofPhotography and 1 also eo
rography 7thEd,) Diazo Nostrand Reinhold Campa=-(Van No5t
rand Reinhold Company) Ju~
Jjjj, U.S. Patent No. 3. /j2. riθμ No. J, 3
0/, No. 671, No. 3°3 Octopus, No. 020, No. z, u!
No. 7.07j, British Patent No. 1. /3/, ior issue, 1st
．． /A7゜777 and Research Disclosure magazine /ri7g June issue 7~/! Beige (RD-/70
2).
また加熱によりカラー像を得る撞々の方法が例えはリサ
ーチ・ディスクロージャー誌ｌり７１年ｊ月号ｊ≠〜ｊ
ｌベージ（几Ｄ−／４ＦＡＡ号）、同１７７６年μ月号
３０〜３２ページ（ＲＤ−／１す３号］、米国特許第３
．りｒｊ、乙！！号、同弘、≠Ａｊ、０７９号、同≠、
≠７≠、 Ｉｔ、７号、同≠、弘７１．２２７号、同≠
、！θ７．Ｊｔｒｏ号、同μ、！００．１！１２乙号、
同弘、弘１３゜りｌ≠号等に提案されている。これらは
いずれも加熱によって色素を生成もしくは放出させ色素
の像様分布を形成させるものであり、短時間で色素の像
様分布が得られる特徴がある。Also, various methods of obtaining color images by heating are described in Research Disclosure magazine, 1971 issue, j≠～j.
l page (几D-/4FAA No.), 1776 μ month issue, pages 30-32 (RD-/1S3), U.S. Patent No. 3
．． Rirj, Otsu! ! No., Dohiro, ≠Aj, No. 079, Same≠,
≠7≠, It, No. 7, same≠, Hiroshi No. 71.227, same≠
,! θ7. Jtro issue, same μ! 00.1!12 No. Otsu,
It has been proposed in Dohiro, Hiro 13゜ri ≠ issue, etc. All of these produce or release dyes by heating to form an image-like distribution of the dye, and are characterized by the ability to obtain an image-like distribution of the dye in a short period of time.
ところが、上記のような従来公知の熱現像感光材料は、
感光材料中にハロゲン化銀を還元する還元剤を内蔵して
いる。このような感光材料においては、経時保存中に還
元剤が徐々に酸化されて消失したり、感光材料中の他の
化合物と反応したりして、画像濃度の低下や、スティン
の上昇を引き起こすという問題点がめった。特（ζ、こ
の傾向は、３−フェニルピラゾリジノン誘導体等、電位
の低い化合物を還元剤として用いている熱現像感光材料
において顕著であった。However, the conventionally known heat-developable photosensitive materials as mentioned above,
The photosensitive material contains a reducing agent that reduces silver halide. In such photosensitive materials, during storage, the reducing agent gradually oxidizes and disappears, or reacts with other compounds in the photosensitive material, causing a decrease in image density and an increase in stain. There were a lot of problems. In particular, this tendency was remarkable in heat-developable photosensitive materials that use compounds with low potential as reducing agents, such as 3-phenylpyrazolidinone derivatives.
〈発明の目的〉
従って、本発明の目的は、生保存性の優れた熱現像感光
材料を提供することにある。さらに本発明の目的は、画
像濃度が高く、スティンが低い画１象を得ることができ
る熱現像感光材料を提供することにある。<Object of the Invention> Accordingly, an object of the present invention is to provide a heat-developable photosensitive material having excellent shelf life. A further object of the present invention is to provide a heat-developable photosensitive material that can provide an image with high image density and low stain.
〈発明の構成〉
本発明の目的は、支持体上に少なくとも感光性ハロゲン
化銀、還元剤および、下記−最大Ｃ１１〜（ＩＶ）で表
される化合物の少なくとも７つｔｉすることを特徴とす
る熱現像感光材料によって達成された。<Structure of the Invention> The object of the present invention is to provide on a support at least a photosensitive silver halide, a reducing agent, and at least seven compounds represented by the following C11 to (IV) at most. This was achieved using heat-developable photosensitive materials.
一般式〔工〕
式中、
Ｚは（１＝／のとき水素原子、アルキル基または−ＣＯ
ＹｔＹはアルキル基、アリール基、シクロアルキル基、
アルコキシ基、置換アミノ基ｅ＆すンを表し、ｎ＝２の
ときＺｎｌたはＮ ｉを表す。General formula [Engine] In the formula, Z is (when 1=/, hydrogen atom, alkyl group or -CO
YtY is an alkyl group, an aryl group, a cycloalkyl group,
It represents an alkoxy group, a substituted amino group e&sun, and when n=2, it represents Znl or Ni.
几１〜几５は水素原子、置換基または化学結合を表す。几1 to 几5 represent a hydrogen atom, a substituent, or a chemical bond.
但しＣの化学結合は、直接または２〜≠価残基金介して
、該残基の価数に応じた数の一般式〔工〕で表される化
合物と結合するものである。However, the chemical bond of C is one that is bonded directly or via a valence group of 2 to ≠ to a number of compounds represented by the general formula [E] according to the valence of the residue.
更に、Ｒ１−Ｒ５の隣合う置換基同士またはｆＬ１〜Ｒ
５のいずれかと上記２〜１価残基とが互いに連結してｊ
−Ａ員環を形成してもよい。Furthermore, adjacent substituents of R1-R5 or fL1-R
5 and the above divalent to monovalent residues are linked to each other, and j
- An A-membered ring may be formed.
−最大（ＩＩ） ／Ｘ几。- maximum (II) /X 几.
−ＸＲ７
＼ｘＲ８
式中、
Ｘは酸素原子、硫黄原子、置換イミノ基（−Ｎ−）を表
す。-XR7\xR8 In the formula, X represents an oxygen atom, a sulfur atom, or a substituted imino group (-N-).
１４６〜几 は水素原子、置換基または化学結合を衣す
。但しこの化学結合に、直接ま−たはλ〜≠価残基を介
しで、該残基のｆｌｆｆｉ数に応じた数の一般式（ｎ）
で表される化合物と結合するものである。146~几 represents a hydrogen atom, a substituent, or a chemical bond. However, in this chemical bond, directly or via a λ~≠valent residue, a number of general formulas (n) corresponding to the flffi number of the residue are added.
It binds to the compound represented by.
更に、几６〜几９の任意の置換基間±または几６〜几９
のいずれかと上記２〜≠価残基とが互いに連結してｖ−
６員環を形成してもよい。Furthermore, between any substituents of 几6-几9± or 几6-几9
and the above di~≠valent residue are connected to each other to form v-
A 6-membered ring may be formed.
−最大（１）
％式％）
式中、
Ｗは、ｎニアのとき水素原子、アンモニウム、−８１，
１１または几 を表し、ｎ＝２のときＺｎまたはＮｉを
表す。-Maximum (1) % formula %) In the formula, W is a hydrogen atom when n nia, ammonium, -81,
11 or 几, and when n=2, it represents Zn or Ni.
ＢＩＧ、Ｂｌｌはアルキル基、複素環残基、−ＣＲＴ（
Ｙは一般式〔Ｉ〕で定義したのと同じ）または（Ｒ１２
〜Ｒ１４は各々アルキル基またはアリール基ｆｔ表す）
を表す。BIG, Bll are alkyl groups, heterocyclic residues, -CRT (
Y is the same as defined in general formula [I]) or (R12
~R14 each represents an alkyl group or an aryl group ft)
represents.
一般式〔■〕
几 −Ｎ Ｂ１６
式中、
几 、Ｒは各々アルキル基、シクロアルキル基、アルケ
ニル基またはアリール基を表し、これらは互いに連結し
てｓ−ｊ員環を形成してもよい。General formula [■] 几 -N B16 In the formula, 几 and R each represent an alkyl group, a cycloalkyl group, an alkenyl group, or an aryl group, and these may be linked to each other to form an sj-membered ring.
本発明の化合物について更に詳しく説明する。The compounds of the present invention will be explained in more detail.
なお以下においてアルキル基、アリール基、複素環基、
シクロアルキル基、アルケニル基、アルコキシ基、その
他の置換基は、他の置換基によって置換されているもの
を含む。In addition, in the following, an alkyl group, an aryl group, a heterocyclic group,
Cycloalkyl groups, alkenyl groups, alkoxy groups, and other substituents include those substituted with other substituents.
一般大ＣＩ’ｌで衣わされる化合物について説明する。Compounds coated with general CI'I will be explained.
式中、Ｚ［ｎニアのとき水素原子、アルキル基（例えば
メチル基、エチル基、プロピル基、インプロピル基％ｎ
−ブチル基、５ｅｅ−ブチル基、ｔｅｒｔ−ブチル基、
ｎ−ペンチル基、５ｅｃ−はメチル基％ｔｅｒｔ−はメ
チル基、ネオペンチル基、ｎ−ヘキシル基、シクロヘキ
シル基、ｎ−オクチル基、ベンジル基なト）、おヨヒ−
Ｃ−Ｙ（Ｙはアルキル基（例えばメチル基・ｔｅｒｔ−
ブチル基なと）、アリール基（例えばフェニル基など）
、シクロアルキル基（例えばシクロヘキシル基など）、
アルコキシ基（例えはメトキシ基、エトキシ基など）、
置換アミノ基（例えはジメチルアミノ基、アニリノ基な
ど）１に＆わす）を衣わす。In the formula, when Z[n near, hydrogen atom, alkyl group (e.g. methyl group, ethyl group, propyl group, inpropyl group %n
-butyl group, 5ee-butyl group, tert-butyl group,
n-pentyl group, 5ec- is methyl group, tert- is methyl group, neopentyl group, n-hexyl group, cyclohexyl group, n-octyl group, benzyl group),
C-Y (Y is an alkyl group (e.g. methyl group, tert-
butyl group), aryl group (e.g. phenyl group, etc.)
, cycloalkyl group (e.g. cyclohexyl group),
Alkoxy group (e.g. methoxy group, ethoxy group, etc.),
A substituted amino group (e.g. dimethylamino group, anilino group, etc.) is added to the base.
また、ｎ＝２のときＺはＺｎまたはＮｉを表わす。几
〜几 は水素原子、を換基または化学結合を表わす。置
換基としては、水酸基、ノ・ロゲン原子、アルキル基（
例えｔｊ、ｔｅｒｔ−ブチル基、ｎ−ブチル基、１ｓｏ
−プロピル基、ネオペンチルａ、ｔ ｅ ｒ ｔ−アミ
ル基、メチル基、エチル基、ジメチルアミノメチル基、
とドロキシメチル基、ベンジル基、エトキシカルボニル
メチル基、ジエチルホスホリルメチル基、カルボキシエ
チル基、アリル基、１ｓｏ−メチル基、ａｅｃ−ヘキシ
ル基、ｎ−オクチル基、ｎ−ウンデシル基ｓ ｎ−オク
タデシル基など）、シクロアルキル基（例えは、シクロ
はメチル基、シクロヘキシル基など）、アリール基（例
えは、フェニル基、ナフチル基、３−ヒドロキシフェニ
ル基、３−クロロフェニル基、弘−アセテルアミノフ壬
ニル基、コーフリル基、−−ピリジル基など）、アルコ
キシ基（例工は、メトキシ基、エトキシ基など）、アリ
ールオキシ基（例えば、フェノキシ基、３−メトキージ
フェノキシ基など）、アルキルチオ基（例えｔｒ！、ｎ
−ｙチルチオ基、ｎ−万りチルチオ基など）、アリール
チオ基（例えけ、フェニルチオ基など）、複素環アミノ
基（例えは、コー（２，弘＋’ ）！Ｊアジン）−ア
ミノ基など）、および
−Ｃ−Ｙ＜Ｙはアルキル基（例えばメチル基、ｔｅｒｔ
−ブチル基など）、アリール基（例えばフェニル基など
）、シクロアルキル基（例工はシクロヘキシル基など）
、アルコキシ基（例えはメトキシ基、エトキシ基など）
、置換アミノ基（例えはジメチルアミノ基、アニリノ基
など）ヲ表わす）などが挙げられる。Further, when n=2, Z represents Zn or Ni.几
〜几 represents a hydrogen atom, a substituent, or a chemical bond. Examples of substituents include hydroxyl group, norogen atom, and alkyl group (
For example, tj, tert-butyl group, n-butyl group, 1so
-propyl group, neopentyl a, tert-amyl group, methyl group, ethyl group, dimethylaminomethyl group,
and droxymethyl group, benzyl group, ethoxycarbonylmethyl group, diethylphosphorylmethyl group, carboxyethyl group, allyl group, 1so-methyl group, aec-hexyl group, n-octyl group, n-undecyl group, n-octadecyl group, etc.) , cycloalkyl group (for example, cyclo means methyl group, cyclohexyl group, etc.), aryl group (for example, phenyl group, naphthyl group, 3-hydroxyphenyl group, 3-chlorophenyl group, Hiro-acetelaminophenyl group, cofuryl group) , --pyridyl group, etc.), alkoxy group (for example, methoxy group, ethoxy group, etc.), aryloxy group (for example, phenoxy group, 3-methoxydiphenoxy group, etc.), alkylthio group (for example, tr!, n
-y tilthio group, n-manritylthio group, etc.), arylthio group (for example, phenylthio group, etc.), heterocyclic amino group (for example, Co(2,Hiro+')!Jazine)-amino group, etc.) , and -C-Y<Y is an alkyl group (e.g. methyl group, tert
-butyl group, etc.), aryl group (e.g., phenyl group, etc.), cycloalkyl group (e.g., cyclohexyl group, etc.)
, alkoxy group (e.g. methoxy group, ethoxy group, etc.)
, a substituted amino group (for example, dimethylamino group, anilino group, etc.).
Ｒ１−Ｒ５が化学結合を表わす場合、その置換位置とλ
〜≠価残基を介して、または直接に、その価数に応じた
数の別の一般式ＣＩ）で表わされる化合物のＲ１〜ｆＬ
５の任意の１つの置換位置で連結する。When R1-R5 represents a chemical bond, the substitution position and λ
~≠ Via valence residues or directly, R1 to fL of a number of other compounds of the general formula CI) depending on their valency
5 at any one substitution position.
この時のλ〜グ価残基としては、例えば（１）−６日２
−
（”Ｈ３
目
−ｃＨ２−
＋８１ （−Ｃ）１２Ｃ１（２Ｃ−０一部１ｌ−ＣＨ
２） ａ０υ ＋Ｃ）ｉ ２ ＣＨ２Ｃ−ＱＣ）１２
ＣＭ ｚ十丁Ｓ■
ＣＨ２
α４１ −８− （１ｓ −ｏ −（１６）
−Ｃ−（１７） −Ｃ１−１２８−ＣＨ２−など力
弾けられる。At this time, the λ ~ group value residue is, for example, (1) - 6 days 2
- ("H3th -cH2- +81 (-C) 12C1 (2C-0 part 1l-CH
2) a0υ +C)i 2 CH2C-QC)12
CM z Jucho S■ CH2 α41 -8- (1s -o -(16)
-C-(17) -C1-128-CH2- etc. can be played with force.
きらに几１〜Ｒ５の隣合うλつの基どうしまたは几１〜
Ｒのいずれかと上記λ〜≠価残基とが互いに結合して１
．＋員環（シクロヘキシル基、スピロクロマン環、クロ
マン環、クマランＪ１ナト）全形成してもよい。Kirani 几1~R5 adjacent λ groups or 几1~
Any one of R and the above λ~≠valent residue are bonded to each other to form 1
．． All +-membered rings (cyclohexyl group, spirochroman ring, chroman ring, coumaran J1 nato) may be formed.
一般式（１）で示されるもののうち本発明の効果の点で
好ましいのは一般式〔１′ 〕で表わされる化合物であ
る。Among the compounds represented by the general formula (1), compounds represented by the general formula [1'] are preferred from the viewpoint of the effects of the present invention.
ＯＨ０１（
一般式〔工′〕
ここで、Ｂは−８−１−８−８−１−〇−１−ＣＨ２−
８−ＣＨ２−１−８Ｏ２−１−８Ｏ−１ＣＨ２−Ｏ−（
）１２−１會示す。OH01 (General formula [Eng']) Here, B is -8-1-8-8-1-〇-1-CH2-
8-CH2-1-8O2-1-8O-1CH2-O-(
) 12-1 meeting.
