JPH0567014B2 - - Google Patents
Info
- Publication number
- JPH0567014B2 JPH0567014B2 JP60083664A JP8366485A JPH0567014B2 JP H0567014 B2 JPH0567014 B2 JP H0567014B2 JP 60083664 A JP60083664 A JP 60083664A JP 8366485 A JP8366485 A JP 8366485A JP H0567014 B2 JPH0567014 B2 JP H0567014B2
- Authority
- JP
- Japan
- Prior art keywords
- silver
- image
- group
- silver halide
- formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 229910052709 silver Inorganic materials 0.000 claims description 58
- 239000004332 silver Substances 0.000 claims description 58
- -1 silver halide Chemical class 0.000 claims description 46
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 27
- 239000000839 emulsion Substances 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 23
- 238000009792 diffusion process Methods 0.000 claims description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 11
- 125000003118 aryl group Chemical group 0.000 claims description 10
- 125000001424 substituent group Chemical group 0.000 claims description 9
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 8
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims description 8
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 125000000962 organic group Chemical group 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 125000004434 sulfur atom Chemical group 0.000 claims description 2
- 239000010410 layer Substances 0.000 description 37
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 14
- 239000000243 solution Substances 0.000 description 13
- 239000003795 chemical substances by application Substances 0.000 description 11
- 239000007788 liquid Substances 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 239000002245 particle Substances 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 229920002678 cellulose Polymers 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- ISAKRJDGNUQOIC-UHFFFAOYSA-N Uracil Chemical compound O=C1C=CNC(=O)N1 ISAKRJDGNUQOIC-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 229920002301 cellulose acetate Polymers 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000002932 luster Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 3
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 3
- 239000011133 lead Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 229920002401 polyacrylamide Polymers 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 150000003378 silver Chemical class 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000002562 thickening agent Substances 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- 229910052724 xenon Inorganic materials 0.000 description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- CRTGSPPMTACQBL-UHFFFAOYSA-N 2,3-dihydroxycyclopent-2-en-1-one Chemical compound OC1=C(O)C(=O)CC1 CRTGSPPMTACQBL-UHFFFAOYSA-N 0.000 description 2
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 description 2
- DUFGYCAXVIUXIP-UHFFFAOYSA-N 4,6-dihydroxypyrimidine Chemical class OC1=CC(O)=NC=N1 DUFGYCAXVIUXIP-UHFFFAOYSA-N 0.000 description 2
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 2
- SHVCSCWHWMSGTE-UHFFFAOYSA-N 6-methyluracil Chemical compound CC1=CC(=O)NC(=O)N1 SHVCSCWHWMSGTE-UHFFFAOYSA-N 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical group CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- 229920001747 Cellulose diacetate Polymers 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 108010010803 Gelatin Proteins 0.000 description 2
- 229920000084 Gum arabic Polymers 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 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 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 241000978776 Senegalia senegal Species 0.000 description 2
- 206010070834 Sensitisation Diseases 0.000 description 2
- 229910021612 Silver iodide Inorganic materials 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000000205 acacia gum Substances 0.000 description 2
- 235000010489 acacia gum Nutrition 0.000 description 2
- 238000005904 alkaline hydrolysis reaction Methods 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 125000004397 aminosulfonyl group Chemical group NS(=O)(=O)* 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920000159 gelatin Polymers 0.000 description 2
- 239000008273 gelatin Substances 0.000 description 2
- 235000019322 gelatine Nutrition 0.000 description 2
- 235000011852 gelatine desserts Nutrition 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 150000003346 selenoethers Chemical class 0.000 description 2
- 230000008313 sensitization Effects 0.000 description 2
- 229940045105 silver iodide Drugs 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- NRUVOKMCGYWODZ-UHFFFAOYSA-N sulfanylidenepalladium Chemical compound [Pd]=S NRUVOKMCGYWODZ-UHFFFAOYSA-N 0.000 description 2
- 150000004763 sulfides Chemical class 0.000 description 2
- 125000000101 thioether group Chemical group 0.000 description 2
- 229940035893 uracil Drugs 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- UDATXMIGEVPXTR-UHFFFAOYSA-N 1,2,4-triazolidine-3,5-dione Chemical compound O=C1NNC(=O)N1 UDATXMIGEVPXTR-UHFFFAOYSA-N 0.000 description 1
- NVHNGVXBCWYLFA-UHFFFAOYSA-N 1,3-diazinane-2-thione Chemical compound S=C1NCCCN1 NVHNGVXBCWYLFA-UHFFFAOYSA-N 0.000 description 1
- LRGBKQAXMKYMHJ-UHFFFAOYSA-N 1,5-diphenyl-1,2,5,6-tetrahydro-[1,2,4]triazolo[1,2-a][1,2,4]triazole-3,7-dithione Chemical compound S=C1NC(C=2C=CC=CC=2)N(C(N2)=S)N1C2C1=CC=CC=C1 LRGBKQAXMKYMHJ-UHFFFAOYSA-N 0.000 description 1
- GGZHVNZHFYCSEV-UHFFFAOYSA-N 1-Phenyl-5-mercaptotetrazole Chemical group SC1=NN=NN1C1=CC=CC=C1 GGZHVNZHFYCSEV-UHFFFAOYSA-N 0.000 description 1
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- ZEQIWKHCJWRNTH-UHFFFAOYSA-N 1h-pyrimidine-2,4-dithione Chemical compound S=C1C=CNC(=S)N1 ZEQIWKHCJWRNTH-UHFFFAOYSA-N 0.000 description 1
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 description 1
