JPH0640201B2 - Method for producing silver halide emulsion - Google Patents
Method for producing silver halide emulsionInfo
- Publication number
- JPH0640201B2 JPH0640201B2 JP61020593A JP2059386A JPH0640201B2 JP H0640201 B2 JPH0640201 B2 JP H0640201B2 JP 61020593 A JP61020593 A JP 61020593A JP 2059386 A JP2059386 A JP 2059386A JP H0640201 B2 JPH0640201 B2 JP H0640201B2
- Authority
- JP
- Japan
- Prior art keywords
- silver halide
- group
- solution
- silver
- emulsion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- -1 silver halide Chemical class 0.000 title claims description 150
- 229910052709 silver Inorganic materials 0.000 title claims description 108
- 239000004332 silver Substances 0.000 title claims description 108
- 239000000839 emulsion Substances 0.000 title claims description 72
- 238000004519 manufacturing process Methods 0.000 title claims description 19
- 239000000243 solution Substances 0.000 claims description 68
- 238000000034 method Methods 0.000 claims description 50
- 150000001875 compounds Chemical class 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 15
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- 239000012452 mother liquor Substances 0.000 claims description 8
- 239000000084 colloidal system Substances 0.000 claims description 5
- 150000004820 halides Chemical class 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 3
- 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 3
- 239000012266 salt solution Substances 0.000 claims description 2
- 239000000725 suspension Substances 0.000 claims description 2
- 239000013078 crystal Substances 0.000 description 29
- 108010010803 Gelatin Proteins 0.000 description 24
- 239000008273 gelatin Substances 0.000 description 24
- 229920000159 gelatin Polymers 0.000 description 24
- 235000019322 gelatine Nutrition 0.000 description 24
- 235000011852 gelatine desserts Nutrition 0.000 description 24
- 239000010410 layer Substances 0.000 description 21
- 239000000463 material Substances 0.000 description 21
- 230000035945 sensitivity Effects 0.000 description 19
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 19
- 239000002245 particle Substances 0.000 description 17
- 229920001577 copolymer Polymers 0.000 description 15
- 125000000217 alkyl group Chemical group 0.000 description 14
- 239000000203 mixture Substances 0.000 description 13
- 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 12
- 229910021612 Silver iodide Inorganic materials 0.000 description 12
- 229940045105 silver iodide Drugs 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 11
- 238000009826 distribution Methods 0.000 description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 10
- 238000011161 development Methods 0.000 description 9
- 230000018109 developmental process Effects 0.000 description 9
- 125000003118 aryl group Chemical group 0.000 description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 8
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 206010070834 Sensitisation Diseases 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 125000003277 amino group Chemical group 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 125000000753 cycloalkyl group Chemical group 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 230000008313 sensitization Effects 0.000 description 6
- 229910021529 ammonia Inorganic materials 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000011033 desalting Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910052736 halogen Inorganic materials 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 125000005843 halogen group Chemical group 0.000 description 4
- 125000005647 linker group Chemical group 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 125000003396 thiol group Chemical group [H]S* 0.000 description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 229910021607 Silver chloride Inorganic materials 0.000 description 3
- SJOOOZPMQAWAOP-UHFFFAOYSA-N [Ag].BrCl Chemical compound [Ag].BrCl SJOOOZPMQAWAOP-UHFFFAOYSA-N 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 239000002612 dispersion medium Substances 0.000 description 3
- 238000000635 electron micrograph Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 150000002367 halogens Chemical group 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical class [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000003926 acrylamides Chemical class 0.000 description 2