几 、几 、几 、Ｒは好ましくは、各々水素原子また
は炭素数／から２０のアルキル基、アリール基、アラル
キル基、アルキルチオ基、ハロケン、アルコキシ基、ア
リールチオ基、アラルキル基、アリルオキシ基、−Ｃ□
Ｂ２９、−ＮＨＣＯ几２９、−ＮＨ８０２Ｒ２９、−
８０□ｌ（，２９、−０−Ｃ’０Ｒ２９、±ＣＨ２十Ａ
を示す。Ｒは水素原子、アルキル基又はアリール基を
示し、几 、几 は各々水素原子、アルキル基、アリー
ル基または互いに結合し、置換されたｊ員もしくは６員
のｆｌ＆を示す。Ｂ２８は水素原子またはメチル基を示
す。几 はアルキル基又はアリール基を示し、几 、Ｒ
は各々水素原子、アルキル基、アリール基、ヘテロ環基
、アラルキル基または互いに結合し、前記した任意の置
換基を有するｊ員もしくはｔ員のへテロ環を示す。八は
エステル基または
次に一般式（Ｉｔ）について説明する。式中、Ｘを表わ
す。几 , 几 , 几 , R are each preferably a hydrogen atom or an alkyl group having from 20 carbon atoms, an aryl group, an aralkyl group, an alkylthio group, a halokene, an alkoxy group, an arylthio group, an aralkyl group, an allyloxy group, -C□
B29, -NHCO几29, -NH802R29, -
80□l(,29,-0-C'0R29,±CH20A
shows. R represents a hydrogen atom, an alkyl group, or an aryl group, and R and R each represent a hydrogen atom, an alkyl group, an aryl group, or a substituted j- or 6-membered fl& bonded to each other. B28 represents a hydrogen atom or a methyl group.几 represents an alkyl group or an aryl group, and 几 , R
each represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an aralkyl group, or a j- or t-membered heterocycle bonded to each other and having any of the above-mentioned substituents. 8 is an ester group.Next, general formula (It) will be explained. In the formula, X is represented.
Ｒ６−Ｒ９は水素原子、置換基ｌたは化学結合を衣す。R6-R9 represent a hydrogen atom, a substituent or a chemical bond.
置換基としてはアルキル基（例え＆′ｉコークロロエチ
ル基、ｎ−ヘキシル基、ｎ−オクチル基、１ｓｏ−デシ
ル基、メチル基、ドデシル基、オフタデフル基など）、
シクロアルキル基（例えばシクロヘキシル基など）、ア
リール基（例えばフェニル基、トルイル基、３−メトキ
シフェニル基、ｒｌ −／ ニー Ａ／フェニル基など
）などが挙げられる。Examples of substituents include alkyl groups (e.g. &′i-cochloroethyl group, n-hexyl group, n-octyl group, 1so-decyl group, methyl group, dodecyl group, ophtadefur group, etc.);
Examples thereof include cycloalkyl groups (eg, cyclohexyl group), aryl groups (eg, phenyl group, tolyl group, 3-methoxyphenyl group, rl −/ni A/phenyl group, etc.).
Ｒ６−Ｒ９が化学結合を表わす場合、その置換位置と、
直接またはλ〜≠価残基を介して、その価数に応じた数
の別の一般式（ｎ）で表わされる化合物のＲ６−Ｒ９の
任意の７つの置換位置で連結する）を衣わす。When R6-R9 represents a chemical bond, the substitution position and
directly or via λ~≠valent residues at any seven substitution positions of R6-R9 of another compound represented by the general formula (n), the number of which corresponds to the valence thereof.
さらに几６〜Ｒ９の任意のλつは互いにまたは上記のλ
〜μ価残基と連結し、弘〜６員環を形成してもよい。Further, any λ of R6 to R9 are mutually or the above λ
It may be linked to a μ-valent residue to form a six-membered ring.
次に一般式（ＤＩ）について説明する。式中、Ｗはｎ＝
ｌのとき水素原子、アンモニウム、畳迅 、Ｒ１１ｔ
、、ｎ−２のときＺ％Ｎｉを扮わす。ＢＩＯ１几１１は
アルキル基（例えばドデシルオキシカルボニルエチル基
、オクタデシルオキシカルボニルエチル基など）、複素
環残基（例えばベンズイミダゾリル基、ベンゾチアゾリ
ル基など）、−Ｃ−Ｙ（Ｙは一般式〔工〕のＹと同じ）
、（Ｒ−Ｒは各々置換されていてもよいアルキル基（例
えばメチル基、ｎ−ブチル基など）アリール基（例えは
フェニル基など）を表わす）を衣わす。Next, general formula (DI) will be explained. In the formula, W is n=
When l, hydrogen atom, ammonium, Tatami Jin, R11t
, , when n-2, Z%Ni is used. BIO1几11 is an alkyl group (e.g., dodecyloxycarbonylethyl group, octadecyloxycarbonylethyl group, etc.), a heterocyclic residue (e.g., benzimidazolyl group, benzothiazolyl group, etc.), -C-Y (Y is of the general formula Same as Y)
, (R-R each represents an optionally substituted alkyl group (eg, methyl group, n-butyl group, etc.) or an aryl group (eg, phenyl group, etc.)).
次に一般式〔ｌｌについて説明する。式中、Ｒ１５、几
１６はアルキル基（例えばメチル基、エチル基なト）、
シクロアルキル基（？ｌｊ、ｔはシクロヘキシル基など
）、アルケニル基（例えはプロペニル基など）、アリー
ル基（例えはフェニル基、ナフチル基など）、を衆わし
、これらは互いに連結してよ〜６員塩を形成してもよい
。Next, general formula [ll] will be explained. In the formula, R15 and 16 are alkyl groups (e.g. methyl group, ethyl group),
A cycloalkyl group (?lj, t is a cyclohexyl group, etc.), an alkenyl group (e.g., a propenyl group, etc.), an aryl group (e.g., a phenyl group, a naphthyl group, etc.), which are connected to each other. A member salt may be formed.
上記−最大ＣＩ）〜（ＩＶ”ｌの化合物は、酸化防止剤
として従来公知の化合物てあシ、たとえは神谷佳男著「
有機酸化反応」（技報堂 ｌり７３）、猿渡、西野、田
端著「酸化防止剤ハンドブック」（大成社ｌり７６）や
梶本他著「抗酸化剤の理論と実際」（三琲書房ｌりｒｐ
）などに細かい記載がある。The above-mentioned compounds (maximum CI) to (IV"l) are conventionally known compounds as antioxidants, such as the one written by Yoshio Kamiya.
``Organic Oxidation Reactions'' (Gihodo Luri 73), ``Antioxidant Handbook'' by Saruwatari, Nishino, and Tabata (Taiseisha Luri 76), and ``Theory and Practice of Antioxidants'' by Kajimoto et al. (Sanki Shobo Luri rp.
) etc. have detailed descriptions.
本発明において、−最大（１）〜〔■〕の化合物は感光
性ハロゲン化銀、還元剤を内蔵する熱現像ｇ光材料にお
いて、内蔵還元剤の酸化防止剤として、大きな効果を有
することがわかった。In the present invention, it has been found that the compounds of -maximum (1) to [■] have great effects as antioxidants for the built-in reducing agent in photosensitive silver halide and heat-developable optical materials containing a reducing agent. Ta.
胤下に一般式ＣＩ）〜〔■〕に表される化合物の具体例
を挙げる。Specific examples of compounds represented by general formulas CI) to [■] are listed below.
一般式（Ｉ）の例 ４Ｈｇ−ｎ ＣＨ３６日。Example of general formula (I) 4Hg-n CH36th.
１３゜
１４゜
Ｏ２ＣＨ３
１５゜
ＣＨａ
１（１，Ｎ＋ＣＨｚＣＨｚＯＨ）ａ
区
Ｎ；
ｂ
２３゜
２６゜
ＵＵ２Ｕ１６ｔｉ３３
ＣＯ２Ｃ１２Ｈ２ｓ
３９゜
４３゜
４５゜
４６゜
Ｃ４Ｈ９
５０゜
５１゜
５２゜
５４゜
５６゜
Ｕ４Ｈ９
一般式（ＩＩ）の例
ｓｓ、 Ｐ＋ＯＣ４１−１９）’３５９、Ｐ土０
Ｃ８Ｈ１７−ｎ）３
６０・ Ｐ十〇Ｃ１２Ｈ２５） ｓ
６１、 Ｐ（−ＯＣＨ２ＣＨＣＨｐ）ａα
２Ｈ５
６４、 （ｎ−Ｃｘ２Ｈ２ｓＯ＋−ｒ−Ｐ −０
Ｈ６６、Ｐ（−ＱＣ１８８３７）ａ
ａｓ、 Ｐ＋ＳＣ１２Ｈ２５） ａ７２゜
７５゜
一般式（Ｉｎ）の例
７９．８
（（Ｃ４Ｈ９）２Ｎ Ｃｂｉ−２Ｚｎ
８１．８
（Ｅｔ２Ｎ Ｃ−８ガーＮｉ
８３゜
８７、 Ｓ（−ＣＨ２ＣＨ２ＣＯ２Ｃ１２Ｈ２５）
２８８゜
５（−ＣＨ２ＣＨ２ＣＯ２Ｃ１４！”１２９）２９０゜
８＋ＣＨ，２ＣＨ２ＣＯ□Ｃ１３Ｈ２７）２９１・
ＣＨａ
■
Ｓ＋ＣＨ−ＣＨ２ＣＯ２Ｃ１８Ｈ３７）２９２゜
ＣＨ３
９４゜
９５゜ ８
９６゜
一般式（ＩＶ〕の例
ＩＱｌ、 ＣＨ３１０２゜
１０３゜
１０４゜
これらの化合物は公知であり、市販品としても入手でき
るし、公知の方法により合成して使用することもできる
。13゜14゜O2CH3 15゜CHa 1 (1,N+CHzCHzOH) a Ward N; b 23゜26゜UU2U16ti33 CO2C12H2s 39゜43゜45゜46゜C4H9 50゜51゜52゜54゜56゜U4H9 General formula (II) Example of ss, P+OC41-19)'359, P Sat0
C8H17-n)3 60・P〇C12H25)s 61, P(-OCH2CHCHp)aα 2H5 64, (n-Cx2H2sO+-r-P -0
H66, P(-QC18837)a as, P+SC12H25) a72°75° Example of general formula (In) 79.8 ((C4H9)2N Cbi-2Zn 81.8 (Et2N C-8 GarNi 83°87, S( -CH2CH2CO2C12H25)
288°5(-CH2CH2CO2C14!”129)290°8+CH,2CH2CO□C13H27)291・
CHa ■ S+CH-CH2CO2C18H37) 292° CH3 94° 95° 8 96° Example of general formula (IV) IQl, CH3102° 103° 104° These compounds are known and can be obtained as commercial products, and can be obtained by known methods. It can also be synthesized and used.
上記の化合物は、感材膜に塗布時、感光性ハロゲン化銀
乳剤層、中間層、保護層他、どの層に添加してもよい。The above-mentioned compound may be added to any layer including the photosensitive silver halide emulsion layer, intermediate layer, and protective layer when coating the sensitive material film.
またその添加方法としては、高沸点有機溶媒と乳化分散
しても、特開昭ｊＰ−／７４ｃｒ３ｏ号に記載されでい
る微分散による固体分散法を用いてもよい。The addition method may be emulsification dispersion with a high boiling point organic solvent, or a solid dispersion method using fine dispersion as described in JP-A-ShojP-/74CR3O.
上記化合物の添加量としては、還元剤の０．００！−１
００倍程度が好ましく、さらに好ましくは、ｏ、ｏｉ〜
ｉｏ倍程度がよい。The amount of the above compound added is 0.00! of the reducing agent! -1
It is preferably about 00 times, more preferably o, oi~
About io times is good.
本発明の熱現像感光要素は、基本的には支持体上に感光
性ハロゲン化銀、バインダー還元剤を有するものであり
、さらに必要に応じて有機金属塩酸化剤、色素供与性化
合物（後述するように還元剤が兼ねる場合がある）など
を含有させることができる。これらの成分は同一の層に
重加することが多いが、反応可能な状態であれば別層に
分割して添加することもできる。例えば着色している色
素供与性化合物にハロゲン化銀乳剤の下層に存在させる
と感度の低下を防げる。還元剤はすべて熱現像感光要素
に内蔵するのが好ましいが、その−部を、例えば後述す
る色素固定要素から拡散させるなどの方法で、外部から
供給するようにしてもよい。The heat-developable photosensitive element of the present invention basically has a photosensitive silver halide and a binder reducing agent on a support, and if necessary, an organometallic salt oxidizing agent and a dye-donating compound (described later). In some cases, it may also serve as a reducing agent). These components are often added to the same layer, but if they are in a reactable state, they can be added separately to separate layers. For example, if a colored dye-providing compound is present in the lower layer of the silver halide emulsion, a decrease in sensitivity can be prevented. It is preferable that all of the reducing agent be incorporated into the photothermographic element, but a portion thereof may be supplied from the outside, for example, by diffusing it from a dye fixing element described below.
イエロー、マゼンタ、シアンの３原色を用いて色度図内
の広範囲の色を得るためには、少なくとも３層のそれぞ
れ異なるスペクトル領域に感光性を持つハロゲン化銀乳
剤層を組み合わせて用いる。In order to obtain a wide range of colors in the chromaticity diagram using the three primary colors yellow, magenta, and cyan, at least three silver halide emulsion layers each sensitive to a different spectral region are used in combination.
例えば宵感層、緑感層、赤感層の３１−の組み合わせ、
緑感層、赤感層、赤外感光層の組み台わせなどがある。For example, a 31- combination of evening sensing layer, green sensing layer, and red sensing layer,
There are assemblies of green-sensitive layers, red-sensitive layers, and infrared-sensitive layers.
各感光層は通常型のカラー感光材料で知られている種々
の配列順序を採ることができる。Each photosensitive layer can be arranged in various arrangements known for conventional color photosensitive materials.
また、これらの各感光層に必要に応じて２層以上に分割
してもよい。Further, each of these photosensitive layers may be divided into two or more layers as necessary.
熱現像感光要素には、保護層、下塗り層、中間Ｌ 黄色
フィルター層、アンチハレーション層、バック層などの
撞々の補助層を設けることができる。The heat-developable photosensitive element can be provided with various auxiliary layers such as a protective layer, an undercoat layer, an intermediate yellow filter layer, an antihalation layer, and a backing layer.
本発明に使用し得るハロゲン化銀は、塩化銀、臭化鏝、
大臭化銀、塩臭化銀、塩沃化銀、虫沃臭化銀のいずれで
もよい。Silver halides that can be used in the present invention include silver chloride, trowel bromide,
Any of silver macrobromide, silver chlorobromide, silver chloroiodide, and silver iodobromide may be used.
本発明で使用するハロゲン化銀乳剤は、衣面潜像型乳剤
であっても、内部潜像型乳剤であってもよい。内部ｍ像
型乳剤は造核剤や元カブラセとを組合わせて直接反転乳
剤として使用される。また、粒子内部と粒子表層が異な
る相を持ったいわゆるコアシェル乳剤であってもよい。The silver halide emulsion used in the present invention may be a surface latent image type emulsion or an internal latent image type emulsion. The internal m-image type emulsion is used as a direct reversal emulsion in combination with a nucleating agent and a former fogging agent. It may also be a so-called core-shell emulsion in which the inside of the grain and the surface layer of the grain have different phases.
ハロゲン化銀乳剤は単分散でも多分散でもよく、単分散
乳剤を混合して用いてもよい。粒子サイズは０．／〜λ
μ、特に０，２〜ｉ、ｒμが好ましい。ハロゲン化銀粒
子の晶癖は立方体、に面体、／≠面体、高アスペクト比
の平板状その他のいずれでもよい。The silver halide emulsion may be monodisperse or polydisperse, or a mixture of monodisperse emulsions may be used. Particle size is 0. /~λ
μ, particularly 0.2 to i, rμ is preferred. The crystal habit of the silver halide grains may be cubic, dihedral, /≠hedral, tabular with a high aspect ratio, or any other form.