- ZBCFPIKHXPYHOK-UHFFFAOYSA-N 3-[(2z)-5-chloro-2-[(2e)-2-[(3-ethyl-1,3-benzothiazol-3-ium-2-yl)methylidene]butylidene]-1,3-benzoxazol-3-yl]propane-1-sulfonate Chemical compound O\1C2=CC=C(Cl)C=C2N(CCCS([O-])(=O)=O)C/1=C/C(/CC)=C/C1=[N+](CC)C2=CC=CC=C2S1 ZBCFPIKHXPYHOK-UHFFFAOYSA-N 0.000 description 1
- NXLJHBVNLXCJJM-UHFFFAOYSA-N 3-phenylimidazole-4-thiol Chemical compound SC1=CN=CN1C1=CC=CC=C1 NXLJHBVNLXCJJM-UHFFFAOYSA-N 0.000 description 1
- IUAKHJPCOAQSAL-UHFFFAOYSA-N 4,6-dichloro-2-hydroxy-1h-triazine;sodium Chemical compound [Na].ON1NC(Cl)=CC(Cl)=N1 IUAKHJPCOAQSAL-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920002284 Cellulose triacetate Polymers 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- KNAHARQHSZJURB-UHFFFAOYSA-N Propylthiouracile Chemical compound CCCC1=CC(=O)NC(=S)N1 KNAHARQHSZJURB-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 1
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 1
- SJOOOZPMQAWAOP-UHFFFAOYSA-N [Ag].BrCl Chemical compound [Ag].BrCl SJOOOZPMQAWAOP-UHFFFAOYSA-N 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- KSZVHVUMUSIKTC-UHFFFAOYSA-N acetic acid;propan-2-one Chemical compound CC(C)=O.CC(O)=O KSZVHVUMUSIKTC-UHFFFAOYSA-N 0.000 description 1
- 230000021736 acetylation Effects 0.000 description 1
- 238000006640 acetylation reaction Methods 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 1
- 229910001864 baryta Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 125000005521 carbonamide group Chemical group 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001923 cyclic compounds Chemical class 0.000 description 1
- QAWTYRYXDYHQNU-UHFFFAOYSA-N diazathiane Chemical class NSN QAWTYRYXDYHQNU-UHFFFAOYSA-N 0.000 description 1
- HULWKEZTVNNHQB-UHFFFAOYSA-N disodium methanol sulfide Chemical compound CO.[S-2].[Na+].[Na+] HULWKEZTVNNHQB-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- HOKNTYWEKQQKGV-UHFFFAOYSA-N disulfonylmethane Chemical class O=S(=O)=C=S(=O)=O HOKNTYWEKQQKGV-UHFFFAOYSA-N 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 238000005213 imbibition Methods 0.000 description 1
- 125000002346 iodo group Chemical group I* 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- AGBQKNBQESQNJD-UHFFFAOYSA-M lipoate Chemical compound [O-]C(=O)CCCCC1CCSS1 AGBQKNBQESQNJD-UHFFFAOYSA-M 0.000 description 1
- 235000019136 lipoic acid Nutrition 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- HNQIVZYLYMDVSB-UHFFFAOYSA-N methanesulfonimidic acid Chemical group CS(N)(=O)=O HNQIVZYLYMDVSB-UHFFFAOYSA-N 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- BJOXIRAGBLTXIZ-UHFFFAOYSA-N n,n-bis(2-methoxyethyl)hydroxylamine Chemical compound COCCN(O)CCOC BJOXIRAGBLTXIZ-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002894 organic compounds 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
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 229960002662 propylthiouracil Drugs 0.000 description 1
- 229940083082 pyrimidine derivative acting on arteriolar smooth muscle Drugs 0.000 description 1
- 150000003230 pyrimidines Chemical class 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000000565 sulfonamide group Chemical group 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000004250 tert-Butylhydroquinone Substances 0.000 description 1
- 235000019281 tert-butylhydroquinone Nutrition 0.000 description 1
- 229960002663 thioctic acid Drugs 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 239000012463 white pigment Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D257/00—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms
- C07D257/02—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D257/04—Five-membered rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D233/84—Sulfur atoms
-
- 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
- G03C8/24—Photosensitive materials characterised by the image-receiving section
- G03C8/243—Toners for the silver image
Description
(産業上の利用分野)
本発明は銀塩拡散転写による画像形成方法並び
にそこで使用するフイルムユニツトに関するもの
である。
(従来の技術)
ハロゲン化銀等の銀塩を使用する拡散転写によ
る画像形成方法は周知である。該方法は具体的に
説明すると、例えば画像露光された感光性ハロゲ
ン化銀乳剤層を現像剤およびハロゲン化銀溶剤を
含むアルカリ水溶液で処理して、露光されたハロ
ゲン化銀粒子を現像剤により銀に還元し、一方未
露光のハロゲン化銀粒子をハロゲン化銀溶剤によ
り転写性の銀錯塩とし、この銀錯塩を前記乳剤層
と重ね合わされた銀沈殿剤含有層(受像層)へイ
ンビビシヨンにより拡散・転写させ、そこで銀錯
塩を銀沈殿剤の助けを借りて現像剤で還元して銀
像を得ることからなる。
この方法を実施するに際しては、例えば通常支
持体上に感光性ハロゲン化銀乳剤層を設けた感光
要素、支持体上に銀沈殿剤を含有する受像層を設
けた受像要素および現像剤、ハロゲン化銀溶剤お
よび増粘剤を含む活性アルカリ水溶液を収納する
破壊可能な容器よりなる処理要素を組み合せてな
るフイルムユニツトが使用される。先ず感光要素
の乳剤層を画像露光したのち、当該乳剤層と受像
要素の受像層とが対向するように感光要素と受像
要素を重ね合わせつつ、その間に処理要素を破壊
して粘性アルカリ水溶液が展開されるように一対
のローラーの間を通し、所定の時間放置したのち
に受像要素を感光要素から剥離することにより受
像層に所望の画像が形成されたプリントを得るこ
とができる。
このようなハロゲン化銀等の銀塩を使用する拡
散転写法においては、一般に銀像は黒ではなく、
褐色もしくは他の許容されない色を呈することが
知られている。そこで、このような拡散転写法に
おける欠点を解消するために色調剤が使用され
る。
従来公知の色調剤としては典型例として1−フ
エニル−5−メルカプト−1,2,3,4−テト
ラゾールが知られている。その他にも米国特許第
3756825号に記載されているようなS−置換ピリ
ミジン誘導体が知られ、高い光学濃度を有する暗
青色の画像を与えることが報告されている。
(発明が解決しようとする問題点)
このように形成された銀画像の色調は画質に大
きく影響するが、現在市場で使用されている画像
の色調は必らずしも好ましいとはいえず、その改
良が望まれている。漆黒調をもつ画像を与え、画
像の金属光沢を少なくし、最大濃度を上昇させる
ような満足すべき色調剤は得られていない。
(発明の目的)
本発明の目的は銀塩拡散転写による新規な画像
形成方法を提供することにある。
本発明の他の目的は、好ましい漆黒調の画像を
与える方法を提供することにある。
(問題点を解決するための手段)
そこで本発明者らは、新しい色調剤を用いて色
調を改良する方法を鋭意検討した結果、スルホ基
もしくはカルボキシ基で置換されたアルキル基ま
たはスルホ基もしくはカルボキシ基で置換された
アリール基をもつ含窒素ヘテロ環状のメルカプタ
ン化合物を用いることにより前記諸目的が達成で
きた。即ち、画像露光された感光性ハロゲン化銀
乳剤層を現像剤、ハロゲン化銀溶剤およびアルカ
リの存在下で現像して、該乳剤層の未露光ハロゲ
ン化銀の少なくとも一部を転写性銀錯塩とし、該
錯塩の少なくとも一部を銀沈殿剤含有受像層へ転
写して該受像層に画像を形成させることを含む銀
塩拡散転写により画像形成方法において、下記一
般式で示される化合物を含有する処理組成物を用
いて画像を形成することを特徴とする銀塩拡散転
写による画像形成方法によつて達成できた。
一般式