- 238000004061 bleaching Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 229920001477 hydrophilic polymer Polymers 0.000 description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- FSQQTNAZHBEJLS-UPHRSURJSA-N maleamic acid Chemical compound NC(=O)\C=C/C(O)=O FSQQTNAZHBEJLS-UPHRSURJSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000013081 microcrystal Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 238000010979 pH adjustment Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical class [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 1
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 description 1
- KJUGUADJHNHALS-UHFFFAOYSA-N 1H-tetrazole Substances C=1N=NNN=1 KJUGUADJHNHALS-UHFFFAOYSA-N 0.000 description 1
- CARFETJZUQORNQ-UHFFFAOYSA-N 1h-pyrrole-2-thiol Chemical class SC1=CC=CN1 CARFETJZUQORNQ-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical class NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 1
- 125000000143 2-carboxyethyl group Chemical group [H]OC(=O)C([H])([H])C([H])([H])* 0.000 description 1
- 125000004200 2-methoxyethyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- XRZDIHADHZSFBB-UHFFFAOYSA-N 3-oxo-n,3-diphenylpropanamide Chemical class C=1C=CC=CC=1NC(=O)CC(=O)C1=CC=CC=C1 XRZDIHADHZSFBB-UHFFFAOYSA-N 0.000 description 1
- RYYXDZDBXNUPOG-UHFFFAOYSA-N 4,5,6,7-tetrahydro-1,3-benzothiazole-2,6-diamine;dihydrochloride Chemical compound Cl.Cl.C1C(N)CCC2=C1SC(N)=N2 RYYXDZDBXNUPOG-UHFFFAOYSA-N 0.000 description 1
- HVBSAKJJOYLTQU-UHFFFAOYSA-N 4-aminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C=C1 HVBSAKJJOYLTQU-UHFFFAOYSA-N 0.000 description 1
- 125000001960 7 membered carbocyclic group Chemical group 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 229920001817 Agar Polymers 0.000 description 1
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical class [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 101150006989 NDEL1 gene Proteins 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- FJWGYAHXMCUOOM-QHOUIDNNSA-N [(2s,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6s)-4,5-dinitrooxy-2-(nitrooxymethyl)-6-[(2r,3r,4s,5r,6s)-4,5,6-trinitrooxy-2-(nitrooxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-3,5-dinitrooxy-6-(nitrooxymethyl)oxan-4-yl] nitrate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O)O[C@H]1[C@@H]([C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@@H](CO[N+]([O-])=O)O1)O[N+]([O-])=O)CO[N+](=O)[O-])[C@@H]1[C@@H](CO[N+]([O-])=O)O[C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O FJWGYAHXMCUOOM-QHOUIDNNSA-N 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 229920006397 acrylic thermoplastic Polymers 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- 235000010419 agar Nutrition 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000000783 alginic acid Substances 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 229960001126 alginic acid Drugs 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000004202 aminomethyl group Chemical group [H]N([H])C([H])([H])* 0.000 description 1
- 150000001448 anilines Chemical class 0.000 description 1
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 229920006318 anionic polymer Polymers 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000000732 arylene group Chemical group 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
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical class [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- RJTANRZEWTUVMA-UHFFFAOYSA-N boron;n-methylmethanamine Chemical compound [B].CNC RJTANRZEWTUVMA-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000006309 butyl amino group Chemical group 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical class [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- VZWXIQHBIQLMPN-UHFFFAOYSA-N chromane Chemical compound C1=CC=C2CCCOC2=C1 VZWXIQHBIQLMPN-UHFFFAOYSA-N 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Chemical class 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 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 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000004851 cyclopentylmethyl group Chemical group C1(CCCC1)C* 0.000 description 1
- 229920005994 diacetyl cellulose Polymers 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000006264 diethylaminomethyl group Chemical group [H]C([H])([H])C([H])([H])N(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- AFOSIXZFDONLBT-UHFFFAOYSA-N divinyl sulfone Chemical compound C=CS(=O)(=O)C=C AFOSIXZFDONLBT-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 125000004705 ethylthio group Chemical group C(C)S* 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000013213 extrapolation Methods 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000005456 glyceride group Chemical group 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 150000002343 gold Chemical class 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical class [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 150000005204 hydroxybenzenes Chemical class 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 150000004693 imidazolium salts Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 1