具体的には、米国特許第弘、、！１００，１．２６号第
ｊＯ欄、同第！、１．．２１，０２／号、リサーチ・デ
ィスクロージャー誌（以下ＲＬ）と略記する）／７０２
り（ｌり７を缶）、特開昭＆、２−２１３／ｊ２号等に
記載されているハロゲン化銀乳剤のいずれもが使用でき
る。Specifically, U.S. Patent No. Hiroshi,,! 100, 1.26 No. jO column, same No.! , 1. ．． 21,02/issue, Research Disclosure magazine (hereinafter abbreviated as RL)/702
Any of the silver halide emulsions described in Japanese Patent Application Laid-open No. 2-213/j2, etc. can be used.
ハロゲン化銀乳剤は未後熟のまま使用してもよいが通常
は化学増感して使用する。通常型感光材料用乳剤で公知
の硫黄増感法、還元増感法、貴金属増感法などを単独ま
たに組合わせて用いることができる。これらの化学増感
を含窒素複素環化合物の存在下で行うこともできる（特
開昭６２−２よ３／ｊり号）。Although the silver halide emulsion may be used unripe, it is usually used after being chemically sensitized. For emulsions for conventional light-sensitive materials, known sulfur sensitization methods, reduction sensitization methods, noble metal sensitization methods, etc. can be used alone or in combination. These chemical sensitizations can also be carried out in the presence of a nitrogen-containing heterocyclic compound (JP-A-62-2, No. 3/j).
本発明において使用される感光性ノ・ロゲン化銀の塗設
ｉｉｉは、銀換算／ダないし１０１／ｍ２の範囲である
。The photosensitive silver halide coating III used in the present invention is in the range of silver equivalent/da to 101/m2.
本発明に用いられるノ・ロゲン化ｓｉ、メチン色素類そ
の他によって分光増感されてもよい。用いられる色素に
は、シアニン色素、メロシアニン色素、複合シアニン色
素、複合メロンアニン色素、ホロポーラ−シアニン色素
、ヘミシアニン色素、スチリル色素およびヘミオキンノ
ール色素が包含される。Spectral sensitization may be performed using rosinated Si, methine dyes, and others used in the present invention. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex melonanine dyes, holopolar-cyanine dyes, hemicyanine dyes, styryl dyes and hemioquinol dyes.
具体的には、米国特許第弘、４１７，２１７ｇ、特開昭
ｒｙ−ｉｒｏｓｊｏ号、同ｔｏ−ｉａｏ３３ｊ号、ｆＬ
Ｄ／７ｏ２り（ｌり７１年）７２〜１３日等に記載の増
感色素が挙げられる。Specifically, U.S. Pat.
Examples include sensitizing dyes described in D/7o2 (1971) 72-13.
これらの増感色素は単独に用いてもよいが、それらの組
合わせを用いてもよく、増感色素の組合わせは特に、強
色増感の目的でしげしげ用いられる。These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization.
増感色素とともに、それ自身分光増感作用をもたない色
素あるいは可視光を実質的に吸収しない化合物であって
、強色増感を示す化合物を乳剤中に官んでもよい（例え
ば米国特許第ｊ、ｂ／ｉ？。Along with the sensitizing dye, a dye that does not itself have a spectral sensitizing effect or a compound that does not substantially absorb visible light and exhibits supersensitization may be incorporated into the emulsion (for example, as described in US Pat. j, b/i?
６弘１号、特願昭ｔ／−コ２４．２タグ号等に記載のも
の）。6 Hiro No. 1, Tokugan Sho t/-ko 24.2 tag number, etc.).
こｎらの増感色素全乳剤中に添加する時期は化学熟成時
もしくはその前後でもよいし、米国特許第！、／１３，
７１Ａ号、同４！、２２１，６６６号に従ってハロゲン
化銀粒子の核形成前後でもよい。飽加童に一般にハロゲ
ン化銀１モル当たりｌ、７Ｂないしｉｏ モル程度
である。These sensitizing dyes may be added to the entire emulsion during or before chemical ripening, and US Patent No. , /13,
No. 71A, same number 4! , 221,666, may be performed before or after nucleation of silver halide grains. Generally, the amount is about 1,7B to io moles per mole of silver halide.
本発明においては、感光性ハロゲン化銀と共に、有機金
属塩を酸化剤として併用することもできる。In the present invention, an organic metal salt can also be used as an oxidizing agent together with photosensitive silver halide.
このような有機金属塩の中、有機銀塩は、特に好ましく
用いられる。Among such organic metal salts, organic silver salts are particularly preferably used.
上記の有機銀塩酸化剤を形成するのに使用し得るＭ機化
合物としては、米国特許第≠、 ｊｏｏ。M-organic compounds that can be used to form the above organic silver salt oxidizing agents include those described in U.S. Pat.
乙２６号第ｊλ〜ｊ３＠等に記載のベンゾトリアゾール
類、脂肪酸その他の化合物がある。また特開昭ｔｏ−ｉ
ｉ３２３ｓ号記載のフェニルプロピオール酸銀なとのア
ルキニル基を有するカルボン酸の銀塩や、特開昭Ａ ／
−２ＩＩりＯ弘≠号記載のアセチレン銀も有用である
。有機銀塩は２種以上を併用してもよい。There are benzotriazoles, fatty acids, and other compounds described in Otsu No. 26, No. jλ to j3@, etc. Also, Tokukai Sho to-i
Silver salts of carboxylic acids having an alkynyl group such as silver phenylpropiolate described in No. i323s, and JP-A-Sho A/
Acetylene silver described in No.-2II, Ohiro≠ is also useful. Two or more types of organic silver salts may be used in combination.
以上の有機銀塩は、感光性ハロゲン化銀１モルあたり、
Ｏ０Ｏ／ないしｉｏモル、好ましくはθ。The above-mentioned organic silver salts contain, per mol of photosensitive silver halide,
O0O/ to io mol, preferably θ.
０／ないし１モルを併用することができる。感光性ハロ
ゲン化銀と有機銀塩の塗布社合計は銀換算でｓｏｍｇな
いし１０り７ｍ２が〕願当である。A combination of 0/1 to 1 mole can be used. The total amount of photosensitive silver halide and organic silver salt coating is expected to be 7 m2 in terms of silver.
本発明においては棟々のカブリ防止剤または写真安定剤
を使用することができる。その例としては、ＲＤ／７Ａ
！ｊ（／Ｆ７！ｒ年）２４４〜，２を頁に記載のアゾー
ル類やアザインデン類、特開昭ｊター／１，１弘≠２号
記載の窒素を含むカルボン酸類およびリン酸類、あるい
は特開昭ｊター／／／４３６号記載のメルカプト化合物
およびその金属塩、特開昭６２−４７７！７号に記載さ
れているアセチレン化合物類などが用いられる。Various antifoggants or photographic stabilizers can be used in the present invention. An example is RD/7A
! azoles and azaindenes described on pages 244-2, nitrogen-containing carboxylic acids and phosphoric acids described in JP-A Shojter/1,1 Hiro≠2, or JP-A Mercapto compounds and metal salts thereof described in Shojter////436, acetylene compounds described in JP-A No. 62-477!7, and the like are used.
本発明に用いる還元剤としては、熱現揮感元材料の分野
で知られているものを用いることができる・筐た・後述
する還元性を有する色素供与性化合物も含まれる（この
場合、その他の還元剤を併用することもできる）。また
、それ自身は還元性を持たないが現像過程で求核試薬や
熱の作用により還元性を発現する還元性プレカーサーも
用いることができる。As the reducing agent used in the present invention, those known in the field of heat developable sensitizing materials can be used. (can also be used in combination with a reducing agent). Further, a reducing precursor which does not itself have reducing properties but exhibits reducing properties by the action of a nucleophile or heat during the development process can also be used.
本発明に用いられる還元剤の例としては、米国特許第弘
、１００．ｔコを号の第μり〜ＳＯ＠。Examples of reducing agents used in the present invention include U.S. Patent No. 100. This is the first issue of tco~SO@.
同第≠、≠１３．り／≠号の第３Ｑ〜３ノ欄、同第弘、
！３０，６１７号、同第≠、ｒｙｏ、ｉｓコ号、特開昭
６０−／４！０３３Ｊ号の第（１７）〜＜ｉｔ）頁、同
！７−４０２１７！号、同ｊｔ−／３１７３４号、同１
９−／７１’Ａｊ１号、同ｊｔターｒ３ｒＪｉ号、同３
？−／ｌ’２４Ｌ４ｔ？号、同よターｉｔ、日！Ｏ号、
同６ｏ−ｉｉり５５５号、同１．０−／２Ｆ！３４号か
ら同１．０−／２１ｒｌｌＪＷ号まで、同６０−１９１
！≠θ号、同６０−ノｔ１７≠λ号、同６／−コ！り２
ｊＪ号、同６．２−コ弘弘０≠参号、Ｆ１４λ−１３１
２５３号から同６２−／３／、２ｊ４号まで、欧州特許
第２２０゜７弘４Ａ、２号の第７ｔ〜りを員等に記載の
還元剤や還元剤プレカーサーがある。Same No.≠,≠13. 3rd Q to 3rd column of ri/≠ issue, same No. Hiroshi,
! No. 30,617, ≠, ryo, isco issue, pages (17) to <it) of JP-A-60-/4!033J, same! 7-40217! No., jt-/31734, No. 1
9-/71'Aj No. 1, Same jt r3r Ji No. 3, Same No. 3
? -/l'24L4t? No., ditto, day! No. O,
6o-ii No. 555, 1.0-/2F! From No. 34 to No. 1.0-/21rll JW, No. 60-191
! ≠θ issue, 60-not 17≠λ issue, 6/-ko! Ri2
jJ No. 6.2-Ko Hirohiro 0≠No. 3, F14λ-131
There are reducing agents and reducing agent precursors described in European Patent Nos. 253 to 62-/3/, 2j4, and European Patent Nos. 220°7-4A, 2, No. 7t.
米国特許第３．θ３り、♂６２号に開示されているもの
のような種々の還元剤の組合せも用いることができる。U.S. Patent No. 3. Combinations of various reducing agents can also be used, such as those disclosed in θ3 and ♂62.
耐拡散性の還元剤を使用する場合には、耐拡散性還元剤
と現像可能なハロゲン化銀との間の電子移動を促進する
ために、必要に応じて電子伝達剤および／または電子伝
達剤プレカーサーを組合せて用いることができる。If a diffusion-resistant reducing agent is used, an electron transfer agent and/or electron transfer agent is optionally added to facilitate electron transfer between the diffusion-resistant reducing agent and the developable silver halide. Combinations of precursors can be used.
電子伝達剤またはそのプレカーサーは、前記した還元剤
またはそのプレカーサーの中から選ぶことができる。電
子伝達剤またはそのプレカーサーはその移動性が耐拡散
性の還元剤（電子供与体）より大きいことが望ましい。The electron transfer agent or its precursor can be selected from the aforementioned reducing agents or its precursors. It is desirable that the mobility of the electron transfer agent or its precursor is greater than that of the diffusion-resistant reducing agent (electron donor).
特に有届な電子伝達剤にｌフェニル−３−ピラゾリドン
類またにアミノフェノール類である。Particularly known electron transfer agents are l-phenyl-3-pyrazolidones and aminophenols.
電子伝達剤と組合騒で用いる耐拡散性の還元剤（′電子
供与体）としては、前記した還元剤の中て感光要素の層
中で実質的に移動しないものであれａｚ＜、好ｔしくは
ハイドロキノン類、スルホンアミドフェノール類、スル
ホンアミドナフトール類、特開昭ｊ３−、１ｉｏｒ、２
７号に電子供与体として記載されている化合物および後
述する耐拡散性で還元性を有する色素供与性化合物等が
挙げられる。The diffusion-resistant reducing agent ('electron donor) used in combination with the electron transfer agent is preferably one of the above-mentioned reducing agents that does not substantially migrate in the layer of the photosensitive element. are hydroquinones, sulfonamidophenols, sulfonamidonaphthols, JP-A-1999-11-2
Examples include compounds described as electron donors in No. 7 and dye-donating compounds having diffusion resistance and reducing properties described below.
本発明に於いては還元剤の浩加＊は銀１モルに対して０
．０１〜−０モル、特に好筐しくは０゜／〜ｉｏモルで
ある。In the present invention, the amount of reducing agent* is 0 per mole of silver.
．． 01 to -0 mol, particularly preferably 0°/~io mol.
本発明においては、画像形成物質として銀を用いること
ができる。また高温状態下で銀イオンが銀に還元される
際、この反応に対応して、あるいは逆対応して可動性色
素を生成するか、あるいは放出する化合物、すなわち色
素供与性化合物を含有することもできる。In the present invention, silver can be used as the image forming material. It may also contain a compound that generates or releases a mobile dye in response to or inversely to this reaction when silver ions are reduced to silver under high temperature conditions, that is, a dye-donating compound. can.
本発明で使用しうる色素供与性化合物の例としてはまず
、酸化カップリング反応によって色素を形成する化合物
（カプラー）を挙げることができる。このカプラーは≠
当量カプラーでも、２当証カプラーでもよい。また、耐
拡散性基を脱離基に持ち、酸化カップリング反応によシ
拡散性色素を形成する２当量カプラーも好ましい。この
耐拡散性基はポリマー鎖をなしていてもよい。カラー現
像薬およびカプラーの具体例はジエームズ著「ザセオリ
ー オブ ザフオトグラフィック プロセス」第φ版（
Ｔ、Ｈ，Ｊａｍｅｓ″Ｔｈｅ Ｔｈｅｏｒｙ ｏｆｔｈ
ｅ ）’ｈｏｔｏｇｒａｐｈｉｃ Ｐｒｏｃｅｓｓ’）
、２り／〜３３≠員、および３ｊ弘〜３６／員、特開昭
！１−／２３ｊ３３号、同３１−／１９０１Ａ／ａ号、
同１１−／≠りＯ≠７号、同よター／／ｌ／≠を号、同
ｊター／２弘３タタ号、同！ター１７参ｔＪｊ号、同ｊ
ター２３／！３Ｙ号、同ｊター２３／ ｊＩＡＯ号、同
６Ｏ−２９ｊＯ号、同４０−２９！１号、同６０−／≠
２≠λ号、同ｔθ−２３≠７≠号、同６Ｏ−４Ａコ≠り
号等に詳しく記載されている。Examples of dye-providing compounds that can be used in the present invention include compounds (couplers) that form dyes through oxidative coupling reactions. This coupler is ≠
It may be an equivalent coupler or a two equivalent coupler. Also preferred are two-equivalent couplers that have a diffusion-resistant group as a leaving group and form a diffusible dye through an oxidative coupling reaction. This diffusion-resistant group may form a polymer chain. Specific examples of color developers and couplers are given in “The Theory of the Photographic Process” by James, φth edition (
T.H.James''The Theory ofth
e)'photographic Process')
, 2ri/~33≠members, and 3j Hiroshi~36/members, Tokukai Sho! 1-/23j No. 33, 31-/1901A/a,
Same 11-/≠riO≠7 issue, sameyo tar//l/≠ issue, same j tar/2hiro 3 Tata issue, same! No. 17 tJj, same j
Tar23/! No. 3Y, No. 23/JIAO, No. 6O-29jO, No. 40-29!1, No. 60-/≠
It is described in detail in No. 2≠λ, No. tθ-23≠7≠, No. 6O-4A≠, etc.
また、別の色素供与性化合物の例として、画像状に拡散
性色素を放出乃至拡散する機能を持つ化合物を挙けるこ
とができる。この型の化合物は次の一般式（ＬＩ〕で表
わすことができる。Further, as another example of the dye-providing compound, there can be mentioned a compound having a function of releasing or diffusing a diffusible dye in an imagewise manner. This type of compound can be represented by the following general formula (LI).
（Ｄｙｅ −Ｙ ＞ｎ−Ｚ ＣＬ Ｉ
ＩＤｙｅは色素基、−時的に短波化された色素基またに
色素前駆体基を表わし、Ｙは単なる結＠または連結基を
表わし、Ｚは画像状に潜像を肩する感元性嫁塩に対応ま
たは逆対応して
（Ｄｙ ｅ −Ｙ ） ｎ−Ｚで畏わされる化合物の拡
散性に差を生じさせるか、またはｓ Ｄｙｅ ｔ−放出
し、放出され７ｊＤｙｅと（Ｄｙｅ Ｙ）ｎ Ｚとの間
に拡散性において差を生じさせるような性質を有する基
を表わし、ｎＦｉ／またはコを表わし、ｎが２の時、２
つのＤｙｅ−Ｙは同一でも異なっていてもよい。(Dye -Y >n-Z CL I
IDye represents a dye group, a dye group temporally shortened or a dye precursor group, Y represents a simple linkage or a linking group, and Z is a sensitive bride salt that carries a latent image in an imagewise manner. Correspondingly or inversely to (Dye -Y)n-Z, causing a difference in the diffusivity of the compound concerned, or sDye t-released and released7jDye and (DyeY)nZ represents a group having properties that cause a difference in diffusivity between
The two Dye-Ys may be the same or different.