(Industrial Application Field) The present invention relates to an image forming method by silver salt diffusion transfer and a film unit used therein. (Prior Art) Image forming methods by diffusion transfer using silver salts such as silver halides are well known. Specifically, the method includes, for example, treating an imagewise exposed photosensitive silver halide emulsion layer with an alkaline aqueous solution containing a developer and a silver halide solvent, and converting the exposed silver halide grains into silver by the developer. On the other hand, unexposed silver halide grains are converted into a transferable silver complex salt using a silver halide solvent, and this silver complex salt is diffused and transferred into a silver precipitant-containing layer (image-receiving layer) overlaid with the emulsion layer by imbivision. It consists of transferring and then reducing the silver complex with a developer with the help of a silver precipitant to obtain a silver image. When carrying out this method, for example, a light-sensitive element having a light-sensitive silver halide emulsion layer on a support, an image-receiving element having an image-receiving layer containing a silver precipitant on a support, a developer, a halogenated A film unit is used which combines a processing element consisting of a breakable container containing an aqueous activated alkaline solution containing a silver solvent and a thickener. First, the emulsion layer of the light-sensitive element is imagewise exposed, and then the light-sensitive element and the image-receiving element are overlapped so that the emulsion layer and the image-receiving layer of the image-receiving element face each other, while the processing element is destroyed and a viscous alkaline aqueous solution is developed. The image-receiving element is passed between a pair of rollers as shown in FIG. In the diffusion transfer method that uses silver salts such as silver halide, the silver image is generally not black;
Known to exhibit brown or other unacceptable colors. Therefore, toning agents are used to overcome these drawbacks in the diffusion transfer method. A typical example of a conventionally known color toning agent is 1-phenyl-5-mercapto-1,2,3,4-tetrazole. Other U.S. patents
S-substituted pyrimidine derivatives, such as those described in US Pat. No. 3,756,825, are known and reported to give dark blue images with high optical density. (Problems to be Solved by the Invention) The color tone of the silver image formed in this manner greatly affects the image quality, but the color tone of the images currently used on the market is not necessarily desirable. Improvements are desired. Satisfactory toning agents have not been available which give images with jet black tones, reduce the metallic luster of the images, and increase the maximum density. (Object of the Invention) An object of the present invention is to provide a novel image forming method using silver salt diffusion transfer. Another object of the present invention is to provide a method that provides a desirable jet-black image. (Means for Solving the Problems) Therefore, as a result of intensive study on a method for improving color tone using a new color toning agent, the present inventors discovered that an alkyl group substituted with a sulfo group or a carboxy group, or The above objects were achieved by using a nitrogen-containing heterocyclic mercaptan compound having an aryl group substituted with a group. That is, the image-exposed photosensitive silver halide emulsion layer is developed in the presence of a developer, a silver halide solvent, and an alkali to convert at least a portion of the unexposed silver halide in the emulsion layer into a transferable silver complex salt. , a process containing a compound represented by the following general formula in an image forming method by silver salt diffusion transfer, which includes transferring at least a portion of the complex salt to an image receiving layer containing a silver precipitant to form an image on the image receiving layer. This was achieved by an image forming method using silver salt diffusion transfer, which is characterized by forming an image using a composition. general formula
【式】
式中、Zは硫黄原子、酸素原子又は
[Formula] In the formula, Z is a sulfur atom, an oxygen atom, or
【式】を表わす。R3は水素原子、置要もし
くは無置換のアルキル基(但し、置換基としてス
ルホ基、カルボキシル基を除く)、又は置換もし
くは無置換のアリール基(但し、置換基としてス
ルホ基、カルボキシル基を除く)を表わす。
R2はスルホ基又はカルボキシ基を少なくとも
1個有する有機基を表わす。 L1は−CONR−、
−NRCO−、−SO2NR−、−NRSO2−、−OCO、
−COO−、−S−、−NR−、−CO−、−SO−、−
SO2−、−OCOO−、−NRCONR1−、−NRCOO
−、−OCONR−、又は−NRSO2NR1−を表わ
し、ここでR,R1は各々水素原子、アルキル基
又はアリール基を表わす。nは0又は1を表わ
す。
一般式のL1におけるR,R1としてはさらに具
体的には各々水素原子、アルキル基(好ましくは
メチル基、エチル基などの低級アルキル基)、又
はアリール基(好ましくはフエニル基)であり、
置換基を有するものも含む。
R2で表わされる有機基としては、さらに具体
的には炭素数1〜20のアルキル基(例えばメチル
基、エチル基、オクチル基など)、炭素数6〜20
のアリール基(例えばフエニル基、ナフチル基な
ど)又はアルキル基、アリール基が−S−、−O
−、−N、−CO−、−SO−、−SO2−などのよう
な連結基を介して構成しているものを挙げること
ができる。R2はカルボキシ基、スルホ基に加え
さらに他の置換基を有するものも含む。他の置換
基としてはアルキル基(メチル基、エチル基な
ど)、アリール基(例えばフエニル基)、ハロゲン
原子(F,C,Brなど)、アルコキシ基(メト
キシ基、メトキシエトキシ基など)、カルボンア
ミド基(アセトアミド基など)、スルホンアミド
基(メタンスルホンアミド基など)、ヒドロキシ
基、またはスルフアモイル基(無置換スルフアモ
イル基、メチルスルフアモイル基など)を挙げる
ことが出来る。
R3としては、さらに具体的には水素原子、炭
素数1〜20の置換もしくは無置換のアルキル基、
炭素数6〜20の置換もしくは無置換のアリール基
であり、置換基としてはR2の置換基と同一のも
のを挙げることが出来る。
本発明に用いられる化合物の好ましい具体例を
以下に挙げる。
1Represents [formula]. R 3 is a hydrogen atom, an optional or unsubstituted alkyl group (excluding sulfo groups and carboxyl groups as substituents), or a substituted or unsubstituted aryl group (excluding sulfo groups and carboxyl groups as substituents) ). R 2 represents an organic group having at least one sulfo group or carboxy group. L 1 is −CONR−,
−NRCO−, −SO 2 NR−, −NRSO 2 −, −OCO,
-COO-, -S-, -NR-, -CO-, -SO-, -
SO 2 −, −OCOO−, −NRCONR 1 −, −NRCOO
-, -OCONR-, or -NRSO2NR1- , where R and R1 each represent a hydrogen atom, an alkyl group, or an aryl group. n represents 0 or 1. More specifically, R and R 1 in L 1 of the general formula are each a hydrogen atom, an alkyl group (preferably a lower alkyl group such as a methyl group or an ethyl group), or an aryl group (preferably a phenyl group),
It also includes those with substituents. More specifically, the organic group represented by R2 includes an alkyl group having 1 to 20 carbon atoms (for example, a methyl group, an ethyl group, an octyl group, etc.), and an alkyl group having 6 to 20 carbon atoms.