- 229940006461 iodide ion Drugs 0.000 description 1
- 150000002497 iodine compounds Chemical class 0.000 description 1
- 125000002346 iodo group Chemical group I* 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002503 iridium Chemical class 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical class [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000006224 matting agent Substances 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
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-N methanesulfonic acid Substances CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 150000002940 palladium Chemical class 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 125000003356 phenylsulfanyl group Chemical group [*]SC1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 150000003057 platinum Chemical class 0.000 description 1
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229940005642 polystyrene sulfonic acid Drugs 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 150000003283 rhodium Chemical class 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Chemical class 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical class [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- HAAYBYDROVFKPU-UHFFFAOYSA-N silver;azane;nitrate Chemical compound N.N.[Ag+].[O-][N+]([O-])=O HAAYBYDROVFKPU-UHFFFAOYSA-N 0.000 description 1
- 238000009751 slip forming Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 229950000244 sulfanilic acid Drugs 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 150000003536 tetrazoles Chemical class 0.000 description 1
- 125000003831 tetrazolyl group Chemical group 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- 239000013598 vector Substances 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
- G03C1/015—Apparatus or processes for the preparation of emulsions
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は高感度化に適した感光性ハロゲン化銀粒子を有
するハロゲン化銀乳剤の製造方法に関する。The present invention relates to a method for producing a silver halide emulsion having photosensitive silver halide grains suitable for increasing sensitivity.
近年写真用のハロゲン化銀乳剤の写真特性に対して、高
感度、優れた粒状性、高鮮鋭性、低いカブリ濃度、高い
最高濃度等、極めて高い水準のものが要求されるに至っ
た。これらの特性の向上は乳剤に含まれるハロゲン化銀
粒子の光に対する感度をいかに高めるかに帰着する。即
ち高感度に粒子を整えることができれば所要の感度の感
光材料を得るためのハロゲン化銀粒子を微細化すること
が可能となり、その画質、カブリ等を改善し得ることは
周知の通りである。従来高感度化の要請は主として沃臭
化銀乳剤を用いるネガ用感光材料に対するものであった
が、最近では比較的低感度でよしとされてきたカラーペ
ーパー用等の塩臭化銀乳剤を用いた感光材料にもプリン
ト作業の能率向上等のため強く高感度化が求められてお
り、種々のハロゲン化銀組成を有するハロゲン化銀粒子
に適用しうる高感度化技術の開発が続けられている現状
である。In recent years, extremely high levels of photographic characteristics of silver halide emulsions for photography, such as high sensitivity, excellent graininess, high sharpness, low fog density and high maximum density, have been demanded. The improvement of these characteristics results in how to increase the sensitivity of the silver halide grains contained in the emulsion to light. That is, it is well known that if the grains can be arranged with high sensitivity, the silver halide grains for obtaining a light-sensitive material having a required sensitivity can be miniaturized, and the image quality and fog can be improved. Conventionally, the demand for higher sensitivity has been mainly for negative photosensitive materials using silver iodobromide emulsions, but recently, silver chlorobromide emulsions for color paper, which have been regarded as good with relatively low sensitivity, have been used. Sensitive materials are strongly required to have high sensitivity in order to improve the efficiency of printing work, etc., and the development of high sensitivity technology applicable to silver halide grains having various silver halide compositions is continuing. Is.
これらの要請にたいして、高感度乳剤としては、沃臭化
銀である沃素を15モル％以下含む乳剤が良く知られてい
る。これらの乳剤を調製する方法としては、従来からア
ンモニア法、中性法、酸性法等のpH条件、pAg条件を制
御する方法、混合法としてはシングルジェット法、ダブ
ルジェット法等が知られている。In response to these requirements, an emulsion containing 15 mol% or less of iodine, which is silver iodobromide, is well known as a high-sensitivity emulsion. As a method for preparing these emulsions, a method of controlling pH conditions such as ammonia method, neutral method, acidic method, pAg condition, etc., and a single jet method, a double jet method, etc. are known as a mixing method. .