−最大（ＬＩＩで弄わされる色素供与性化合物の具体例
としては下記の■〜■の化合物を挙げることができる。- Maximum (Specific examples of dye-providing compounds that can be treated with LII include the following compounds (1) to (2).
なお、下記の■〜■はハロゲン化銀の現像に逆対応して
拡散性の色素像（ポジ色素像）を形成するものであり、
■と■はハロゲン化銀の現像に対応して拡散性の色素像
（ネガ色素像）を形成するものである。Note that ■ to ■ below are those that form a diffusive dye image (positive dye image) in reverse response to silver halide development.
(2) and (2) form a diffusive dye image (negative dye image) in response to silver halide development.
■米国特許部３．／３≠、７６≠号、同第３゜３６１、
ｌｒ／り号、同第３．！２７，２００号、同第３．！≠
≠、おり号、同第３．≠ｔλ、り７−号等に記載されて
いる、ハイドロキノン系現像薬と色素成分を連結した色
素現は薬。この色素現１票薬はアルカリ性の環境下で拡
散性であるが、ハロゲン化銀と反応すると非拡散性にな
るものである。■U.S. Patent Department 3. /3≠, 76≠ issue, same number 3゜361,
lr/ri issue, same No. 3. ! No. 27,200, No. 3. ! ≠
≠, No. 3. ≠tλ, a dye developer in which a hydroquinone developer and a dye component are linked, as described in No. 7-, is a drug. This dye agent is diffusible in an alkaline environment, but becomes non-diffusible when it reacts with silver halide.
■米国特許第弘、３０３．／３７号等に記されている通
り、アルカリ性の環境下で拡散性色素を放出するがハロ
ゲン化銀と反応するとその能力を失う非拡散性の化合物
も使用できる。その例としては、米国特許筒３．２ｇｏ
、≠７２号等に記載された分子円求核置侠反応によシ拡
散性色素を放出する化合物、米国特許筒≠、／り２．３
よ≠号等に記載されたインオキサシロン環の分子内巻き
換え反応によシ拡散住色素を放出する化合物が挙けられ
る。■US Patent No. 303. As described in No. 37, etc., non-diffusible compounds that release diffusible dyes in an alkaline environment but lose this ability when reacted with silver halide can also be used. An example is the U.S. patent cylinder 3.2go
, ≠ No. 72, etc., a compound that releases a diffusible dye by a molecular circular nucleophilic reaction, US Patent No. ≠, / 2.3
Compounds that release a diffusing pigment due to an intramolecular rewinding reaction of the inoxacilone ring, as described in the ≠ issue, etc., can be mentioned.
■米国特許第≠、５６り、２９０号、欧州特許筒２２０
．７１１６１’２号、公開液＄ｌｌｆ ７−１ ／ ９
り尋に記されている通）、現像によって酸化されずに残
った還元剤と反応して拡散性色素を放出する非拡散性の
化合物も使用できる。■US Patent No. ≠, No. 56, No. 290, European Patent No. 220
．． 71161'2, publication liquid $llf 7-1/9
Non-diffusible compounds can also be used which react with the reducing agent remaining unoxidized by development to release a diffusible dye (as described in Rihiro et al.).
その例としては、米国特許に≠、／３り、３１２号、同
第弘、／３り、３７２号、特開昭ｔｙ−／ｒ！、３３Ｊ
号、同ｊ７−４１１ＩＩｊＪ号等に記載されている還元
さｎた後に分子内の求核１を侯反応により拡散性の色素
を放出する化合物、米国特許筒≠、２３コ、１０７号、
特開昭ｊター１０／６弘２号、同６／−♂ｔ２！７号、
ＲＤコ≠Ｏコ！（ｌりＩ≠年）等に記載された還元され
た後に分子内の電子移動反応により拡散性の色素を放出
する化合物、***特許筒３，００１．ｊ−ｒｒＡ号、特
開昭６４−／弘２ｊ３Ｄ号、米国特許第弘、３μＪ、Ｉ
り３号、同第≠、４／り、ｒｒ弘号等に記載されている
還元後に一重結合が開裂して拡散性の色素を放出する化
合物、米国特許筒μ、μｊＯ１２２３号等に記載されて
いる電子受容後に拡散性色素を放出するニトロ化合物、
米国特許第弘。Examples include U.S. Pat. , 33J
No. J7-411IIJJ, etc., a compound which releases a diffusible dye by a reaction with nucleophilic 1 in the molecule after reduction, U.S. Patent No. 23, No. 107,
Tokukai Shojter 10/6 Hiro2 No. 2, same 6/-♂t2!7,
RD Ko≠O Ko! A compound that releases a diffusive dye by an intramolecular electron transfer reaction after being reduced, described in (I≠) et al., West German Patent No. 3,001. J-rrA No., JP-A-64-/Ko2j3D, U.S. Patent No. Hiroshi, 3μJ, I
Compounds whose single bonds are cleaved after reduction to release a diffusible dye are described in U.S. Patent No. 3, U.S. Pat. nitro compounds that release diffusible dyes after accepting electrons,
U.S. Patent No.
６０り、 ６ｉｏ号等に記載されている電子受容後に拡
散性色素を放出する化合物などが挙げられる。Examples include compounds that release a diffusible dye after accepting electrons, as described in No. 60, No. 6io, and the like.
また、より好ましいものとして、欧州特許筒２２０．７
≠６λλ号、公開枝振１７−６／Ｐり、％願昭Ｊ、２−
Ｊ４ｔり５３号、同６２−ｊ４Ｌり！≠号等に記された
一分子内にＮ−Ｘ結＠（Ｘは酸素、硫黄または窒素原子
を表す）と電子吸引性基を有する化合物、特願昭６２−
ｉｏｔｒｒｊ号に記された一分子内に８０２−Ｘ（Ｘは
上記と同義）と電子吸引性基に有する化合物、特願昭６
２−１０６１ｚｊ号に記された一分子内にＰＯ−Ｘ結合
（Ｘは上記と同義ンと電子吸引性基を有する化合物、特
願昭６２−１０１ｓＪ＃７号に記された一分子内にｃ−
ｘ’結合（Ｘ′はＸと同義かまたは−８０２−ヲ表す）
と電子吸引性基を有する化合物が挙げられる。Moreover, as a more preferable one, European patent tube 220.7
≠6λλ issue, published branch 17-6/P, % Gansho J, 2-
J4tri No. 53, same 62-j4Lri! Compounds having an N-X bond @ (X represents oxygen, sulfur, or nitrogen atom) and an electron-withdrawing group in one molecule as indicated in the ≠ number, etc., patent application 1982-
A compound having 802-X (X has the same meaning as above) and an electron-withdrawing group in one molecule described in No. iotrrj, patent application 1983
A compound having a PO-X bond (X has the same meaning as above) and an electron-withdrawing group in one molecule as described in No. 2-1061zz; −
x' bond (X' is synonymous with X or represents -802-wo)
and a compound having an electron-withdrawing group.
この中でも特に−分子内にＮ−Ｘ結合と電子吸引性基を
有する化合物が好ましい。その具体例は欧州特許筒２．
２（７，７１１６Ａ、コに記載された化合物（１）〜（
３）、（７）〜（１０）、（／２）、（／３）、（／ｊ
）、（２３）〜（λ６）、（３／）、（３２）、（３ｊ
）、（３Ａ）、（≠Ｏ）、 （ｔＩ／ ）、 （弘≠
ン、 （夕３ ）〜ＨＬ？）、 （６μ）、（７０）、
公開枝振ｆ ７−１ ／タタの化合物（／ｌ）〜（２３
）などである。Among these, compounds having an N-X bond and an electron-withdrawing group in the -molecule are particularly preferred. A specific example is European patent cylinder 2.
2 (7,7116A, Compounds (1) to (
3), (7) to (10), (/2), (/3), (/j
), (23) ~ (λ6), (3/), (32), (3j
), (3A), (≠O), (tI/ ), (Hiroshi≠
N, (Evening 3) ~HL? ), (6μ), (70),
Public branch f 7-1 / Tata compound (/l) ~ (23
) etc.
■拡散性色素を脱離基に持つカプラーであって還元剤の
敵化体との反応にエリ拡散性色素を放出する化合物（Ｄ
ＤＲカプラー）。具体的には、英国時ｆｆｆ第１，３３
０．ｊ２’１号、特公昭ｌＡｌ−３ｙ、ｉｔｓ号、米国
特許筒３．≠弘３．２弘Ｏ号、同第４＜、＄７４＜、Ｆ
Ａ７号、同第ｉｔ、ａｙ３．ｙ／４ｃ号等に記載された
ものがある。■A compound that is a coupler with a diffusible dye as a leaving group and releases an eli-diffusible dye upon reaction with the enemy of a reducing agent (D
DR coupler). Specifically, UK time fff 1st, 33rd
0. J2'1 No. 1, Special Publication Showa Al-3y, its No. 3, US Patent No. 3. ≠Hiro 3.2 Hiro O No. 4<, $74<, F
A7, same No. it, ay3. There are those described in No. y/4c, etc.
■ハロゲン化銀または有機銀塩に対して還元性であり、
相手を還元すると拡散性の色素を放出する化合物（Ｄ８
几化合物）。この化合物は他の還元剤を用いなくてもよ
いので、還元剤の酸化分解物による画像の汚染という問
題がなく好ましい。■Reducing to silver halide or organic silver salt,
A compound that releases a diffusible dye upon reduction of its partner (D8
compound). Since this compound does not require the use of any other reducing agent, it is preferable since there is no problem of image staining due to oxidative decomposition products of the reducing agent.
その代表例は、米国特許筒３．２．２ｒ、３１２号、同
第φ、０１３．Ｊ／λ号、同第≠、０！！、≠コ１号、
同第弘、３３４．３２λ号、特開昭！ター６ｚｒ３ｙ号
、同ｔｙ−ｔｙｒＪｙ号、同ｊ３−３ｔｉｒ号、同ｊ／
−１０１ｆｉ、３１Ａ！号、ＲＤ／７≠６ｊ号、米国特
許筒３，７コｊ、ａｔＪ号、同第３，７２１．／／Ｊ号
、同第Ｊ、 ４ｃ＠ｊ、 タ３り号、特開昭１１１−／
／ｌ、３３７号、同ｊ７−／７２を弘Ｑ号、米国特許筒
μ、ＺＯ０，４２を号等に記載されている。ＤＲ几几合
物の具体例としては前述の米国特許第弘、！００，６２
６号の第ココ欄〜第参μ欄に記載の化合物を挙げること
ができるが、なかでも前記米国特許に記載の化合物（１
）〜（３）、（／θ）〜（／３）、（１６）〜（／２）
、（，２ｊ）〜（ｊ□）、（３３） 〜（３ｊ）、（３
１） 〜（４１）、（弘２）〜（ハリが好ましい。ま九
米国特許第≠。Typical examples are U.S. Patent No. 3.2.2r, No. 312, U.S. Patent No. φ, 013. J/λ issue, same issue ≠, 0! ! ,≠Ko1,
The same No. 334.32λ, Tokukai Sho! 6zr3y, ty-tyrJy, j3-3tir, j/
-101fi, 31A! No., RD/7≠6j, U.S. Patent No. 3,7, atJ, No. 3,721. //J issue, same number J, 4c@j, Ta 3ri issue, JP-A-111-/
/1, No. 337, J7-/72 in Kou Q, U.S. Patent No. μ, ZO0,42, etc. A specific example of a DR compound is the above-mentioned U.S. Patent No. Hiroshi! 00,62
Among them, the compounds described in the above-mentioned US patent (1) can be mentioned.
) ~ (3), (/θ) ~ (/3), (16) ~ (/2)
, (,2j) ~ (j□), (33) ~ (3j), (3
1) - (41), (Hiroshi 2) - (Hardness is preferred. Maku U.S. Patent No. ≠.
Ａ３ヂ、弘Ｏｒ号第３７〜３２欄に記載の化合物も有用
である。Also useful are the compounds described in columns 37-32 of A3ji, Hiro Or.
その他、上記に述べたカプラーや一般式（ＬＩ ）以外
の色素供与性化合物として、有機銀塩と色素金結侶した
色素銀化合物（リサーチ・ディスクロージャー誌／９７
１年！月号、ｊ弘〜ｓｒ頁等）、熱現像銀色素漂白法に
用いられるアゾ色素（米国特許第≠、２３１．り５７号
、リサーチ・ティスフロージャー誌、／り７６年弘月号
、３０〜３コ頁８）、ロイコ色素（米国特許第３．りＩ
ｊ、ｊ６よ号、同弘、０２コ、６７７号等）なども使用
で籾る。In addition, as dye-donating compounds other than the above-mentioned couplers and general formula (LI), dye silver compounds bonded with organic silver salts and dye gold (Research Disclosure Magazine/97
1 year! Azo dyes used in heat-developable silver dye bleaching methods (U.S. Patent No. 231, No. 57, Research Tissue Flower, Hirotsuki issue, 1976, 30) -3 pages 8), leuco dyes (U.S. Patent No. 3.
j, j6yo, Dohiro, 02ko, 677, etc.) can also be used.
色素供与性化合物、耐拡散性還元剤などの疎水性添加剤
は米国特許第２，３λλ、０２７号記載の方法などの公
知の方法により感光要素の層中に導入することができる
。この場合には、特開昭ｊター１３１！≠号、同ｊター
ｉ７ｒ≠ｊ１号、同！デー／７ｒｌＡｊＪ号、同！？−
／７１弘ｊ３号、同ｊＰ−／７♂弘！≠号、同ｊターｉ
７ｙ弘！！号、同ｊター／７１１１７１７号などに記載
のような高沸点Ｍ機溶媒を、必要に応じて沸点ｊＯ°Ｃ
〜／ｌＯ”ｃの低沸点有機溶媒と併用して、用いること
ができる。Hydrophobic additives such as dye-donating compounds and diffusion-resistant reducing agents can be incorporated into the layers of the photosensitive element by known methods such as those described in US Pat. No. 2,3λλ,027. In this case, JP-A-131! ≠ issue, same jter i7r ≠ j1 issue, same! Day/7rlAjJ issue, same! ? −
/71 Hiroj No. 3, same jP-/7♂Hiro! ≠ issue, same j ter i
7y Hiro! ! If necessary, a high boiling point M solvent such as that described in No. 7111717, etc.
It can be used in combination with a low boiling point organic solvent of ~/lO''c.
高沸点Ｍ機溶媒の量は用いられる色素供与性化合物ｉｔ
に対してｉｏｙ以下、好ましくは夕を以下である。また
、バインダーｉｙに対して／ＣＣ以下、ｌｌダニＯ、ｊ
ｃＸ：、以下、特にｏ、３ｃｃ以下が適轟である。The amount of high boiling point solvent is the amount of dye-donating compound used.
It is less than or equal to ioy, preferably less than or equal to ioy. Also, for binder iy /CC below, ll mite O, j
cX: Below, o, 3cc or less is suitable.
特公昭ｊ／−Ｊり１１３号、特開昭！／−ｊりＰ≠３号
に記載されている重合物による分散法も使用てきる。Tokuko Shoj/-Jri No. 113, Tokukai Sho! The dispersion method using a polymer described in No. 3 of P≠3 can also be used.
水に実質的に不溶な化合物の場合には、前記方法以外に
パインダニ中に微粒子にして分散含有させることができ
る。In the case of a compound that is substantially insoluble in water, it can be made into fine particles and dispersed and contained in the pine mites in addition to the above-mentioned method.