aryl group (e.g. phenyl group, naphthyl group, etc.) or alkyl group, aryl group is -S-, -O
-, -N, -CO-, -SO-, -SO2- , etc. can be mentioned. In addition to a carboxy group and a sulfo group, R 2 also includes those having other substituents. Other substituents include alkyl groups (methyl group, ethyl group, etc.), aryl groups (e.g. phenyl group), halogen atoms (F, C, Br, etc.), alkoxy groups (methoxy group, methoxyethoxy group, etc.), carbonamide Examples include a group (such as an acetamide group), a sulfonamide group (such as a methanesulfonamide group), a hydroxy group, or a sulfamoyl group (such as an unsubstituted sulfamoyl group and a methylsulfamoyl group). More specifically, R 3 includes a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms,
It is a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, and examples of the substituent include the same substituents as R2 . Preferred specific examples of the compounds used in the present invention are listed below. 1
【式】 2【formula】 2
【式】 3【formula】 3
【式】 4【formula】 4
【式】 5【formula】 5
【化】 6[ka] 6
【化】 7[ka] 7
【化】 8[ka] 8
【化】 9[ka] 9
【化】 10[ka] Ten
【化】 11[ka] 11
【化】 12[ka] 12
【化】 13[ka] 13
【化】 14[ka] 14
【化】 15[ka] 15
【化】 16[ka] 16
【式】 17【formula】 17
【化】 18[ka] 18
【化】 19[ka] 19
【化】 20[ka] 20
【化】 21[ka] twenty one
【化】 22[ka] twenty two
【化】 23[ka] twenty three
【化】
上記の化合物の使用量は、処理組成物100g当
り10-4〜1gが好ましく5×10-4〜0.5gがさら
に好ましく、10-3〜0.2gが最も好ましい。
一般式で示される化合物は以下の文献に記載さ
れている公知の方法により合成することが出来
る。ジヤーナル・オブ・アメリカン・ケミカル・
ソサイエテイ(J.Am.Chem.Soc.)、第44巻1502
〜1510頁、米国特許3017270号、英国特許940169
号、特公昭49−8334号、特開昭55−59463、ヘテ
ロ環化学の進歩(Advanced in Heterocyclic
Chemistry)、9,165〜209(1968)ヘテロ環化合
物の化学(Khim.Geterotsikl.Soedin)、7、
(7)、1905〜9、西独特許2716707号。
以下、本発明を更に詳細に説明する。
本発明の画像形成方法並びにフイルムユニツト
において、現像剤は感光要素もしくは処理要素に
存在しうる。現像剤はたとえばヒドロキノン、第
三ブチルヒドロキノン、p−アミノフエノールな
どのようなパラまたはオルト位にヒドロキシ基及
び/又はアミノ基を有するベンゼンまたはナフタ
レン系の有機化合物が用いられる。
さらに米国特許3615440号に記載されているよ
うなレダクチン酸や米国特許3730716号に記載さ
れているようなα,β−エンジオールが好ましく
用いられる。さらに、米国特許3287125号及び同
3293034号に記載されているようなヒドロキシル
アミン現像剤が特に好ましく用いられる。
現像剤の使用量は処理液100g当り0.1g〜40g
含有させることが好ましく、1〜20gが最も好ま
しい。
また、現像剤として特公昭49−13580号公報発
明に記載されている1−アリール−3−ピラゾリ
ジノン化合物を上記現像剤と併用しても良い。
ハロゲン化銀溶剤は処理要素、感光要素および
受像要素の少なくとも1つに存在しうる。その中
でも処理要素が最も好ましい。米国特許第
2857274号、同第2857275号および同第2857276号
に記載されている環状化合物が適しており、中で
もウラシル、ウラゾール、6メチルウラシルなど
が好ましい例である。
更にアルカリ金属チオ硫酸塩、特にナトリウム
またはカリウム塩が好ましく、また米国特許第
3958992号、同第3976647号、同第4009167号、同
第4032538号、同第4046568号、同第4047954号、
同第4047955号、同第4107176号および特開昭47−
330のジスルホニルメタン化合物や米国特許第
4126459号、同第4150228号、同第4211559号およ
び同第4211562号のチオエーテル基をもつジヒド
ロキシピリミジン化合物などや米国特許第
4251617号、同第4267254号および同第4267256号
のアミノチオエーテルから選ぶことができる。こ
れらは単独または複数で使用することもでき、二
種以上の環状イミド化合物やチオエーテル基をも
つジヒドロキシピリミジン化合物を併用する場合
には長期間プリントを保存してもその表面に白い
結晶が析出することがなくなる利点がある。
ハロゲン化銀溶剤の添加量は処理組成物100g
当り0.1〜30g含有させることが好ましく、0.5g
〜10gが最も好ましい。
本発明に用いる処理液を重ね合された感光要素
と受像要素との間に薄い層として分布させること
によりこれを適用する場合、処理液は重合体フイ
ルム形成剤、濃厚化剤あるいは増粘剤を含んでい
ることが好ましい。ヒドロキシエチルセルロース
およびナトリウムカルボキシメチルセルロース
は、この目的のために特に有用であり、拡散転写
写真法の公知の原理により適当な粘度を与えるの
に効果的な濃度で処理液中に含有させる。処理液
はさらに、銀塩拡散転写法において公知の別の助
剤、例えばかぶり防止剤、色調剤(toning
agents)、安定化剤等を含有させてもよい。特に、
オキシエチルアミノ化合物、例えばトリエタノー
ルアミンを含有させることは、米国特許第
3619185号に記載のように、処理液の貯蔵寿命を
増加させるのに有用である。
上述のような処理液は、好ましくは破壊可能な
容器に収納されて処理要素とされる。破壊可能な
容器およびその材質については、公知のいかなる
ものを使用することもでき、これらについては例
えば米国特許3056491号、同3056492号、同
3173580号、同3750907号、同3833381号、同
4303750号、同4303751号等に詳しく記載されてい
る。
本発明における受像要素は、銀沈殿剤を含有す
る受像層を担持する支持体、例えばバライタ紙、
三酢酸セルロースあるいはポリエステル類を包含
する。このような受像要素は、好ましくは、銀沈
殿剤を分散させた適当なセルロースエステル、例
えば二酢酸セルロースの被覆用溶液で、必要によ
り、下塗した支持体を被覆することによりつくる
ことができる。えられたセルロースエステルの層
をアルカリ加水分解させて、セルロースエステル
の深度方向の少くとも一部分をセルロースに変え
る。特に有用な具体例において、銀沈殿剤および
(あるいは)下にある加水分解を受けなかつた下
層のセルロースエステル、例えば二酢酸セルロー
スを含有するセルロースエステル層の加水分解を
受けなかつた部分は、銀転写像の色調、安定性あ
るいは他の写真的性質を改良するのに適している
1種あるいはそれ以上のメルカプト化合物を含ん
でいる。このようなメルカプト化合物はインビビ
シヨン中に、これが最初に置かれた位置から拡散
して利用される。この型の受像要素は米国特許
3607269号に記載されている。
適当な銀沈殿剤の例としては、重金属、例えば
鉄、鉛、亜鉛、ニツケル、カドミウム、スズ、ク
ロム、銅、コバルト、特に貴金属、例えば金、
銀、白金およびパラジウムがある。他の有用な銀
沈殿剤は重金属の硫化物およびセレン化物、特に
水銀、銅、アルミニウム、亜鉛、カドミウム、コ
バルト、ニツケル、銀、鉛、アンチモン、ビスマ
ス、セリウム、マグネシウム、金、白金及びパラ
ジウムの硫化物、および鉛、亜鉛、アンチモンお
よびニツケルのセレン化物をあげることができ
る。銀塩拡散転写法において銀沈殿剤の如き材料
の働きについては、例えば米国特許2774667号に
記載されている。
さらに、受像層と色調剤や安定剤を含有する層