これらの公知技術を基礎にして、更に高感度、微細粒状
性、高鮮鋭度、低カブリを達成するためより精緻な技術
手段が開発され沃臭化銀乳剤においては、晶癖、粒度分
布はもとより、個々のハロゲン化銀粒子内での沃素の濃
度分布まで制御された乳剤が研究されている。Based on these known techniques, more sophisticated technical means have been developed to achieve higher sensitivity, fine graininess, high sharpness and low fog. In silver iodobromide emulsion, not only crystal habit and grain size distribution but also Emulsions in which the concentration distribution of iodine within individual silver halide grains is controlled have been studied.
上述のような高い写真性能を達成するための最も正統的
な方法はハロゲン化銀粒子の量子効率を高めることであ
るが、量子効率を理論的に計算し粒度分布の影響を考察
した研究が、例えば写真の進歩に関する1980年東京シン
ポジュームの予稿集“インターラクションズ ビトウィ
ーン ライト アンド マテリアルズ フォ フォトグ
ラフィックアプリケーションズ”91頁に記載されてい
る。The most orthodox way to achieve high photographic performance as described above is to increase the quantum efficiency of silver halide grains, but research that theoretically calculated quantum efficiency and considered the influence of grain size distribution, For example, it can be found on page 91 of the 1980 Tokyo Symposium proceedings on photographic progress, "Interactions Between Vienna Light and Materials for Photographic Applications".
この研究によれば粒度分布を狭くした単分散乳剤を用い
ることが量子効率を向上させるのに有効であることが示
唆されている。更に粒子形成後に行なわれる化学増感の
工程において、低いカブリを保ったまま効率良く高感度
を達成するためにも単分散乳剤が有利であると考えられ
る。This study suggests that using a monodisperse emulsion with a narrow grain size distribution is effective in improving quantum efficiency. Further, in the process of chemical sensitization performed after grain formation, the monodisperse emulsion is considered to be advantageous for efficiently achieving high sensitivity while keeping low fog.
工業的に単分散乳剤をつくるためには、特開昭55-48521
号に記載されているように厳密なpAg及びpHの制御のも
とに、理論上求められた銀イオン及びハロゲンイオンの
反応系への供給速度の制御及び十分な攪拌が必要とされ
る。こうした条件下で製造されるハロゲン化銀粒子は立
方体、８面体、14面体のいずれかの形状を有しているい
わゆる正常晶から成っており、高感度化し得ることが知
られている。特公昭55-42737号には、よりカブリの少な
いものとして(110)面を持つ菱12面体の塩臭化銀粒子を
含む写真乳剤が開示されている。To industrially produce a monodisperse emulsion, JP-A-55-48521
Under the strict control of pAg and pH as described in No. 3, it is necessary to control the theoretically required supply rate of silver ions and halogen ions to the reaction system and to perform sufficient stirring. It is known that the silver halide grains produced under such conditions are so-called normal crystals having a cubic, octahedral or tetradecahedral shape and can be highly sensitive. Japanese Examined Patent Publication No. 55-42737 discloses a photographic emulsion containing rhombodecahedral silver chlorobromide grains having a (110) face with less fog.
また、特公昭60-222842号及び特願昭59-158111号には、
よりカブリの少ないものとして、表面が沃臭化銀からな
る(110)結晶面であるハロゲン化銀粒子が開示されてい
る。In addition, in Japanese Patent Publication No. 60-222842 and Japanese Patent Application No. 59-158111,
As a material with less fog, silver halide grains whose surface is a (110) crystal plane of silver iodobromide are disclosed.
一方特願昭59-206765号には(110)面の中央に稜線を有す
る結晶面を持つ臭化銀、沃臭化銀粒子が開示されてお
り、これにより高感度化し得ることが示されている。こ
の結晶面は、非常に高次な結晶面であると考えられ、ミ
ラー指数は決定できないがその特性については、特願昭
59-206765号に述べられており、便宜的に準(110)面と名
付けられている。On the other hand, Japanese Patent Application No. 59-206765 discloses silver bromide and silver iodobromide grains having a crystal plane having a ridge in the center of the (110) plane, and it has been shown that the sensitivity can be increased. There is. This crystal plane is considered to be a very high-order crystal plane, and the Miller index cannot be determined.