疎水性化合物を親水性コロイドに分散する際に框、檀々
の界面活性剤上用いることができる１例えげ特開昭ｊタ
ー／ｊ７６３６号の第（３７）〜（３ｔ）頁に界面活性
剤として挙けたもの金使うことができる。An example of a surfactant that can be used as a surfactant when dispersing a hydrophobic compound in a hydrophilic colloid is described in Japanese Patent Application Laid-Open No. 7636, pages (37) to (3t). You can use the money mentioned above.
本発明においては感光要素に現像の活性化と同時に画像
の安定化を図る化合物を用いることができる。好ましく
用いられる具体的化合物については米国特許第≠、１０
０，６２４号の第ｊ／〜！コＭ＆Ｃ記載されている。In the present invention, a compound that activates development and simultaneously stabilizes images can be used in the photosensitive element. For specific compounds preferably used, see U.S. Patent No. ≠, 10.
No. 0,624 No. j/~! Co M&C is listed.
色素の拡散転写により画＊Ｖ形成するシステムにおいて
は感光要素と共に色素固定要素が用いられる。色素固定
要素は感光要素とは別々の支持体′上に別個に塗設され
る形態であっても、感光要素と同一の支持体上に自設芒
れる形態て必ってもよい。感光要素と色素固定要素相互
の関係、支持体との関係、白色反射層との関係は米国特
許第≠。In systems that form images by diffusion transfer of dyes, dye-fixing elements are used in conjunction with photosensitive elements. The dye fixing element may be coated separately on a support separate from the photosensitive element, or it may be self-coated on the same support as the photosensitive element. The relationship between the photosensitive element and the dye fixing element, the relationship with the support, and the relationship with the white reflective layer are described in US Patent No. ≠.
、ｔｏｏ、 ６２６号の第よ７個に記載の関係が本願に
も適用て色る。, too, No. 626, No. 7, applies to the present application as well.
本発明に好ましく用いられる色素固定要素は媒染剤とバ
インターを言むｊ−を少なくとも１層有する。媒染剤は
写真分野で公知のものを用いることができ、その具体例
としては米国特許第≠、ｊＯｏ、ｔコを号笛５ｉｒＮｔ
り欄や特開昭６７〜ｒｒ２よｔ号笛（３コ）〜（４Ｌ／
）頁に記載の媒染剤、特開昭６２−２１１−ＩＩＯ弘３
号、同６コー２弘≠０３を号等に記載のものを挙けるこ
とができる。また、米国特許第弘、≠６３．０７Ｐ号に
記載されているような色素受容性の高分子化合物音用い
てもよい。The dye fixing element preferably used in the present invention has at least one layer of a mordant and a binder. As the mordant, those known in the photographic field can be used, and specific examples thereof include U.S. Patent No.
R column and JP-A-67~RR2 T whistle (3 pieces)~(4L/
), the mordant described in JP-A-62-211-IIO Ko 3
No. 6, Ko 2 Hiro ≠ 03, etc. can be mentioned. Furthermore, dye-receptive polymeric compounds such as those described in US Pat. No. 63.07P may also be used.
色素固定要素には必゛要に応じて保護層、剥離層、カー
ル防止層などの補助１＠を設けることができる。The dye fixing element can be provided with auxiliary materials such as a protective layer, a peeling layer, and an anti-curl layer, if necessary.
特に保護層を設けるのは有用である。In particular, it is useful to provide a protective layer.
感光要素や色素固定要素の構成層のバインダーには親水
性のものが好筐しく用いられる。その例としては特開昭
６２−２ｊ３／ｊり号の（２６）貞〜（，２Ｆ）負に記
載されたものが挙げられる。具体的には、透明か半透明
の親水性バインダーが好ましく、例えばゼラチン、ゼラ
チン誘導体等のタンパク質またはセルロース誘導体、デ
ンプン、アラビアゴム、テキストラン、プルラン等の多
糖類のような天然化＠物と、ポリビニルアルコール、ホ
リヒニルビロリドン、アクリルアミド重合体、その他の
８成高分子化＠物が挙げられる。また、特開昭６一−λ
弘１２６０号等に記載の高吸水性ポリマー、すなわち−
ＣＯＯＭ−ｐ次は−８Ｏａ Ｍ （Ｍは水素原子または
アルカリ金属）ｔ−肩するビニルモノマーの単独重合体
ま九はこのビニルモノマー同士もしくは他のビニルモノ
マーとの共重合体（例えばメタクリル酸ナトリウム、メ
タクリル酸アンモニウム、注文化学■製スミカゲルＬ−
ｊＨ）も使用される。これらのバインターは、２種以上
組み合わせて用いることもできる。Hydrophilic binders are preferably used for the constituent layers of the photosensitive element and the dye fixing element. An example of this is JP-A No. 62-2J3/J, (26) Sada~(, 2F), which is written in the negative. Specifically, a transparent or translucent hydrophilic binder is preferred, and for example, gelatin, proteins such as gelatin derivatives, or cellulose derivatives, starch, natural substances such as polysaccharides such as gum arabic, textolan, pullulan, etc. Examples include polyvinyl alcohol, hollyhinylpyrrolidone, acrylamide polymer, and other 8-component polymers. Also, JP-A-61-λ
The superabsorbent polymer described in Hiroshi No. 1260 etc., i.e. -
COOM-pThe next is -8Oa M (M is a hydrogen atom or an alkali metal) t-A homopolymer of vinyl monomers on the shoulder.9) A copolymer of these vinyl monomers with each other or with other vinyl monomers (for example, sodium methacrylate, Ammonium methacrylate, Sumikagel L- manufactured by Custom Chemical Co., Ltd.
jH) is also used. These binders can also be used in combination of two or more types.
倣濾の水を供給して熱現像を行うシステムを採用する場
合、上記の高吸水性ポリマーを用いることにより、水の
吸水を迅速に行うことが可能となる。また、高吸水性ポ
リマー、を色素固定層やその保護層に使用すると、転写
後に色素が色素固定要素から他のものに再転写するのを
防止することができる。When employing a system in which thermal development is performed by supplying copy filter water, the use of the above-mentioned super absorbent polymer makes it possible to quickly absorb water. Furthermore, when a highly water-absorbing polymer is used in the dye fixing layer or its protective layer, it is possible to prevent the dye from being retransferred from the dye fixing element to another object after transfer.
本発明において、バインダーの塗布量ｔｌ／ｍ”当たり
２Ｏｆ以下が好ましく、特にｌＯ１以）、更には７２以
下にするのが適当である。In the present invention, the coating amount of the binder is preferably 2Of or less per tl/m'', particularly 1O1 or less, and more preferably 72 or less.
感光要素や色素固定要素の構成層に用いる硬膜剤として
は、米国特許第弘、６７１，７３２号第≠／欄、特開昭
ｊター／／６Ａｚｓ号、同６コー２１Ａｊ２６／号、同
＋／−ｔｔｙ４ｃａ号等に記載の硬膜剤が挙げられる。Hardeners used in the constituent layers of light-sensitive elements and dye-fixing elements include those described in U.S. Pat. Examples include hardening agents described in No. /-tty4ca and the like.
より具体的には、アルデヒド系硬膜剤（ホルムアルデヒ
ドなど）、アジリジン系硬膜剤、エポ午シ糸硬膜剤
なト）、ビニルスルホン系硬膜剤（Ｎ、Ｎ’−エチレン
−ビス（ビニルスルホニルアセタミド）エタンなど）、
Ｎ−メチロール系硬膜剤（ジメチロール尿素などン、あ
るいは高分子硬膜剤（特開昭６２−２ＪＩＡ／ １７号
などに記載の化合物）が挙げられる。More specifically, aldehyde hardeners (formaldehyde, etc.), aziridine hardeners, epoxy thread hardeners, vinyl sulfone hardeners (N,N'-ethylene-bis(vinyl sulfonylacetamide) ethane, etc.),
Examples include N-methylol hardeners (such as dimethylol urea) and polymer hardeners (compounds described in JP-A-62-2 JIA/17, etc.).
本発明において感光要素及び／又は色素固定要素には画
像形成促進剤を用いることができる。画像形成促進剤に
は銀塩酸化剤と還元剤との酸化還元反応の促進、色素供
与性物質からの色素の生成または色素の分解あるいは拡
散祥色素の放出等の反応の促進および、感光材料層から
色素固定層への色素の移動の促進等の機能があり、物理
化学的な機能からは塩基または塩基プレカーサー、求核
性化名物、高沸点Ｍ機溶媒（オイルン、熱溶剤１面活性
剤、銀または銀イオンと相互作用を持つ化合物等に分類
される。ただし、これらの物理群は一般に複合機能を有
しており、上記の促進効果のいくつかの合せ持つのが常
である。これらの詳細については米国特許弘、６７ｇ、
７３２号第３ｇ〜ＩＡ０欄に記載されている。In the present invention, an image formation accelerator can be used in the photosensitive element and/or the dye fixing element. Image formation accelerators include accelerating redox reactions between silver salt oxidizing agents and reducing agents, accelerating reactions such as generation of dyes from dye-donating substances, decomposition of dyes, and release of diffused dyes, and photosensitive material layers. It has functions such as promoting the movement of the dye from the dye to the dye fixing layer, and from a physicochemical function, it has a base or base precursor, a nucleophilic specialty, a high boiling point M solvent (oilon, a hot solvent single-surface active agent, It is classified as a compound that interacts with silver or silver ions. However, these physical groups generally have complex functions and usually have some of the above-mentioned promoting effects. For details, see U.S. Patent Hong, 67g,
No. 732, No. 3g to IA0 columns.
塩基プレカーサーとしては、熱により脱炭酸する有機酸
と塩基の塩、分子内求核置換反応、ロッセン転位ま７′
Ｃハベツクマン転位によりアミン類を放出する化合物な
どがある。その具体例は米国特許弘、 ｊ１／、弘７３
号、特開昭６２−６！θ３♂号等に記載されている。Base precursors include salts of organic acids and bases that are decarboxylated by heat, intramolecular nucleophilic substitution reactions, Rossen rearrangements, and
There are compounds that release amines through C-Habetsukman rearrangement. A specific example is U.S. Patent Ko, j1/, Ko 73.
No., JP-A-62-6! It is described in θ3♂ issue etc.
小波の水の存在下に熱現像と色素の転位を同時に行うシ
ステムにおいてに、塩基及び／又は塩基プレカーサーは
色素固定要素に含有させるのが感光要素の保存性を高め
る意味で好ましい。In a system in which thermal development and dye rearrangement are carried out simultaneously in the presence of small waves of water, it is preferable to include a base and/or a base precursor in the dye fixing element in order to improve the storage stability of the photosensitive element.
上記の他に、欧州特許公開２１０，６６０号に記載され
ている難俗性金楓化合物およびこの＃！浴住金属化合物
を構成する金属イオンと錯形成反応しうる化合物（錯形
成化合物という）の組合せや、特開昭６１−２３コ弘ｊ
１号に記載されている電解により塩基を発生する化合物
なども塩基プレカーサーとして使用できる。特に前者の
方法は効果的である。こ０難溶性金属化合物と錯形成化
合物は、感光要素と色素固定要素に別々に添加するのが
有利である。In addition to the above, there is also the difficult-to-produce gold maple compound described in European Patent Publication No. 210,660 and this #! Combinations of compounds that can undergo complex-forming reactions with metal ions constituting bath metal compounds (referred to as complex-forming compounds), and JP-A-61-23 Cohiroj
Compounds that generate bases by electrolysis as described in No. 1 can also be used as base precursors. The former method is particularly effective. It is advantageous to add the slightly soluble metal compound and the complex-forming compound to the light-sensitive element and the dye-fixing element separately.
熱現像工程での７）Ｄ熱温度は、約ｒ００Ｃ〜約２ｊＯ
°Ｃで現像可能であるが、特に約ｔｏ”ｃ〜約ｔｒｏ
ｏｃが１用である。色素の拡散転写工程は熱現像と同時
に行ってもよいし、熱現像工程終了後に行ってもよい。7)D heat temperature in the heat development process is about r00C to about 2JO
can be developed at temperatures between about to”c and about tro.
oc is for 1. The dye diffusion transfer step may be performed simultaneously with the heat development, or may be performed after the heat development step is completed.
後者の揚台、転写工程でのカロ熱温度に、熱現像工程に
おける温度から室撫の範囲で転写可能であるが、特に１
００（：以上で熱現像工程に３ける温度よりも約１００
（：低い温度までがより好着しい。Transfer is possible in the temperature range from the temperature in the heat development process to room temperature in the latter stage and in the transfer process.
00 (approximately 100% higher than the temperature in the heat development process)
(: Lower temperatures are more preferable.
色素の移動は熱のみによっても生じるが、色素移動を促
進するために溶媒を用いてもよい。Dye migration can also be caused by heat alone, but a solvent may be used to promote dye migration.
また、特開昭ｊターコｌ翻り３号、同Ａｌ−２ＪＩＯｊ
ｔ号等に詳述されるように、少量の溶媒（特に水）の存
在下で加熱して現像と転写を同時または連続して行う方
法も有用である。この方式においては、加熱温度はｊＯ
’（以上で溶媒の沸点以下が好ましい。例えば溶媒が水
の場合はｊｏ Ｏｃ以上１００ ０Ｃ以下が望ましい
。In addition, Tokukai Shoj Turco l Fari No. 3, same Al-2JIOj
As detailed in No. t, etc., a method in which development and transfer are performed simultaneously or successively by heating in the presence of a small amount of solvent (particularly water) is also useful. In this method, the heating temperature is jO
(The above is preferably below the boiling point of the solvent. For example, when the solvent is water, the temperature is desirably above 100°C and below 100°C.
現像の促進および／または拡散性色素の色素固定層への
移動のために用いる溶媒の例としては、水まｆＣ，は無
機のアルカリ金属塩や有機の塩基を含む塩基性の水溶液
（これらの塩基としては画像形成促進剤の項で記載した
ものが用いられる）を挙げることができる。また、低沸
点溶媒、または低沸点溶媒と水もしくは塩基性の水浴液
との混合溶液なども使用することができる。また界面活
性剤、カブリ防止剤、難溶性金属塩と錯形成化合物等を
溶媒中に含ませてもよい。Examples of solvents used to accelerate development and/or transfer the diffusible dye to the dye fixed layer include water, fC, a basic aqueous solution containing an inorganic alkali metal salt or an organic base (such as As examples, those described in the section of image formation accelerators can be used. Furthermore, a low boiling point solvent or a mixed solution of a low boiling point solvent and water or a basic water bath liquid can also be used. Further, a surfactant, an antifoggant, a complex-forming compound with a sparingly soluble metal salt, etc. may be included in the solvent.
ｃｎらの溶媒は、色素固定要素、感光要素またはその両
者に付与する方法で用いることができる。The solvent of cn et al. can be used in a method of applying it to a dye fixing element, a photosensitive element, or both.
その使用量は全塗布膜の最大膨潤体積に相当する溶媒の
重量以下（特に全塗布膜の最大膨潤体積に相当する溶媒
の重量から全塗布膜の本社を差引いた童以下）という少
量でよい。The amount used may be as small as less than the weight of the solvent corresponding to the maximum swelling volume of the entire coating (particularly less than the weight of the solvent corresponding to the maximum swelling volume of the entire coating minus the weight of the entire coating).
感光層または色素固定層に溶媒を付与する方法としては
、例えは、特開昭Ａ／−／ｌｌ−７２弘参号（コロ）負
に記載の方法がある。筐た、溶剤をマイクロカプセルに
閉じ込めるなどの形で予め感光要素もしくは色素固定要
素またはその両省に内蔵させて用いることもできる。As a method for applying a solvent to the photosensitive layer or the dye-fixing layer, there is, for example, the method described in Japanese Patent Application Laid-Open No. 1999-11-11-72 Kosan No. (Coro) Negative. It can also be used by preliminarily incorporating the solvent into the photosensitive element or the dye fixing element, or both, by enclosing the solvent in a microcapsule.
また色素移動を促進するために、常温でに固体であり高
温では溶解する親水性熱浴剤を感光要素または色素固定
要素に内蔵嘔せる方式も採用できる。親水性熱溶剤は感
光要素、色素固定要素のいずれに内蔵させてもよく、両
方に内蔵させてもよい。また内蔵させる層も乳剤層、中
間層、保護層、色素固定層いずれてもよいが、色素固定
層および／筐たはその隣接層ＶＣＦＰ３蔵させるのが好
ましい。Furthermore, in order to promote dye transfer, a method may be adopted in which a hydrophilic heat bath agent that is solid at room temperature and dissolves at high temperatures is built into the photosensitive element or dye fixing element. The hydrophilic thermal solvent may be incorporated into either the photosensitive element or the dye fixing element, or may be incorporated into both. Further, the layer to be incorporated may be an emulsion layer, an intermediate layer, a protective layer, or a dye fixing layer, but it is preferable to include the dye fixing layer and/or the casing or its adjacent layer VCFP3.