の間に中間層を設けることが好ましい。中間層と
して好ましいものは、アラビアゴム、ポリビニル
アルコール、ポリアクリルアミドなどを挙げるこ
とができる。
また受像層の表面には、処理液展開後の剥離時
に処理液が受像層の表面に付着するのを防止する
為に、剥離層を設けることが好ましい。このよう
な剥離層として好ましいものは、アラビアゴム、
ヒドロキシエチルセルロース、メチルセルロー
ス、ポリビニルアルコール、ポリアクリルアミ
ド、アルギン酸ソーダの他に、米国特許3772024
号、同3820999号および英国特許1360653号に記載
されているものを挙げることができる。
本発明に用いる化合物は受像要素の中間層及び
剥離層の少なくとも1つの塗布組成物として含ま
せること、又はアルカリ加水分解用ケン化液組成
物として含ませることが好ましい。
本発明の特別な態様においては受像層を以下に
述べる感光要素の中に組み込むことができる。例
えば、ポリエチレンテレフタレートシートの上
に、順に銀沈殿剤を含有する受像層、二酸化チタ
ンなどの白色顔料を含む光反射層、カーボンブラ
ツクのような光吸収性物質を含む遮光層、感光性
ハロゲン化銀乳剤層を設けたものは、その好まし
い例である。このような態様においては、拡散転
写処理後に感光性ハロゲン化銀乳剤を剥離しなく
とも、光反射層により背後の層が遮蔽されるの
で、ポリエチレンテレフタレートシートを通して
受像層に形成された像を観察することができる。
更に、本発明では感光性ハロゲン化銀乳剤を支
持体上に塗布して得られる感光要素が好ましく用
いられる。
本発明に用いる感光性ハロゲン化銀乳剤にはハ
ロゲン化銀として臭化銀、沃臭化銀、沃塩臭化
銀、塩臭化銀および塩化銀のいずれを用いてもよ
い。好ましいハロゲン化銀は10モル%以下の沃化
銀を含む沃臭化銀または沃塩臭化銀である。特に
好ましいのは3モル%から10モル%までの沃化銀
を含む沃臭化銀である。
感光性乳剤中のハロゲン化銀粒子の平均粒子サ
イズ(球状または球に近似の粒子の場合は粒子直
径、立方体粒子の場合は稜長を粒子サイズとし、
投影面積にもとづく平均で表わす)は特に問わな
いが3μ以下が好ましく、さらに1.5μ以下が好まし
いが、特に好ましいのは0.8〜1.2μである。
粒子サイズ分布はせまくても広くてもいずれで
もよい。
感光性乳剤中のハロゲン化銀粒子は、立方体、
八面体のような等軸晶系結晶形を有するものでも
よく、また球状、板状などのような異形結晶形を
もつもの、あるいはこれらの結晶形の複合形をも
つものでもよい。種々の結晶形の粒子の混合物か
ら成つていてもよい。
ハロゲン化銀粒子は内部と表層とが異なる相で
構成されていても、均一な相から成つていてもよ
い。また潜像が主として表面に形成されるような
粒子でもよく、粒子内部に主として形成されるよ
うな粒子であつてもよい。潜像が主として表面に
形成される粒子の方が好ましい。
感光性乳剤層の厚さは0.5〜8.0μ、特に0.6〜
6.0μであり、ハロゲン化銀粒子の塗布量は0.1〜
3g/m2、好ましくは0.2〜1.5g/m2である。
感光性乳剤はハロゲン化銀写真乳剤として通常
用いられる方法で調製され、化学増感、分光増感
が必要に応じてなされ、乳剤へはカブリ防止剤、
安定剤、硬膜剤、塗布助剤、帯電防止剤などを含
有せしめうる。又乳剤にはゼラチンなどのベヒク
ルを使用する。
写真像を得るための露光は通常の方法を用いて
行なえばよい。すなわち、自然光(日光)、タン
グステン電灯、螢光灯、水銀灯、キセノンアーク
灯、炭素アーク灯、キセノンフラツシユ灯、陰極
線管フライングスポツトなど公知の多種の光源を
いずれでも用いることができる。露光時間は通常
カメラで用いられる1/1000秒から1秒の露光時間
はもちろん、1/1000秒より短い露光、たとえばキ
セノン閃光灯や陰極線管を用いた1/104〜1/
106秒の露光を用いることもできるし、1秒より
長い露光を用いることもできる。必要に応じて色
フイルターで露光に用いられる光の分光組成を調
節することができる。露光にレーザー光を用いる
こともできる。また電子線、X線、γ線、α線な
どによつて励起された螢光体から放出される光に
よつて露光してもよい。
以上説明したような感光要素、受像要素および
処理要素を組み合わせてフイルムユニツトとする
ための各要素の配置ならびに結合方法について
は、例えばネブレツト(Neblette′s)、ハンド
ブツク オブ フオトグラフイ アンド リプロ
グラフイ(HAND BOOK OF
PHOTOGRAPHY AND REPROGRAPHY)、
第7版、第282〜285頁に記載されており、特に好
ましい態様は米国特許3350991号に詳しく説明さ
れているので、これらを参考にすることができ
る。
(本発明の効果)
本発明によれば、一般式で示される化合物の存
在下で、好ましい色調(漆黒調)をもつ画像を得
ることができるが、とくに、処理液に一般式で示
される化合物を用いると、画像の金属光沢がなく
なつたり、最高濃度が上昇するという効果が得ら
れる。
(実施例)
以下、本発明を実施例に基き、更に具体的に説
明するが本発明はこれら実施例により何等限定さ
れるものではない。
実施例 1
感光シート
シングルジエツト法によりハロゲン化銀粒子を
形成し通常の方法により物理熟成し、脱塩処理
し、更に化学熟成して沃臭化銀乳剤(ヨード含量
5.5モル%)を得た。この乳剤に含まれるハロゲ
ン化銀粒子の平均直径は0.9ミクロンであつた。
この乳剤1Kg中には0.65モルのハロゲン化銀が含
まれていた。この乳剤を1Kgずつポツトに採取
し、50℃の恒温バス中において溶解した。
それぞれにオルソ増感色素 3−{5−クロロ
−2−〔2−エチル−3−(3−エチル−2−ベン
ゾチアゾリニリデン)プロペニル〕−3−ベンズ
オキサゾリオ}プロパン−スルホナート、パンク
ロ増感色素(4−{2−〔(3−エチルベンゾチア
ゾリン−(2−イリデン)−2−メチル−1−プロ
ペニル〕−3−ベンゾチアゾリオ}ブタン−スル
ホナート)と4−ヒドロキシ−6−メチル−1,
3,3a,7−テトラザインデンの1重量%水溶
液10ml、2−ヒドロキシ−4,6−ジクロロトリ
アジンナトリウム塩の1重量%水溶液10ml、更に
ドデシルベンゼンスルホン酸ナトリウムの1重量
%水溶液10ml、リポ酸0.1重量%メタノール溶液
10mlとを添加し40℃のもとで混合攪拌した。この
完成乳剤を下塗り済の二酸化チタン含有のポリエ
チレンテレフタレートフイルムベースに乾燥膜厚
が3ミクロンとなるように塗布、乾燥して試料を
得た。同時に、ゼラチン水溶液にポリメチルメタ
クリレートのラテツクス(平均サイズ3.5μ)を添
加し乾燥膜厚が1ミクロンとなるように塗布し
た。塗布された銀量は0.5g/m2であつた。
受像シート
ポリエチレンラミネート紙の上に次の表で示す
ようなセルロースアセテート(酢化度54%)18g
とスチレン−無水マレイン酸共重合体12g又はア
クリル酸−アルキルアクリーレート共重合体12g
とをアセトン270mlとメタノール30mlに溶解した
溶液を54ml/m2の厚さで塗布乾燥した。この上
に、3,6−ジフエニール−1,4−ジメルカプ
ト−3H,6H−2,3a,5,6a−テトラザペンタ
レン(0.05g/m2)の10%セルロースアセテート
アセトン溶液を乾燥膜厚が10g/m2となるように
塗布した。更にこの上にポリアクリルアミドの5
%水溶液にジメチロール尿素(5%)水溶液と酢
酸(50%)をそれぞれ5%、1,25%濃度で添加
混合し、25ml/m2の塗布厚で塗布した。更にこの
上に、3%セルロースアセテートのアセトン/メ
タノール(9/1)溶液に硫化パラジウムが微分
散された液を塗布した。この塗布液には1.25×
10-6モル/m2の塗布量となるように1−フエニル
−5−メルカプトイミダゾールを含有させた。乾
燥膜厚は0.8μmであつた。この塗布物に下記のア
ルカリ液を18ml/m2の割合で塗布し、水洗乾燥し
て受像シートを作製した。上記の硫化パラジウム
分散液は、セルロースアセテートの5.3%アセト
ン/メタノール(9/1)混合溶液に7×10-3モ
ルの硫化ナトリウムメタノール溶液と7×10-3モ
ルの塩化パラジウムナトリウムのメタノール溶液
を添加しよく攪拌して作つた。
処理液
水酸化カリウム(85%) 260g
二酸化チタン 3g
ウラシル 45g
6−メチルウラシル 45g
ヒドロキシエチルセルロース 70g
酸化亜鉛 10g
N,N−ビスメトキシエチルヒドロキシルアミ
ン 50g
トリエタノールアミン 7g
テトラヒドロピリミジンチオン 0.4g
2,4−ジメルカプトピリミジン 0.35g
6−nプロピルチオウラシル 0.35g
この処理液に次の化合物0.1gを添加し、さら
に水を加えて総量が2Kgに上記の処理液を前記感
光シートと受像シートとの間に展開した後、45秒
経過してから剥離した。
その時の色調と最高濃度および相対感度(D=
0.6)を表−1に示す。最低濃度はいずれの場合
も0.10の値を示した。embedded image The amount of the above compound used is preferably 10 −4 to 1 g, more preferably 5×10 −4 to 0.5 g, and most preferably 10 −3 to 0.2 g per 100 g of the treatment composition. The compound represented by the general formula can be synthesized by a known method described in the following literature. Journal of American Chemical