No. 59-206765, it is named quasi (110) plane for convenience.
前記のようにハロゲン化銀粒子の結晶面と写真特性の関
係に甚だ深いものがあり、その間に潜んでいる関係を更
に詳細に検討することによって更に優れた特性を示すハ
ロゲン化銀乳剤が開発される可能性を有している。As described above, there is a deep relationship between the crystal planes of silver halide grains and photographic characteristics, and a silver halide emulsion exhibiting even more excellent characteristics was developed by studying the relationship hidden between them. Have the potential to
前記のように写真特性にハロゲン化銀粒子の結晶面が深
甚な影響を及ぼすことが明らかにされて来た時点で、前
記された(100)面、(110)面、(111)面或は前記に謂う準
(110)面を明確に作り分ける技術が必要であり、本発明
に於ては準(110)面に囲まれ明瞭な24面体のハロゲン化
銀粒子を調製する技術を確立し更に該準(110)面を有す
る粒子を含む乳剤の製造方法を提供し、該24面体粒子を
含む乳剤によって一層高感度、低かぶり、高画質のハロ
ゲン化銀写真感光材料を提供しようとするものである。As described above, when it has been revealed that the crystal planes of silver halide grains have a profound effect on photographic properties, the (100) plane, (110) plane, (111) plane or So-called above
It is necessary to have a technique for making distinct (110) faces, and in the present invention, a technique for preparing clear 24-sided silver halide grains surrounded by quasi (110) faces has been established and the quasi (110) The present invention aims to provide a method for producing an emulsion containing grains having a (1) plane, and to provide a silver halide photographic light-sensitive material having higher sensitivity, lower fog, and higher image quality by using the emulsion containing the tetrahedral grains.
前記特願昭59-206725号に於て、「(110)面の中央に稜線
を有する結晶面」が開示され、仮に準(110)面と称され
「稜線を共有する屋根型の２つの準(110)面の交角は110
°より鈍角である」旨記載されている。In the above-mentioned Japanese Patent Application No. 59-206725, "a crystal plane having a ridgeline at the center of a (110) plane" is disclosed, and it is tentatively called a quasi (110) plane "two roof-shaped quasi-shades sharing a ridgeline". The intersection angle of the (110) plane is 110
It is an obtuse angle than °. "
第１図は準(110)結晶面のみで外表面が構成されたとき
のハロゲン化銀微結晶全体の形態を示す図である。また
第２図は直線b1b2の方向から見た側面図である。準(11
0)結晶面として表わされる等価な結晶面は24個存在す
る。このため、すべての外表面が準(110)結晶面で構成
される結晶は24面体の形態をとり、外表面を構成する各
表面は鈍角三角形となる。頂点は２種類ものが存在し、
すなわち、第１図におけるa1と等価な６頂点とb1と等価
な８頂点である。頂点a1では８平面が境を接しており、
頂点b1では３平面が接している。辺もまた２種類のもの
が存在する。即ち第１図における辺a1b1に等価な24個の
辺と、a1a2に等価な12個の辺である。FIG. 1 is a diagram showing the morphology of the whole silver halide microcrystal when the outer surface is constituted only by quasi (110) crystal planes. FIG. 2 is a side view seen from the direction of the straight line b 1 b 2 . Quasi (11
0) There are 24 equivalent crystal planes represented as crystal planes. For this reason, a crystal in which all outer surfaces are quasi (110) crystal faces has a shape of a dodecahedron, and each surface constituting the outer surface is an obtuse triangle. There are two types of vertices,
That is, there are 6 vertices equivalent to a 1 and 8 vertices equivalent to b 1 in FIG. At apex a 1 , 8 planes are in contact with each other,
Three planes are in contact with each other at the vertex b 1 . There are also two types of edges. That is, there are 24 sides equivalent to sides a 1 b 1 and 12 sides equivalent to a 1 a 2 in FIG.