親水性熱溶剤の例としては、尿素類、ピリジン類、アミ
ド類、スルホンアミド類、イミド類、アルニール類、オ
キシム類その他の複素環類がある。Examples of hydrophilic heat solvents include ureas, pyridines, amides, sulfonamides, imides, alnyls, oximes, and other heterocycles.
また、色素移動を促進するために、高沸点Ｍ機浴剤を感
ｆｔＳ要素及び／又は色素固定要素に含有させておいて
もよい。Further, in order to promote dye transfer, a high boiling point M bath agent may be included in the sensitive ftS element and/or the dye fixing element.
現像および／′！たは転写工程における７１０熱方法と
しては、加熱芒ねたブロックやプレートに接触きせたり
、熱板、ホットプレッサー、熱ローラ−、ハロゲンラン
プヒーター、赤外および遠赤外ランプヒーターなどに接
触させたり、高温の雰囲気中を通過させるなどがある。Development and /′! The 710 heat method in the transfer process includes contact with a heated block or plate, contact with a hot plate, hot presser, heat roller, halogen lamp heater, infrared and far infrared lamp heater, etc. , passing through a high-temperature atmosphere, etc.
また、感光要素または色素固定要素に抵抗発熱体層を設
け、これに通電して加熱してもよい。発熱体Ｉ−として
は特開昭６／−／１ｌｊｊ≠弘号等に記載のものが利用
できる。Alternatively, a resistive heating layer may be provided on the photosensitive element or the dye fixing element, and the layer may be heated by supplying electricity to the layer. As the heating element I-, those described in JP-A No. 6/-/1ljj≠Hiroshi can be used.
感光要素と色素固定要素とを重ね台わせ、密着させる時
の圧力条件や圧力を加える方法は特開昭Ａ／−／１Ｉｔ
７コ≠≠号（２７）目に記載の方法が適用できる。The pressure conditions and method of applying pressure when placing the photosensitive element and the dye fixing element on top of each other and bringing them into close contact are described in Japanese Patent Application Laid-Open No. 2001-111111.
The method described in item 7≠≠ (27) can be applied.
本発明の写真要素の処理には種々の熱現像装置のいずｎ
もが使用できる。例えば、特開昭！？−７ハ日７号、同
！？−７７７よ≠７号、同ｊター／Ｉ／３ｊＪ号、同４
０−／ｆり５７号、実開昭ｊＪ−２１２≠１号等に記載
されている装置などが好’ＥＬ＜便用される。Any of a variety of thermal development equipment may be used to process the photographic elements of this invention.
You can also use it. For example, Tokukai Akira! ? -7 Ha day issue 7, same! ? -777 ≠ No. 7, No. 777, No. 7, No. 4
The devices described in No. 0-/fri No. 57, Utility Model Publication No. 212≠1, etc. are preferably used.
実施例１
表／に示す、多層構成のカラー感光材料１０／を作成し
た。Example 1 A color photosensitive material 10/ having a multilayer structure as shown in Table 1 was prepared.
水溶性ポリマー（１）＊
スミカゲルＬ−ｊ（Ｈ） 注文化学■製水溶性ポリマ
ー（２）＊
界面活性剤（１）＊
エーロゾルＯＴ
界面活性剤（２）８
界面活性剤（３）＊
界面活性剤Ｃ４）＊
硬膜剤（１）＊
／、！−ビス（ビニルスルフォニルアセトアミド）エタ
ン
高沸点有機溶媒（１）＊
トリシクロへキシルフォスフェート
カブリ防止剤口）＊
増感色素（１）＊
イエロー色素供与性物質（１）＊
マゼンタ色素供与性物質（２）＊
シアン色素供与性物質（３）＊
電子供与体（１）＊
０■（
電子伝達剤（ｌ）＊
還元剤（１）＊
第１層用の乳剤（１）の作υ方について詠べる。Water-soluble polymer (1) * Sumikagel L-j (H) Water-soluble polymer (2) manufactured by Custom Kagaku ■ Surfactant (1) * Aerosol OT Surfactant (2) 8 Surfactant (3) * Surfactant Agent C4)* Hardener (1)* /,! -Bis(vinylsulfonylacetamido)ethane High-boiling organic solvent (1)* Tricyclohexylphosphate antifoggant)* Sensitizing dye (1)* Yellow dye-donating substance (1)* Magenta dye-donating substance (2) ) * Cyan dye-donating substance (3) * Electron donor (1) * 0 ■ ( Electron transfer agent (l) * Reducing agent (1) * Write a poem about how to make the emulsion (1) for the first layer. Ru.
良く攪拌しているゼラチン水溶液（水ｉｏｏ。A well-stirred gelatin aqueous solution (water ioo.
ｍｌ中にゼラチン２０ｇと塩化ナトリウム３ｇを含み７
ｊ０Ｃに保温したもの）に塩化ナトリウムと臭化カリウ
ムを含有している水溶液１．００ｍ１と硝酸銀水溶液（
水ｔ００ｍｌに硝酸＠Ｏ０！２モルを溶解させたもの）
を同時にｑＯ分間にわたって等流量で添加した。このよ
うにして平均粒子サイズ０．３ｊμの単分散立方体塩臭
化銀乳剤（臭素１０モルチ）を調製した。Contains 20g of gelatin and 3g of sodium chloride in 7ml
1.00ml of an aqueous solution containing sodium chloride and potassium bromide (kept at 0C) and a silver nitrate aqueous solution (
Nitric acid @O0!2 mole dissolved in t00ml of water)
were simultaneously added at equal flow rates over qO minutes. In this way, a monodisperse cubic silver chlorobromide emulsion (10 mol of bromine) with an average grain size of 0.3 jμ was prepared.
水洗、脱塩後チオ硫酸ナトリウムｓｍｇと弘−ヒドロキ
シ−２−メチル−／、Ｊ、Ｊａ、７−チトラザインデン
、２０ｍｇを添加してｇｏ ０ｃで化学増感を行なった
。乳剤の収量は６００ｇであつた。After washing with water and desalting, smg of sodium thiosulfate and 20 mg of Hiro-hydroxy-2-methyl-/, J, Ja, 7-titrazaindene were added to perform chemical sensitization at go 0c. The yield of emulsion was 600 g.
次に第３層用の乳剤（ＩＩ）の作り方についてのべる。Next, we will discuss how to prepare emulsion (II) for the third layer.
良く攪拌しているゼラチン水溶液（水１０１００Ｏ中に
ゼラチン２０ｇと塩化ナトリウム３ｇを含み７！０Ｃに
保温したもの）に塩化ナトリウムと臭化カリウムを含有
している水溶液ＡＯＯｍｌと硝酸銀水溶液（水６００ｍ
１に硝酸銀０．２２モルを溶解させたもの）と以下の色
素溶液（りとを、同時に≠θ分にわたって等流量で添加
した。Add AOOml of an aqueous solution containing sodium chloride and potassium bromide to a well-stirred aqueous gelatin solution (20g of gelatin and 3g of sodium chloride in 10100O of water kept at 7!0C) and an aqueous solution of silver nitrate (600ml of water).
1 in which 0.22 mol of silver nitrate was dissolved) and the following dye solution (rito) were simultaneously added at equal flow rates over ≠θ minutes.
このようにして平均粒子サイズ０．３ｊμの色素を吸着
させた単分散立方体塩臭化銀乳剤（臭素ｔＯモルチ）を
調製した。In this way, a monodisperse cubic silver chlorobromide emulsion (bromine tO mole) having an average grain size of 0.3 jμ adsorbed with a dye was prepared.
水洗、脱塩後チオ硫酸ナトリウムｊｎ１ｇとｐ −ヒド
ロキシ−６−メチル−／、３．３ａ、７−チトラザイン
デン２０ｍｇを添加してＡｏ ０Ｃで化学増感を行なっ
た。乳剤の収量は４００ｇであった。After washing with water and desalting, 1 g of sodium thiosulfate and 20 mg of p-hydroxy-6-methyl-/, 3.3a, 7-chitrazaindene were added, and chemical sensitization was performed at Ao 0C. The yield of emulsion was 400 g.
色素溶液（１）・・・増感色素（２）＊／ ｇ ｏ ｍ
ｇをメタノールダ００ｍ１ｊに溶解したも
増感色素（２）＊
次に第５層用の乳剤（Ｉｌｌ）の作り方について述べる
。Dye solution (1)...sensitizing dye (2)*/ g o m
Sensitizing dye (2)* in which g was dissolved in methanol da 00ml. Next, the method for preparing the emulsion (Ill) for the fifth layer will be described.
良く攪拌しているゼラチン水溶液（水１０１００Ｏ中に
ゼラチン２０ｇとアンモニウムを溶解させｊｏ ０ｃに
保温したもの）に沃化カリウムと臭化カリウムを含有し
ている水溶液１０１００Ｏと硝酸銀水溶液（水１００１
００ｏに硝酸銀１モルを溶解させたもの）を同時にｐＡ
ｇを一定に保ちつつ添加した。このようにして平均粒子
サイズθ。A well-stirred aqueous gelatin solution (20 g of gelatin and ammonium dissolved in 10,100 O of water and kept warm at 100 C) was mixed with an aqueous solution of 10,100 O containing potassium iodide and potassium bromide and an aqueous solution of silver nitrate (1,000 O of water).
00o dissolved in 1 mol of silver nitrate) at the same time as pA
g was added while keeping it constant. In this way the average particle size θ.
ｊμの単分散八面体沃臭化銀乳剤（沃素！モルチ）を調
製した。A monodisperse octahedral silver iodobromide emulsion (Iodine!Morch) of jμ was prepared.
水洗、脱塩後塩化金酸（≠水塩）ｊｍｇとチオ硫酸ナト
リウムＪｇを添加してｔｏ ０ｃで金および硫黄増感を
施した。乳剤の収量は／ｋｇであった。After washing with water and desalting, jmg of chloroauric acid (≠water salt) and Jg of sodium thiosulfate were added to perform gold and sulfur sensitization at to 0c. The yield of emulsion was /kg.
次に色素供与性物質のゼラチン分散物の作り方について
述べる。Next, we will describe how to make a gelatin dispersion of a dye-donating substance.
イエローの色素供与性物質（ｌｌ ＊／ Ｊ ｇ 、高
沸点有機溶媒（１）をｔ、よｇ、電子供与体（１）＊ｒ
、♂ｇ、シクロヘキサノン３７ｍ１に添加溶解し、１０
チゼラチン溶液１００ｇとドデシルベンゼンスルホン酸
ソーダの２．７％水溶液１．０ｍ１ｌとを攪拌混合した
後、ホモジナイザーで７０分間、１１００００ｒｐにて
分散した。この分散液をイエローの色素供与性物質の分
散物と言う。Yellow dye-donating substance (ll * / J g , high boiling point organic solvent (1) t, yog, electron donor (1) * r
, ♂g, added and dissolved in 37ml of cyclohexanone, 10
After stirring and mixing 100 g of tisgelatin solution and 1.0 ml of a 2.7% aqueous solution of sodium dodecylbenzenesulfonate, the mixture was dispersed using a homogenizer at 110,000 rpm for 70 minutes. This dispersion is called a yellow dye-providing substance dispersion.
マゼンタの色素供与性物質（２） ＊／ Ａ 、ｒ ｇ
、高沸点有機溶媒（ｌｌ＊ｒ、弘ｇ、電子供与体（１
）＊♂。Magenta dye-donating substance (2) */ A, r g
, high boiling point organic solvent (ll*r, Hiroshig, electron donor (1
)＊♂.
Ａｇｓをシクロヘキサノン３７ｍ１に添加溶解し、／θ
チゼラチン溶液１００ｇ、 ドデシルベンゼンスルホ
ン酸ソーダのｊ、ｔ％水溶液ＡＯｍｌとを攪拌混合した
後、ホモジナイザーで７０分間、ｌｏｏｏｏｒｐｍにて
分散した。この分散液をマゼンタの色素供与性物質の分
散物と言う。Ags was added and dissolved in 37ml of cyclohexanone, /θ
After stirring and mixing 100 g of tisgelatin solution and AO ml of j,t% aqueous solution of sodium dodecylbenzenesulfonate, the mixture was dispersed using a homogenizer at LOOOORPM for 70 minutes. This dispersion is called a dispersion of a magenta dye-providing substance.
シアンの色素供与性物質（３１＊／ｊ、μｇ、高沸点有
機溶媒ｍ＊７．７ｇ、電子供与体（１）ｆ、コｇをシク
ロヘキサノン３７ｍ１に添加溶解し、ｌＯ％セラチン溶
液１００ｇとドデシルベンゼンスルホン酸ソーダの２．
１％水溶液１．Ｏｍｌとを攪拌混合した後、ホモジナイ
ザーで１０分間、ｌ１００ｏｏｒｐにて分散した。この
分散液をシアンの色素供与性物質の分散物と言う。Cyan dye-donating substance (31*/j, μg, high boiling point organic solvent m*7.7g, electron donor (1) f, cog was added and dissolved in 37ml of cyclohexanone, and 100g of lO% Seratin solution and dodecylbenzene were added. 2. Sodium sulfonate.
1% aqueous solution 1. After stirring and mixing with Oml, the mixture was dispersed using a homogenizer at 1100 oorp for 10 minutes. This dispersion is called a dispersion of a cyan dye-providing substance.
次に色素固定材料の作り方について述べる。Next, we will discuss how to make the dye fixing material.
ポリエチレンでラミネートした紙支持体上に次表の構成
で塗布し色素固定材料Ｒ−７を作った。A dye fixing material R-7 was prepared by coating on a paper support laminated with polyethylene according to the composition shown in the following table.
シリコーンオイル＊１
界面活性剤＊２
エアロゾルＯＴ
界面活性剤＊３
Ｃ８Ｆ、７８０□ＮＣＨ２Ｃ００Ｋ
３Ｈ７
界面活性剤＊４
ポリマー＊５
ビニルアルコールアクリル酸ナトリウム共重合体（７ｊ
／コ！モル比）
ポリマー＊７
デキストラン（分子量７万）
媒染剤＊６
高沸点有機溶媒＊８
レオフオスタ！（味の素＠’Ｂ）
硬膜剤＊９
マット剤＊１０
ベンゾグアナミン樹脂
平均粒子サイズ７０μ
上記感光材料１０／の第１．ｊ、ｊ層に、表３に示すよ
うに本発明における化合物（，２４）、（４０）、（／
４）、（４７）、（ｒｊ）（／／３）を各色素供与性化
合物と共に乳化、分散して添加した以外は、感光材料１
０／と全く同じ組成の感光材料１０．２〜１０７をそれ
ぞれ作成した。Silicone oil *1 Surfactant *2 Aerosol OT Surfactant *3 C8F, 780□NCH2C00K 3H7 Surfactant *4 Polymer *5 Vinyl alcohol sodium acrylate copolymer (7j
/Ko! Molar ratio) Polymer *7 Dextran (molecular weight 70,000) Mordant *6 High boiling point organic solvent *8 Rheofuosta! (Ajinomoto @'B) Hardening agent *9 Matting agent *10 Benzoguanamine resin average particle size 70μ No. 1 of the above photosensitive material 10/. As shown in Table 3, the compounds (,24), (40), (/
4), (47), and (rj)(//3) were added by emulsifying and dispersing them together with each dye-providing compound.
Photosensitive materials 10.2 to 107 having exactly the same composition as 0/ were prepared, respectively.
表 ３
ｉｏｉ −−１０コ
（コｔ） ｏ、ｉ。Table 3 ioi --10 pieces
(Kot) o, i.
１０３ （コｏ） ｏ、ｏｙ１０≠
（ｔＡ） ｏ、ｏ＆ｔｏｒ
（ｇ７） ｏ、ｏｚ１０４ （ｌ
ｔ） ０．０．２上記多層構成のカラー感光材
料にタングステン電球を用い、連続的に濃度が変化して
いるＢ、Ｇ。103 (koo) o, oy10≠
(tA) o, o&tor
(g7) o, oz104 (l
t) 0.0.2 B and G in which a tungsten light bulb is used as the multilayered color photosensitive material and the density changes continuously.