Society (J.Am.Chem.Soc.), Volume 44, 1502
~1510 pages, US Patent No. 3017270, UK Patent No. 940169
No. 49-8334, JP-A-55-59463, Advance in Heterocyclic
Chemistry), 9 , 165-209 (1968) Chemistry of heterocyclic compounds (Khim.Geterotsikl.Soedin), 7,
(7), 1905-9, West German Patent No. 2716707. The present invention will be explained in more detail below. In the image forming method and film unit of the present invention, the developer may be present in the photosensitive element or the processing element. As the developer, a benzene- or naphthalene-based organic compound having a hydroxyl group and/or an amino group in the para or ortho position, such as hydroquinone, tert-butylhydroquinone, p-aminophenol, etc., is used. Furthermore, reductic acid as described in US Pat. No. 3,615,440 and α,β-enediol as described in US Pat. No. 3,730,716 are preferably used. Furthermore, U.S. Patent No. 3,287,125 and
Hydroxylamine developers such as those described in No. 3293034 are particularly preferably used. The amount of developer used is 0.1g to 40g per 100g of processing solution.
The content is preferably 1 to 20 g, most preferably 1 to 20 g. Further, as a developer, a 1-aryl-3-pyrazolidinone compound described in the invention disclosed in Japanese Patent Publication No. 49-13580 may be used in combination with the above developer. The silver halide solvent may be present in at least one of the processing element, the light-sensitive element and the image-receiving element. Among these, the processing element is the most preferred. US Patent No.
The cyclic compounds described in No. 2857274, No. 2857275, and No. 2857276 are suitable, and among them, uracil, urazol, 6-methyluracil, etc. are preferred examples. Further preferred are alkali metal thiosulfates, especially the sodium or potassium salts, and also as described in U.S. Pat.
No. 3958992, No. 3976647, No. 4009167, No. 4032538, No. 4046568, No. 4047954,
No. 4047955, No. 4107176 and JP-A-47-
330 disulfonylmethane compounds and U.S. patent no.
4126459, 4150228, 4211559, and 4211562, dihydroxypyrimidine compounds with thioether groups, and U.S. Patent No.
It can be selected from the aminothioethers of No. 4251617, No. 4267254 and No. 4267256. These can be used alone or in combination; if two or more types of cyclic imide compounds or dihydroxypyrimidine compounds with thioether groups are used together, white crystals may precipitate on the surface even if the print is stored for a long time. This has the advantage of eliminating The amount of silver halide solvent added is 100g of the processing composition.
It is preferable to contain 0.1 to 30g per serving, and 0.5g
~10g is most preferred. When the processing liquid used in the present invention is applied by distributing it as a thin layer between a superposed photosensitive element and an image receiving element, the processing liquid may contain a polymeric film forming agent, a thickening agent, or a thickening agent. It is preferable that it contains. Hydroxyethylcellulose and sodium carboxymethylcellulose are particularly useful for this purpose and are included in the processing solution at concentrations effective to provide the appropriate viscosity according to known principles of diffusion transfer photography. The processing solution may further contain other auxiliary agents known in the silver salt diffusion transfer process, such as antifoggants, toning agents, etc.
agents), stabilizers, etc. may also be included. especially,
The inclusion of oxyethylamino compounds, such as triethanolamine, is described in U.S. Pat.
No. 3,619,185, it is useful for increasing the shelf life of processing fluids. The processing liquid as described above is preferably stored in a breakable container to serve as a processing element. Any known breakable container and its material can be used; for example, US Pat. No. 3,056,491, US Pat.
No. 3173580, No. 3750907, No. 3833381, No.