外表面が準(110)面から構成されるほぼ完全な24面体ハ
ロゲン化銀粒子の電子顕微鏡写真を第12図に示す。FIG. 12 shows an electron micrograph of nearly perfect tetrahedral silver halide grains whose outer surface is composed of quasi (110) planes.
次に断面図を用いて準(110)面、(111)面、(110)面の関
係を説明する。第１図の24面体の直線b1b2を含み、三角
形a1a2b1、及び三角形a1a2b2に垂直な平面ｄにおける断
面図を第３図の実線１で示す。Next, the relationship between the quasi (110) plane, the (111) plane, and the (110) plane will be described with reference to cross-sectional views. It includes straight b 1 b 2 of 24 tetrahedra of FIG. 1, indicated by a triangle a 1 a 2 b 1, and a solid line 1 in cross section a third view in a plane perpendicular d into triangles a 1 a 2 b 2.
すなわち、第３図において、実線１は前記平面dと準(11
0)面との交線を表わしている。１方、破線２は(110)
面、１点鎖線３は(111)面を表わしたものであり、準(11
0)面、(110)面、(111)面それぞれの法線ベクトルを，
，で示した。従って面の方向は （n≧２，nは自然数）＝〔110〕でありまた、 と表すことができる。従って面自身は夫々(nn1)、(110)
及び(111)と表わされる。θは辺a1a2を境に隣接する２
個の(nn1)結晶面のなす角であり、n≧２，nは自然数と
いう制限から110°＜θ＜180°である。That is, in FIG. 3, the solid line 1 is quasi (11
It represents the line of intersection with the 0) plane. One side, broken line 2 is (110)
The plane and the alternate long and short dash line 3 represent the (111) plane.
The normal vectors of the (0) plane, the (110) plane, and the (111) plane are
, Indicated by. Therefore the direction of the surface is (N ≧ 2, n is a natural number) = [110], and It can be expressed as. Therefore, the faces themselves are (nn1) and (110), respectively.
And (111). 2 θ adjacent boundary edges a 1 a 2
Is an angle formed by (nn1) crystal planes, and n ≧ 2 and n are 110 ° <θ <180 ° due to the limitation of natural numbers.
以上により、本発明に係わる準(110)結晶面は(nn1)面と
表示されるものであり、ハロゲン化銀微結晶において従
来から知られている(111)結晶面及び(110)結晶面とは全
く異なる結晶面であることは明らかである。また(110)
結晶面と異なることは特に説明を要しないであろう。From the above, the quasi- (110) crystal plane according to the present invention is represented as a (nn1) plane, and the conventionally known (111) crystal plane and (110) crystal plane in silver halide microcrystals are Are clearly different crystal planes. Also (110)
The difference from the crystal plane does not require any particular explanation.
ハロゲン化銀微粒子の結晶面を固定するためには、基板
上に配向させて、塗布された乳剤の粉末法Ｘ線回析（ブ
レンティン・オブ・ザ・ソサエティ・オブ・サイエンテ
ィフィック・フォトグラフィー・オブ・ジャパン(Bulle
tin of the society of ScientificPhotography of Jap
an)13巻、５頁参照）が屡々用いられる。In order to fix the crystal plane of silver halide fine grains, X-ray diffraction by powder method of the emulsion which was orientated on the substrate and coated (Brentin of the Society of Scientific Photography) was used.・ Japan (Bulle
tin of the society of Scientific Photography of Jap
an) Volume 13, page 5) is often used.