Ｒ及びグレーの色分解フィルターを通して２０００ルク
スで１７１０秒間露光した。Exposure was made for 1710 seconds at 2000 lux through R and gray color separation filters.
との露光済みの感光材料を線速２０ｍｍ／ｓｅｃで送り
ながら、その乳剤面に／ｊｍｌ／ｍ２の水をワイヤーパ
ーで供給し、その後直ちに受像材料と膜面が接するよう
に重ね合わせた。While transporting the exposed photosensitive material at a linear speed of 20 mm/sec, /jml/m2 of water was supplied to the emulsion surface using a wire purr, and then immediately the image-receiving material and the film surface were superimposed so that they were in contact with each other.
吸水した膜の温度が、ｒｊｏＣとなるように温度調節し
たヒートローラーを用い、２０秒間加熱した。次に受像
材料からひきはがすと、受像材料上にＢＸＧ、Ｒおよび
グレーの色分解フィルターに対応してブルー、グリーン
、レッド、グレーの鮮明な像がムラなく得られた。The film was heated for 20 seconds using a heat roller whose temperature was adjusted so that the temperature of the water-absorbed film was rjoC. Next, when it was peeled off from the image-receiving material, clear blue, green, red, and gray images corresponding to the BXG, R, and gray color separation filters were uniformly obtained on the image-receiving material.
グレ一部のシアン、マゼンタ、イエローの各色の最高濃
度（Ｄｍａｘ）と最低濃度（Ｄｍｉｎ）を測定した結果
を表≠に示す。Table ≠ shows the results of measuring the maximum density (Dmax) and minimum density (Dmin) of each color of cyan, magenta, and yellow in the gray part.
次に感光材料１０／〜１０７をｒｏ ０ｃ湿度ｔＯ％の
条件下、１週間保存した後、同様の露光、現像処理を行
った。このときのグレ一部のイエロー、マゼンタ、シア
ンのＤｍ ａ Ｘ ％ Ｄ ｍ ｊ ｎを測定した結果
を表！に示す。Next, the photosensitive materials 10/-107 were stored for one week under the conditions of ro 0c and humidity tO%, and then subjected to the same exposure and development treatments. The table below shows the results of measuring the yellow, magenta, and cyan Dm a Shown below.
表μ、表！より、本発明の化合物（，２４）、（コ０）
、（／、４）、（＋７）、（ｉｔ）、（／／３）をそれ
ぞれ加えた感光材料ｉｏｓ〜１０７では、ｚｏ ０ｃｔ
ｏ％ＲＨ／週間の保存前後のいずれにおいても、画像濃
度が高く、スティンの低い画像が得られた。Tableμ, table! Therefore, the compounds of the present invention (,24), (co0)
, (/, 4), (+7), (it), (//3), respectively, in the photosensitive material ios~107, zo 0ct
Images with high image density and low stain were obtained both before and after storage at o%RH/week.
実施例２
感光材料１０／で第１．３、！層にそれぞれ０゜０３ｇ
／ｍ２ずつ加えた電子伝達剤（１）＊を下記に示す電子
伝達剤（２）＊（各層添加量ｏ、ｏコｇ／ｍ２）に変え
た以外は、全く同じ組成の感光材料２０／を作成した。Example 2 Photosensitive material 10/1.3,! 0゜03g for each layer
A photosensitive material 20/ of the same composition was used, except that the electron transfer agent (1)* added at a rate of /m2 was changed to the electron transfer agent (2)* shown below (addition amount o, o g/m2 in each layer). Created.
電子伝達剤Ｃ２）＊
α
次に、感光材料λＯ／の第２、参層に本発明の化合物（
２ｔ）、（２０）、（／ｊ）、（ｔ７）、（♂ｊ）、（
／１３）を以下に示す方法で乳化分散したものを表２の
ように添加した以外は感光材料、２０／と全く同じ組成
の感光材料２０２〜２０７を作成した。Electron transfer agent C2)*α Next, the compound of the present invention (
2t), (20), (/j), (t7), (♂j), (
Photographic materials 202 to 207 having exactly the same composition as photographic material 20/ were prepared except that emulsified and dispersed material /13) was added as shown in Table 2 by the method shown below.
ここで化合物（ｊ４）のゼラチン分散物の作り方につい
て述べる。Here, a method for preparing a gelatin dispersion of compound (j4) will be described.
化合物（、ｚ＋）ｊｇｓ高沸点有機溶媒２ｇを酢酸エテ
ル１０ｍ１に添加溶解し、１０％ゼラチン水溶液２０ｇ
とドデシルベンゼンスルホン酸ソーダの２．ｊ％溶液／
２ｍｌとを攪拌混合した後、ホモジナイザーでｉｏ分間
１１００００ｒｐにて分散した。この分散液を化合物（
コ乙）の分散物という。Add and dissolve 2 g of compound (,z+)jgs high boiling point organic solvent in 10 ml of ethyl acetate, and dissolve 20 g of 10% gelatin aqueous solution.
and 2. of sodium dodecylbenzenesulfonate. j% solution/
After stirring and mixing with 2 ml, the mixture was dispersed using a homogenizer at 110,000 rpm for io minutes. This dispersion is mixed with a compound (
It is called a dispersion of
化合物（−〇）、（／６）、（６７）、（Ｉｊ）、（／
／３）についても、上記方法と同様の方法で分散物を作
成した。Compound (-〇), (/6), (67), (Ij), (/
For /3), a dispersion was also prepared in the same manner as above.
感光材料コＯ／〜２０７をｚｏｏｃ、湿度６０係の条件
下、１週間保存した。この保存処理の前後で、実施例／
と同様の露光、現像処理を行い、グレ一部のイエロー、
マゼンタ、シアンのＤｍ ａ Ｘ ％ Ｄｍ ｊ ｎを
測定したところ、実施例／と同様、感光材料２０２〜コ
０７はコ０／に比べてスティンが低く、特に保存後にお
けるＤｍｉｎ値は、２０２〜２０７で各色０．１７〜Ｏ
，コｌであったのに対し、２０１では各色約Ｏ０≠であ
った。本実施例においても、−最大１〜■の化合物の添
加により、感材の生保存性が向上したと言える。The photosensitive material KO/~207 was stored in a zooc at a humidity of 60% for one week. Before and after this preservation treatment, Example/
The same exposure and development process was carried out, and some yellow and gray areas were removed.
When magenta and cyan Dm a 0.17~O for each color
, 1, whereas in 201, each color was approximately O0≠. In this example as well, it can be said that the raw storage stability of the light-sensitive material was improved by adding the compounds of -1 to ■ at most.
実施例３
表７に示す多層構成のカラー感光材料３０／を作成した
。なお、各層に用いられる物質は、特にことわらない限
り、感光材料１０／と同じものを使用した。Example 3 A color photosensitive material 30/ having a multilayer structure shown in Table 7 was prepared. The materials used in each layer were the same as those used in Photosensitive Material 10/, unless otherwise specified.
塩基プレカーサー（１）＊ ｐ−クロルフェニルスルフォニル酢酸クアニジン 電子供与体（２）＊ 高沸点有機溶媒（２）＊ （ｉｓｏ−ＣｇＨｌｇＯ）３Ｐ＝０ なお有機銀塩乳剤は以下のようにして調製した。Base precursor (1)* p-Chlorphenylsulfonylacetate quanidine Electron donor (2)* High boiling point organic solvent (2) * (iso-CgHlgO)3P=0 The organic silver salt emulsion was prepared as follows.
ゼラチン２０ｇとび一アセチルアミノフェニルプロピオ
ール酸！、７ｇを０．１％水酸化ナトリウム水溶液１０
１００Ｏとエタノール−ｏｏｍｌに溶解した。20g of gelatin and 1 acetylaminophenylpropiolic acid! , 7g in 0.1% sodium hydroxide aqueous solution 10
Dissolved in 100O and ethanol-ooml.
この溶液をグ０°Ｃに保ち攪拌した。This solution was kept at 0°C and stirred.
この溶液に硝酸銀＋、ｔｇを水２００ｍ１に溶かした液
を５分間で加えた。A solution prepared by dissolving silver nitrate+, tg in 200 ml of water was added to this solution over a period of 5 minutes.
この分散物のｐＨを調整し、沈降させ過剰の塩を除去し
た。この後、ｐＨを６．３に合わせ収量３ｏｏｇの有機
銀塩の分散物を得た。The pH of the dispersion was adjusted and excess salt was removed by settling. Thereafter, the pH was adjusted to 6.3 to obtain a dispersion of organic silver salt with a yield of 30g.
次に、感光材料３０／の第１．３、ｊ層（感光層）と、
第２、ｊ層（中間層）に表ｒに示すように本発明の化合
物を添加した以外は、３０１と全く同じ組成の感光材料
３０．２〜３０りを作成した。Next, the 1.3rd and j layer (photosensitive layer) of the photosensitive material 30/,
Photosensitive materials 30.2 to 30 were prepared having exactly the same composition as 301 except that the compound of the present invention was added to the second j layer (intermediate layer) as shown in Table r.
なお、添加物を添加する際、感光層に添加するときには
、色素供与性物質と共に乳化、分散して添加し、中間層
に添加するときには、感光材料２０２〜コ０７に添加し
たのと同じ方法で乳化、分散して添加した。When adding additives to the photosensitive layer, they are added by emulsifying and dispersing them together with the dye-providing substance, and when adding them to the intermediate layer, they are added by the same method as added to photosensitive materials 202 to 07. It was added after being emulsified and dispersed.
次に色素固定材料の作り方について述べる。Next, we will discuss how to make the dye fixing material.
ポリ（アクリル酸メチルーコーＮ 、Ｎ 、Ｎ−）ジメ
チル−Ｎ−ビニルベンジルアンモニウムクロライド）（
アクリル酸メチルとビニルベンジルアンモニウムクロラ
イドの比率は／：／）ｌＯｇを２００ｍＪｌの水に溶解
し、ＩＯ％石灰処理ゼラチン１００ｇと均一に混合した
。この混合液に硬膜剤を加え二酸化チタンを分散したポ
リエチレンでラミネートした紙支持体上のりｏｐｍのウ
ェット膜厚に均一に塗布した。この試料を乾燥後、媒染
層を有する色素固定材料として用いる。Poly(methyl acrylate-N,N,N-)dimethyl-N-vinylbenzylammonium chloride) (
The ratio of methyl acrylate to vinylbenzylammonium chloride is /:/) 10g was dissolved in 200mJl of water and mixed uniformly with 100g of IO% lime-treated gelatin. A hardening agent was added to this mixed solution, and the mixture was uniformly coated to a wet film thickness of 0.0 pm on a paper support laminated with polyethylene in which titanium dioxide was dispersed. After drying, this sample is used as a dye fixing material having a mordant layer.
実施例１と同様に露光した後、１ｊＯ０Ｃに加 。After exposure in the same manner as in Example 1, 1jO0C was added.
熱したヒートブロック上で、２０秒間均一に加熱した。It was heated evenly for 20 seconds on a heated heat block.
色素固定材料の膜面側に７ｍ２当り２０ｍ１の水を供給
した後、加熱処理の終った上記感光材料をそれぞれ膜面
が接するように固定材料と重ね合せた。After supplying 20 ml of water per 7 m 2 to the film surface side of the dye fixing material, the heat-treated photosensitive materials were stacked on the fixing material so that their film surfaces were in contact with each other.
ｒｏ ０ｃのヒートブロック上で６秒間加熱した後、色
素固定材料を感光材料からひきはがすと、固定材料上に
実施例／と同様の色像が得られた。After heating on a heat block at ro 0c for 6 seconds, the dye fixing material was peeled off from the light-sensitive material, and a color image similar to Example/ was obtained on the fixing material.
グレ一部のイエロー、マゼンタ、シアンのＤｍ’ａ Ｘ
％ ” ｍ ｉ ｎを測定した結果を表りに示す。Gray, some yellow, magenta, and cyan Dm'a
The results of measuring %” min are shown in the table.
次に感光材料３０／〜３０Ｆを、ｚｏ ０ｃ湿度ｔｏ％
の条件下、７日間保存した後、同様の露光現像処理を行
った。この時のグレ一部のイエロー、マゼンタ、シアン
のＤｍａＸＸＤｍｉｎの測定結果を表ＩＯに示す。表７
０より、本発明の化合物（２ｔ）、（λＯ）、（／ｌ）
、（１０）を添加した感光材料３０２〜３０りでは３０
／に比べて、保存後のＤ ｍ ｉ ｎが著しく低く、保
存性に優れていることがわかる。Next, the photosensitive material 30/~30F was heated to 0c humidity to%
After being stored for 7 days under the following conditions, the same exposure and development treatment was performed. Table IO shows the measurement results of DmaXXDmin of yellow, magenta, and cyan in the gray part at this time. Table 7
From 0, the compound of the present invention (2t), (λO), (/l)
, 30 for the photosensitive material 302 to 30 containing (10).
It can be seen that the D min after storage is significantly lower than that of /, indicating that the storage stability is excellent.
実施例ダ
表／／に示す多層構成のカラー感光材料１７０／を作成
した。EXAMPLE A color photosensitive material 170/ having a multilayer structure shown in Table 1 was prepared.
以下に記載するもの以外は実施例１の感光材料１０／に
記載のものを使用した。Except for those described below, those described in Photosensitive Material 10/ of Example 1 were used.
還元剤（１）＊
シアンカプラー（３）
マゼンタカプラー（２）
イエローカプラー（１）
次に、感光材料ａｏｉの第１．３．５層ならびに、第２
、≠層に表７２に示すように本発明の化合物を加えた以
外は、１７０／と全く同じ組成の感光材料μＯコ〜≠Ｏ
りを作成した。Reducing agent (1) * Cyan coupler (3) Magenta coupler (2) Yellow coupler (1)
, ≠ photosensitive material μO co~≠O having the same composition as 170/ except that the compound of the present invention was added as shown in Table 72 in the ≠ layer.
I created a new version.
上記グ０／〜ｐｏりの多層構成のカラー感光材料にタン
グステン電球を用い、連続的に濃度が変化しているＢ、
Ｇ、Ｈの三色分解フィルムを通して、２０００ルクスで
１秒間露光した。B, in which a tungsten bulb is used in the color photosensitive material with a multilayer structure of 0/~po, and the density changes continuously;
It was exposed for 1 second at 2000 lux through a G, H tricolor separation film.
この露光済みの感光材料の乳剤面に２０ｍ１７ｍ２のグ
アニジン炭酸塩！チ水溶液をワイヤーバーで供給し、ポ
リエチレンテレフタレートフィルムを重ねて、り！″Ｃ
に加熱したヒートブロック上で２ｃ秒間加熱した。この
ようにして処理した感光材料を、さらに、漂白、定着処
理の後、水洗、乾燥を行った。その結果Ｂ、Ｇ、Ｈの露
光に対応した部分にイエロー、マゼンタ、シアンの鮮明
なネガ像が得られた。20m17m2 of guanidine carbonate on the emulsion surface of this exposed light-sensitive material! Supply the aqueous solution using a wire bar, overlay the polyethylene terephthalate film, and ri! "C
The mixture was heated for 2 c seconds on a heat block heated to . The photosensitive material thus processed was further subjected to bleaching and fixing treatments, followed by washing with water and drying. As a result, clear negative images of yellow, magenta, and cyan were obtained in the areas corresponding to the B, G, and H exposures.
このときの、イエロー、マゼンタ、シアンのＤｍ ａ
Ｘ ％ Ｄｍ ｌ ｎを測定した結果を表７３に示す。At this time, yellow, magenta, and cyan Dm a
Table 73 shows the results of measuring X % Dml n.
次に、感光材料１７０／−≠Ｏりをｕｏ ０ｃ、湿度７
０％の条件下、７日間保存後に同様の露光、現像処理を
行った。このときのイエロー、マゼンタ、シアンのＤｍ
ａ Ｘ ｓ Ｄｍ １ ｎを測定した結果を表１≠に
示す。Next, the photosensitive material 170/-≠O is set at uo 0c, humidity 7
After storage for 7 days under 0% conditions, the same exposure and development treatments were performed. Yellow, magenta, and cyan Dm at this time
The results of measuring a X s Dm 1 n are shown in Table 1≠.