It is described in detail in No. 4303750, No. 4303751, etc. The image-receiving element in the present invention includes a support carrying an image-receiving layer containing a silver precipitant, such as baryta paper,
Includes cellulose triacetate or polyesters. Such image receiving elements can be prepared by coating an optionally subbed support with a coating solution of a suitable cellulose ester, such as cellulose diacetate, preferably having a silver precipitating agent dispersed therein. The obtained cellulose ester layer is subjected to alkaline hydrolysis to convert at least a portion of the cellulose ester in the depth direction into cellulose. In a particularly useful embodiment, the unhydrolyzed portion of the cellulose ester layer containing the silver precipitant and/or the underlying unhydrolyzed cellulose ester, such as cellulose diacetate, is the silver transfer agent. Contains one or more mercapto compounds suitable for improving image tone, stability or other photographic properties. Such mercapto compounds are utilized during imbibition by diffusing from the position where they are initially placed. This type of receiving element is patented in the US
Described in No. 3607269. Examples of suitable silver precipitants include heavy metals such as iron, lead, zinc, nickel, cadmium, tin, chromium, copper, cobalt, especially noble metals such as gold,
There are silver, platinum and palladium. Other useful silver precipitating agents are sulfides and selenides of heavy metals, especially sulfides of mercury, copper, aluminum, zinc, cadmium, cobalt, nickel, silver, lead, antimony, bismuth, cerium, magnesium, gold, platinum and palladium. and selenides of lead, zinc, antimony and nickel. The function of materials such as silver precipitants in silver salt diffusion transfer methods is described, for example, in US Pat. No. 2,774,667. Furthermore, it is preferable to provide an intermediate layer between the image-receiving layer and the layer containing a toning agent or stabilizer. Preferred materials for the intermediate layer include gum arabic, polyvinyl alcohol, and polyacrylamide. Further, it is preferable to provide a peeling layer on the surface of the image-receiving layer in order to prevent the treatment liquid from adhering to the surface of the image-receiving layer during peeling after spreading the treatment liquid. Preferred materials for such a release layer include gum arabic,
In addition to hydroxyethylcellulose, methylcellulose, polyvinyl alcohol, polyacrylamide, and sodium alginate, US Patent 3772024
No. 3,820,999 and British Patent No. 1,360,653. The compound used in the present invention is preferably included as a coating composition for at least one of the intermediate layer and release layer of the image-receiving element, or as a saponifying liquid composition for alkaline hydrolysis. In particular embodiments of the invention, image-receiving layers can be incorporated into the photosensitive elements described below. For example, on a polyethylene terephthalate sheet, an image-receiving layer containing a silver precipitant, a light-reflecting layer containing a white pigment such as titanium dioxide, a light-shielding layer containing a light-absorbing substance such as carbon black, and a photosensitive silver halide A preferred example is one provided with an emulsion layer. In such an embodiment, the light-reflecting layer shields the layer behind the light-reflecting layer without peeling off the photosensitive silver halide emulsion after the diffusion transfer process, so the image formed on the image-receiving layer can be observed through the polyethylene terephthalate sheet. be able to. Furthermore, in the present invention, a photosensitive element obtained by coating a photosensitive silver halide emulsion on a support is preferably used. In the photosensitive silver halide emulsion used in the present invention, any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride may be used as the silver halide. Preferred silver halides are silver iodobromide or silver iodochlorobromide containing 10 mol % or less of silver iodide. Particularly preferred is silver iodobromide containing from 3 mol % to 10 mol % silver iodide. Average grain size of silver halide grains in a light-sensitive emulsion (grain diameter for spherical or approximately spherical grains, edge length for cubic grains,
(expressed as an average based on the projected area) is not particularly limited, but is preferably 3μ or less, more preferably 1.5μ or less, and particularly preferably 0.8 to 1.2μ. The particle size distribution may be narrow or wide. The silver halide grains in the light-sensitive emulsion are cubic,
It may have an equiaxed crystal form such as an octahedron, it may have an irregular crystal form such as a spherical shape or a plate shape, or it may have a composite form of these crystal forms. It may also consist of a mixture of particles of various crystalline forms. The interior and surface layers of the silver halide grains may be composed of different phases, or may be composed of a uniform phase. Further, the particles may be particles in which the latent image is mainly formed on the surface, or may be particles in which the latent image is mainly formed inside the particles. Particles in which latent images are mainly formed on the surface are preferred. The thickness of the photosensitive emulsion layer is 0.5~8.0μ, especially 0.6~
6.0μ, and the coating amount of silver halide grains is 0.1~
3 g/m 2 , preferably 0.2 to 1.5 g/m 2 . The light-sensitive emulsion is prepared by a method commonly used for silver halide photographic emulsions, chemical sensitization and spectral sensitization are performed as necessary, and antifoggants, antifoggants, etc. are added to the emulsion.
It may contain stabilizers, hardeners, coating aids, antistatic agents, and the like. Also, a vehicle such as gelatin is used in the emulsion. Exposure to obtain a photographic image may be carried out using a conventional method. That is, any of the various known light sources can be used, such as natural light (sunlight), tungsten electric lamps, fluorescent lamps, mercury lamps, xenon arc lamps, carbon arc lamps, xenon flash lamps, cathode ray tube flying spots, and the like. Exposure times include not only exposure times of 1/1000 seconds to 1 second, which are normally used with cameras, but also exposure times shorter than 1/1000 seconds, such as 1/10 4 to 1/1 seconds using xenon flash lamps and cathode ray tubes.
Exposures of 10 6 seconds can be used, or exposures longer than 1 second can be used. If necessary, the spectral composition of the light used for exposure can be adjusted using a color filter. Laser light can also be used for exposure. Alternatively, exposure may be performed using light emitted from a phosphor excited by electron beams, X-rays, γ-rays, α-rays, or the like. The arrangement and combination method of each element to form a film unit by combining the photosensitive element, image receiving element, and processing element as described above can be found in, for example, Neblette's Handbook of Photography and Reprography.
PHOTOGRAPHY AND REPROGRAPHY),
7th Edition, pages 282-285, and particularly preferred embodiments are detailed in US Pat. No. 3,350,991, which may be referred to. (Effects of the present invention) According to the present invention, an image having a preferable color tone (jet black tone) can be obtained in the presence of the compound represented by the general formula, but in particular, the compound represented by the general formula can be used in the processing liquid. When used, the effect of eliminating the metallic luster of the image and increasing the maximum density can be obtained. (Examples) Hereinafter, the present invention will be explained in more detail based on Examples, but the present invention is not limited to these Examples in any way. Example 1 Photosensitive sheet Silver halide grains were formed by a single-jet method, physically ripened by a conventional method, desalted, and chemically ripened to form a silver iodobromide emulsion (with an iodo content of
5.5 mol%) was obtained. The average diameter of the silver halide grains contained in this emulsion was 0.9 microns.
0.65 mol of silver halide was contained in 1 kg of this emulsion. Each 1 kg of this emulsion was collected in a pot and dissolved in a constant temperature bath at 50°C. Ortho-sensitizing dye 3-{5-chloro-2-[2-ethyl-3-(3-ethyl-2-benzothiazolinylidene)propenyl]-3-benzoxazolio}propane-sulfonate, panchlorosensitizing dye Sensitive dye (4-{2-[(3-ethylbenzothiazoline-(2-ylidene)-2-methyl-1-propenyl]-3-benzothiazolio}butane-sulfonate) and 4-hydroxy-6-methyl-1,
10 ml of a 1 wt% aqueous solution of 3,3a,7-tetrazaindene, 10 ml of a 1 wt% aqueous solution of 2-hydroxy-4,6-dichlorotriazine sodium salt, 10 ml of a 1 wt% aqueous solution of sodium dodecylbenzenesulfonate, and lipoic acid. 0.1 wt% methanol solution
10 ml was added and mixed and stirred at 40°C. This completed emulsion was coated on a polyethylene terephthalate film base containing titanium dioxide which had been primed to a dry film thickness of 3 microns, and dried to obtain a sample. At the same time, polymethyl methacrylate latex (average size 3.5 μm) was added to the gelatin aqueous solution and coated to a dry film thickness of 1 μm. The amount of silver coated was 0.5 g/m 2 . Image-receiving sheet: 18 g of cellulose acetate (degree of acetylation 54%) as shown in the following table on polyethylene laminated paper.
and 12 g of styrene-maleic anhydride copolymer or 12 g of acrylic acid-alkyl acrylate copolymer
A solution prepared by dissolving this in 270 ml of acetone and 30 ml of methanol was applied to a thickness of 54 ml/m 2 and dried. On top of this, a 10% cellulose acetate acetone solution of 3,6-diphenyl-1,4-dimercapto-3H,6H-2,3a,5,6a-tetrazapentalene (0.05 g/m 2 ) was added to a dry film thickness. It was applied so that the amount was 10 g/m 2 . Furthermore, on top of this, polyacrylamide 5
Dimethylol urea (5%) aqueous solution and acetic acid (50%) were added and mixed to the % aqueous solution at concentrations of 5%, 1, and 25%, respectively, and coated at a coating thickness of 25 ml/m 2 . Furthermore, a liquid in which palladium sulfide was finely dispersed in an acetone/methanol (9/1) solution of 3% cellulose acetate was applied on top of this. This coating solution has 1.25×
1-phenyl-5-mercaptoimidazole was contained in a coating amount of 10 -6 mol/m 2 . The dry film thickness was 0.8 μm. This coated material was coated with the following alkaline solution at a rate of 18 ml/m 2 , washed with water and dried to produce an image-receiving sheet. The above palladium sulfide dispersion was prepared by adding a 7 x 10 -3 mol sodium sulfide methanol solution and a 7 x 10 -3 mol sodium palladium chloride methanol solution to a 5.3% acetone/methanol (9/1) mixed solution of cellulose acetate. Add it and stir well. Treatment liquid Potassium hydroxide (85%) 260g Titanium dioxide 3g Uracil 45g 6-Methyluracil 45g Hydroxyethyl cellulose 70g Zinc oxide 10g N,N-bismethoxyethylhydroxylamine 50g Triethanolamine 7g Tetrahydropyrimidinethione 0.4g 2,4-di Mercaptopyrimidine 0.35g 6-n Propylthiouracil 0.35g 0.1g of the following compound was added to this treatment solution, and water was further added to make a total amount of 2Kg.The above treatment solution was spread between the photosensitive sheet and the image receiving sheet. After that, it was peeled off after 45 seconds. Color tone, maximum density and relative sensitivity at that time (D=
0.6) is shown in Table-1. The minimum concentration showed a value of 0.10 in all cases.
【表】
なお、剥離時間5分におけるプリント表面の金
属光沢は比較例の無添加のサンプルだけが、わず
かに金属光沢を示したが他のサンプルはいずれも
それを示さなかつた。
表1から本発明に用いる化合物の場合(1−1
〜1−10)には漆黒調の色調が得られると同時に
高い最大濃度を示すこと、とくに無添加の場合
(1〜13)より最大濃度が高くなることが明らか
である。[Table] Regarding the metallic luster on the print surface after a peeling time of 5 minutes, only the additive-free sample of the comparative example showed a slight metallic luster, but none of the other samples showed it. From Table 1, in the case of compounds used in the present invention (1-1
It is clear that in cases of 1-1-10), a jet-black color tone is obtained and at the same time a high maximum density is exhibited, especially that the maximum density is higher than that in the case of no additives (1-13).
Claims (1)
現像剤、ハロゲン化銀溶剤およびアルカリの存在
下で現像して、該乳剤層の未露光ハロゲン化銀の
少なくとも一部を転写性銀錯塩とし、該錯塩の少
なくとも一部を銀沈殿剤含有受像層へ転写して該
受像層に画像を形成させることを含む銀塩拡散転
写による画像形成方法において、下記一般式で示
される化合物を含有する処理組成物を用いて画像
を形成することを特徴とする銀塩拡散転写による
画像形成方法。 一般式 【式】 式中、Zは硫黄原子、酸素原子又は
【式】を表わす。R3は水素原子、置換もし くは無置換のアルキル基(但し、置換基としてス
ルホ基、カルボキシル基を除く)、又は置換もし
くは無置換のアリール基(但し、置換基としてス
ルホ基、カルボキシル基を除く)を表わす。 R2はスルホ基又はカルボキシ基を少なくとも
1個有する有機基を表わす。 L1は−CONR−、
−NRCO−、−SO2NR−、−NRSO2−、−OCO
−、−COO−、−S−、−NR−、−CO−、−SO−、
−SO2−、−OCOO−、−NRCONR1−、−
NRCOO−、−OCONR、−又は−NRSO2NR1−
を表わし、ここでR,R1は各々水素原子、アル
キル基又はアリール基を表わす。nは0又は1を
表わす。[Scope of Claims] 1. An imagewise exposed photosensitive silver halide emulsion layer is developed in the presence of a developer, a silver halide solvent and an alkali to remove at least a portion of the unexposed silver halide in the emulsion layer. In an image forming method by silver salt diffusion transfer, which includes using a transferable silver complex salt and transferring at least a portion of the complex salt to an image receiving layer containing a silver precipitant to form an image on the image receiving layer, the method is represented by the following general formula. An image forming method by silver salt diffusion transfer, characterized in that an image is formed using a processing composition containing a compound. General formula [Formula] In the formula, Z represents a sulfur atom, an oxygen atom, or [Formula]. R 3 is a hydrogen atom, a substituted or unsubstituted alkyl group (excluding sulfo groups and carboxyl groups as substituents), or a substituted or unsubstituted aryl group (excluding sulfo groups and carboxyl groups as substituents) represents. R 2 represents an organic group having at least one sulfo group or carboxy group. L 1 is −CONR−,
−NRCO−, −SO 2 NR−, −NRSO 2 −, −OCO
-, -COO-, -S-, -NR-, -CO-, -SO-,
−SO 2 −, −OCOO−, −NRCONR 1 −, −
NRCOO−, −OCONR, − or −NRSO 2 NR 1 −
, where R and R 1 each represent a hydrogen atom, an alkyl group or an aryl group. n represents 0 or 1.
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP8366485A JPS61241749A (en) | 1985-04-19 | 1985-04-19 | Formation of image by silver salt diffusion transfer |
US06/853,835 US4683189A (en) | 1985-04-19 | 1986-04-21 | Toners for silver halide diffusion transfer image with sulfo or carboxyl groups |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP8366485A JPS61241749A (en) | 1985-04-19 | 1985-04-19 | Formation of image by silver salt diffusion transfer |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS61241749A JPS61241749A (en) | 1986-10-28 |
JPH0567014B2 true JPH0567014B2 (en) | 1993-09-24 |
Family
ID=13808724
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP8366485A Granted JPS61241749A (en) | 1985-04-19 | 1985-04-19 | Formation of image by silver salt diffusion transfer |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS61241749A (en) |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS57164734A (en) * | 1981-04-03 | 1982-10-09 | Fuji Photo Film Co Ltd | Black-and-white photographic sensitive silver halide material |
JPS58189628A (en) * | 1982-04-28 | 1983-11-05 | Konishiroku Photo Ind Co Ltd | Thermodevelopable image recording material |
-
1985
- 1985-04-19 JP JP8366485A patent/JPS61241749A/en active Granted
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS57164734A (en) * | 1981-04-03 | 1982-10-09 | Fuji Photo Film Co Ltd | Black-and-white photographic sensitive silver halide material |
JPS58189628A (en) * | 1982-04-28 | 1983-11-05 | Konishiroku Photo Ind Co Ltd | Thermodevelopable image recording material |
Also Published As
Publication number | Publication date |
---|---|
JPS61241749A (en) | 1986-10-28 |
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