表７４ｔより、感光材料≠θ／に比べ、本発明の化合物
（λＡ）、（コ０）、（／ｌ）、（１０）をそれぞれ加
えたグθ２〜≠０２では、保存後のＩ）ｍａｘの低下、
Ｄｍｉｎの上昇が少なく、保存性が改良されていること
がわかる。From Table 74t, compared to the photosensitive material ≠ θ/, the I) max after storage is decline in
It can be seen that the increase in Dmin was small and the storage stability was improved.
実施例！
表１！に示す多層構成のカラー感光材料１０／を作成し
た。Example! Table 1! A color photosensitive material 10/ having a multilayer structure shown in FIG.
以下に記載のもの以外は実施例／の感光材料１０／に記
載のものを使用した。Except for those described below, those described in Example/Photosensitive Material 10/ were used.
界面活性剤（５）＊ 還元剤（２）＊ 増感色素（２）＊ 増感色素（３）＊ 増感色素（４）＊ 増感色素（５）＊ 造核剤（１）＊ シアン色素供与化合物（４）＊ Ｈ すしｔｓｈ３３ マゼンタ色素供与化合物（５）＊ イエロー色素供与化合物（６）＊ 現像調節剤プレカーサー（１）＊ Ｏ 内部潜像型乳剤（ＩＶ）の調製法について述べる。Surfactant (5)* Reducing agent (2) * Sensitizing dye (2)* Sensitizing dye (3)* Sensitizing dye (4)* Sensitizing dye (5)* Nucleating agent (1)* Cyan dye-providing compound (4)* H Sushi tsh33 Magenta dye-providing compound (5)* Yellow dye-providing compound (6)* Development regulator precursor (1)* O The method for preparing the internal latent image type emulsion (IV) will be described.
臭化カリウムの水溶液と硝酸銀の水溶液を銀／したゼラ
チン水溶液に激しく攪拌しながら７ｊ０Ｃで２０分を要
して同時に添加し、平均粒径がＯ０μμｍの八面体単分
散臭化銀乳剤を得た。An aqueous solution of potassium bromide and an aqueous solution of silver nitrate were simultaneously added to an aqueous silver/gelatin solution over 20 minutes at 7J0C with vigorous stirring to obtain an octahedral monodispersed silver bromide emulsion with an average grain size of 00 μm.
この乳剤に銀１モルあたりそれぞれＡｍｇのチオ硫酸ナ
トリウム（ｊ水塩）および塩化金酸（≠水塩）を加え、
７！０Ｃで１０分間加熱することにより化学増感処理を
行なった。こうして得た臭化銀粒子をコアとして、コア
粒子形成時と同じ沈澱環境下で更にμθ分間臭化カリウ
ムと硝酸銀を添加することにより、最終的に平均粒子径
０．７μｍの八面体単分散コア／シェル臭化銀乳剤を得
た。水洗・脱塩後との乳剤に銀７モル当υ、それぞれｉ
、ｒｍｇ量のチオ硫酸ナトリウムおよび塩化金酸（弘水
塩）を加え、Ａｏ ０Ｃで６０分間加熱して化学増感処
理を行ない、内部潜像型乳剤を得た。To this emulsion were added Amg of sodium thiosulfate (j hydrate) and chloroauric acid (≠ hydrate) per mole of silver,
Chemical sensitization treatment was performed by heating at 7!0C for 10 minutes. Using the silver bromide particles thus obtained as cores, potassium bromide and silver nitrate were further added for μθ minutes in the same precipitation environment as when forming the core particles, to finally form octahedral monodisperse cores with an average particle diameter of 0.7 μm. /shell silver bromide emulsion was obtained. After washing with water and desalting, the emulsion contains 7 moles of silver, i
, rmg of sodium thiosulfate and chloroauric acid (Horohydrochloride) were added, and chemical sensitization was carried out by heating at Ao 0C for 60 minutes to obtain an internal latent image type emulsion.
内部潜像型乳剤（Ｖ）の調製法について述べる。The method for preparing the internal latent image type emulsion (V) will be described.
臭化カリウムの水溶液と硝酸銀の水溶液を臭化カリウム
を含むゼラチン水溶液（水７００ｍ１中にゼラチン３０
ｇ、臭化カリウム４ｇを含む）中に激しく攪拌しながら
７ｊ’Ｃで６０分間要して、同時に混合することにより
臭化銀乳剤を得た。添加中のｐＡｇはｒ、ｒに保った。An aqueous solution of potassium bromide and an aqueous solution of silver nitrate were added to an aqueous gelatin solution containing potassium bromide (30 g of gelatin in 700 ml of water).
(containing 4 g of potassium bromide) with vigorous stirring at 7j'C for 60 minutes to obtain a silver bromide emulsion. The pAg during addition was kept at r, r.
沈澱を行なう前（同時混合する前）にゼラチン水溶液に
ハロゲン化銀溶剤として、銀１モル当りｉｚｇを添加し
た。Before precipitation (before simultaneous mixing), izg per mole of silver was added as a silver halide solvent to the aqueous gelatin solution.
沈澱が終了すると平均粒子径がｏ、ｒｐｍの粒子サイズ
の揃った八面体臭化銀結晶が生成した。When the precipitation was completed, octahedral silver bromide crystals with a uniform grain size and an average grain size of o and rpm were formed.
この臭化銀粒子に、つぎに銀７モルあたジチオ硫酸ナト
リウム４（、ｒｍｇ（ｊ水塩）、および塩化金酸（り水
塩）２．＜ｊｍｇを加え７ｓ ０ｃでｔ。To the silver bromide grains, 4 (rmg (j hydrate)) of sodium dithiosulfate and 2.<j mg (j hydrate) of sodium dithiosulfate per 7 moles of silver were added, and the mixture was heated at 7 s 0c.
分間加熱することにより化学増感処理を行なった。Chemical sensitization treatment was performed by heating for minutes.
このようにして化学増感を施した、コア臭化銀乳剤にコ
ア粒子形成時と同じｐＡｇで臭化カリウムと硝酸銀の水
溶液を≠！分間かけて、同時混合添加を行ない、コア／
シェル乳剤を沈澱させ、さらに酸化剤として過酸化水素
を銀１モルあたり２゜３ｇ加えて７ｊ０Ｃでｆ分間加熱
したあと、水洗して、平均粒子径／μｍの八面体臭化銀
乳剤を得た。次に、この内部潜像型コア／シェル臭化銀
乳剤に銀１モルあたりチオ硫酸ナトリウム（ｊ水塩）０
．７層ｍｇおよびポリ（Ｎ−ビニルピロリドン）コｏｍ
ｇを加えｔｏ ０ｃで１０分間加熱し、粒子表面の化学
増感を行なった。An aqueous solution of potassium bromide and silver nitrate is added to the core silver bromide emulsion, which has been chemically sensitized in this way, at the same pAg as when forming the core grains! Simultaneous mixing and addition was carried out over a period of
The shell emulsion was precipitated, and 2.3 g of hydrogen peroxide was added per mole of silver as an oxidizing agent, heated at 7J0C for f minutes, and washed with water to obtain an octahedral silver bromide emulsion with an average grain size/μm. . Next, this internal latent image type core/shell silver bromide emulsion was added with 0 sodium thiosulfate (j hydrate) per mole of silver.
．． 7 layer mg and poly(N-vinylpyrrolidone) co om
g was added and heated for 10 minutes at to 0c to chemically sensitize the particle surface.
なお、本、コア／シェル乳剤調製に用いた銀水溶液濃度
はコア部、シェル部とも１モルＡｇＮＯ３／／、２！ｌ
であシ、コア部の粒子形成のために銀０層３Ａモルを添
加し、シェル部の形成のために銀０層３参モルを添加し
た。In this case, the concentration of the silver aqueous solution used in the preparation of the core/shell emulsion was 1 mol AgNO3//, 2! for both the core and shell parts. l
Next, 3 A mol of silver 0 layer was added to form particles in the core portion, and 3 A mol of silver 0 layer was added to form a shell portion.
臭化カリウム水溶液の濃度はコア部、シェル部とも１モ
ルＫＢｒ／／ｌであった。The concentration of the potassium bromide aqueous solution was 1 mol KBr//l in both the core and shell parts.
次に、感光材料ｊＯ／の第１．ｇ、７層および第２．５
層に本発明の化合物（，２Ａ）、（コＯ）、（／６）、
（１０）をそれぞれ表／乙のように添加した以外は、！
Ｏ７と全く同じ組成の感光材料よＯλ〜ｊＯりを作成し
た。感光材料ｊｔＯ／〜！Ｏりを実施例／と同様に露光
し、実施例１で用いた色素固定材料と同じものを用いて
現像処理を行ったところ、露光に対応して、イエロー、
マゼンタ、シアン、グレーのポジ画像が得られた。Next, the first photosensitive material jO/. g, 7 layers and 2.5
The compound of the present invention (,2A), (CoO), (/6), in the layer
Except that (10) was added as shown in Table/B, respectively!
Photosensitive materials Oλ~jO were prepared with exactly the same composition as O7. Photosensitive material jtO/~! When the dye was exposed in the same manner as in Example 1 and developed using the same dye fixing material used in Example 1, yellow, yellow, and
Positive images of magenta, cyan, and gray were obtained.
さらに感光材料３θノ〜ｊＯりを≠ｏ ’Ｃ，湿度７０
％の条件下、７日間保存の後、同様の露光、現像を行っ
た。保存の前後において、各色のＤｍａＸｓ Ｄｍｌｎ
を比較すると、実施例３と同様に、感光材料よ０／にく
らべて３０２〜３０りでは色像のスティンが低く、Ｓ／
Ｎの良好な画像が得られた。このことから、本発明の化
合物（λ６）、〈コθ）、（／２）、（／θンを添加し
た、感光材料！０２〜ｊＯりでは、ｓｏｉにくらべ、保
存性が改良されたと言える。Furthermore, the photosensitive material 3θ~jO ≠o 'C, humidity 70
After storage for 7 days under conditions of %, exposure and development were performed in the same manner. DmaXs Dmln of each color before and after storage
As in Example 3, the stain of the color image is lower in the photosensitive material 302 to 30 compared to the photosensitive material 0/;
A good image of N was obtained. From this, it can be said that the storage stability of the photosensitive materials !02~jO to which the compounds of the present invention (λ6), <Kθ), (/2), and (/θ) were added was improved compared to SOI. .
特許出願人 富士写真フィルム株式会社手続補正書Patent Applicant: Fuji Photo Film Co., Ltd. Procedural Amendment
Claims (1)
び下記一般式〔 I 〕〜〔IV〕で表される化合物の少な
くとも１つを有することを特徴とする熱現像感光材料。 一般式〔 I 〕 ▲数式、化学式、表等があります▼ 式中、 Ｚはｎ＝１のとき水素原子、アルキル基または−ＣＯＹ
（Ｙはアルキル基、アリール基、シクロアルキル基、ア
ルコキシ基、置換アミノ基を表す）を表し、ｎ＝２のと
きＺｎまたはＮｉを表す。 Ｒ＾１〜Ｒ＾５は水素原子、置換基または化学結合を表
す。但しこの化学結合は、直接または２〜４価残基を介
して、該残基の価数に応じた数の一般式〔 I 〕で表さ
れる化合物と結合するものである。 更に、Ｒ＾１〜Ｒ＾５の隣合う２つの基同士またはＲ＾
１〜Ｒ＾５のいずれかと上記２〜４価残基とが互いに連
結して５〜６員環を形成してもよい。 一般式〔II〕 ▲数式、化学式、表等があります▼ 式中、 Ｘは酸素原子、硫黄原子、置換イミノ基 ▲数式、化学式、表等があります▼を表す。 Ｒ＾６〜Ｒ＾９は水素原子、置換基または化学結合を表
す。但しこの化学結合は、直接または２〜４価残基を介
して、該残基の価数に応じた数の一般式〔II〕で表され
る化合物と結合するものである。 更に、Ｒ＾６〜Ｒ＾９の任意の置換基同士またはＲ＾６
〜Ｒ＾９のいずれかと上記２〜４価残基とが互いに連結
して４〜６員環を形成してもよい。 一般式〔III〕 ▲数式、化学式、表等があります▼ 式中、 Ｗは、ｎ＝１のとき水素原子、アンモニウム、−ＳＲ＾
１１またはＲ＾１＾１を表し、ｎ＝２のときＺｎまたは
Ｎｉを表す。 Ｒ＾１＾０、Ｒ＾１＾１はアルキル基、複素環残基、−
ＣＳＹ（Ｙは一般式〔 I 〕で定義したのと同じ）また
は▲数式、化学式、表等があります▼ （Ｒ＾１＾２〜Ｒ＾１＾４は各々アルキル基またはアリ
ール基を表す）を表す。 一般式〔IV〕 ▲数式、化学式、表等があります▼ 式中、 Ｒ＾１＾５、Ｒ＾１＾６は各々アルキル基、シクロアル
キル基、アルケニル基またはアリール基を表し、これら
は互いに連結して５〜６員環を形成してもよい。[Scope of Claims] A heat-developable photosensitive material comprising at least a photosensitive silver halide, a reducing agent, and at least one compound represented by the following general formulas [I] to [IV] on a support. . General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, Z is a hydrogen atom, an alkyl group, or -COY when n=1
(Y represents an alkyl group, an aryl group, a cycloalkyl group, an alkoxy group, or a substituted amino group), and when n=2 represents Zn or Ni. R^1 to R^5 represent a hydrogen atom, a substituent, or a chemical bond. However, this chemical bond is one that is bonded directly or via a divalent to tetravalent residue to the compound represented by the general formula [I], the number of which corresponds to the valence of the residue. Furthermore, two adjacent groups of R^1 to R^5 or R^
Any one of 1 to R^5 and the above divalent to tetravalent residue may be linked to each other to form a 5- to 6-membered ring. General formula [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, X represents an oxygen atom, a sulfur atom, a substituted imino group ▲There are mathematical formulas, chemical formulas, tables, etc.▼. R^6 to R^9 represent a hydrogen atom, a substituent, or a chemical bond. However, this chemical bond is one that is bonded directly or via a divalent to tetravalent residue to the compound represented by the general formula [II], the number of which corresponds to the valence of the residue. Furthermore, any substituents of R^6 to R^9 or R^6
-R^9 and the above divalent to tetravalent residue may be linked to each other to form a 4- to 6-membered ring. General formula [III] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, W is a hydrogen atom, ammonium, -SR^ when n=1
11 or R^1^1, and when n=2, it represents Zn or Ni. R^1^0, R^1^1 are alkyl groups, heterocyclic residues, -
CSY (Y is the same as defined in general formula [I]) or ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (R^1^2 to R^1^4 each represent an alkyl group or an aryl group) represent. General formula [IV] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R^1^5 and R^1^6 each represent an alkyl group, a cycloalkyl group, an alkenyl group, or an aryl group, and these are linked to each other. A 5- to 6-membered ring may be formed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33556987A JPH01177029A (en) | 1987-12-28 | 1987-12-28 | Thermal development photosensitive material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33556987A JPH01177029A (en) | 1987-12-28 | 1987-12-28 | Thermal development photosensitive material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01177029A true JPH01177029A (en) | 1989-07-13 |
Family
ID=18290050
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP33556987A Pending JPH01177029A (en) | 1987-12-28 | 1987-12-28 | Thermal development photosensitive material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01177029A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5370988A (en) * | 1994-02-28 | 1994-12-06 | Minnesota Mining And Manufacturing Company | Print stabilizers and antifoggants for photothermography |
| US6013408A (en) * | 1997-08-19 | 2000-01-11 | Fuji Photo Film Co., Ltd. | Silver halide light-sensitive material comprising support, hardening layer and light-sensitive layer |
-
1987
- 1987-12-28 JP JP33556987A patent/JPH01177029A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5370988A (en) * | 1994-02-28 | 1994-12-06 | Minnesota Mining And Manufacturing Company | Print stabilizers and antifoggants for photothermography |
| US6013408A (en) * | 1997-08-19 | 2000-01-11 | Fuji Photo Film Co., Ltd. | Silver halide light-sensitive material comprising support, hardening layer and light-sensitive layer |
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