しかし、本発明に係る(nn1)面については、すべての外
表面が(nn1)面で構成された24面体粒子であっても粒子
体積に対する１つの表面の面積の比が、立方体、８面
体、菱形、12面体等に比べて著しく小さい。このため(n
n1)面をもって基板上に配向させることが困難である。
また、(nn1)面が高次であるためその回析強度も小さ
い。以上の理由により(nn1)面の同定に粉末法Ｘ線回析
を用いることはできず、現在のところ、電子顕微鏡写真
から２種類の辺の長さの比、２個の面の間の角度等を求
め、面のミラー指数を同定せざるを得ない。これによれ
ば、本発明に係る(nn1)面はnの値の広い範囲で、存在す
ることがわかった。However, regarding the (nn1) plane according to the present invention, the ratio of the area of one surface to the particle volume is a cube, an octahedron, even if all the outer surfaces are tetrahedral particles composed of the (nn1) plane. Remarkably smaller than diamonds and dodecahedrons. Therefore (n
It is difficult to align the n1) plane on the substrate.
Further, since the (nn1) plane is of higher order, its diffraction strength is also small. For the above reasons, powder method X-ray diffraction cannot be used to identify the (nn1) plane, and at present, from electron micrographs, the ratio of the two side lengths and the angle between the two planes are shown. Therefore, we have no choice but to identify the Miller index of the surface. According to this, it was found that the (nn1) plane according to the present invention exists in a wide range of the value of n.
本発明に係わるハロゲン化銀粒子のハロゲン銀組成は実
質的に、臭化銀または沃臭化銀からなり、本発明の効果
を阻害しない範囲で臭化銀および沃臭化銀以外のハロゲ
ン化銀、例えば塩化銀を含有してもよい。The silver halide composition of the silver halide grains according to the present invention consists essentially of silver bromide or silver iodobromide, and silver bromide other than silver iodobromide and silver iodobromide is contained within a range not impairing the effects of the present invention. , For example, silver chloride may be contained.
具体的には塩化銀の場合、その比率は５モル％以下であ
ることが望ましく、１モル％以下であることが更に望ま
しい。Specifically, in the case of silver chloride, the ratio is preferably 5 mol% or less, more preferably 1 mol% or less.
本発明に係るハロゲン化銀粒子の沃化銀の比率は好まし
くは０〜40モル％で、更に好ましくは０〜20モル％であ
り、０〜15モル％の範囲が特に好ましい。The ratio of silver iodide in the silver halide grains according to the present invention is preferably 0 to 40 mol%, more preferably 0 to 20 mol%, particularly preferably 0 to 15 mol%.
また本発明に係るハロゲン化銀粒子は、粒子内の組織が
均一であってもよいし、複数の組成相を有した、例えば
コア／シェル構造であってもよい。複数の組成相には塩
化銀、塩臭化銀が含まれてもよい。The silver halide grain according to the present invention may have a uniform structure within the grain, or may have, for example, a core / shell structure having a plurality of composition phases. The plural composition phases may include silver chloride and silver chlorobromide.
また複数の組成相がコア／シェル構造をなす時には、コ
ア或はシェルの組成相は均一であってもよいし、相互に
連続して成分組成が移り変る形をとってもよい。Further, when a plurality of composition phases form a core / shell structure, the composition phase of the core or shell may be uniform, or the composition may change continuously with each other.
最も好ましい形態の１つは粒子内深部に高沃化銀相を有
するものである。即ち、粒子表面もしくは表面層より粒
子深部に沃化銀含有量の多い層（複数層でよい）もしく
はコアを有するハロゲン化銀粒子である。One of the most preferable forms is one having a high silver iodide phase deep inside the grain. That is, it is a silver halide grain having a layer (a plurality of layers may be included) having a high silver iodide content or a core deeper in the grain than the grain surface or the surface layer.
本発明に係るハロゲン化銀粒子の粒径は特に制約はな
く、好ましくは0.1〜3.0μmの範囲で本発明は少なくと
も有効である。なお、本明細書において、ハロゲン化銀
の粒径は、その体積に等しい立方体の一辺の長さで表わ
す。The grain size of the silver halide grains according to the present invention is not particularly limited, and the present invention is effective at least in the range of preferably 0.1 to 3.0 μm. In the present specification, the grain size of silver halide is represented by the length of one side of the cube which is equal to the volume.
本発明に係るハロゲン化銀粒子は通常ゼラチン等の分散
媒を含む母液に分散された形態、すなわち乳剤と称され
るハロゲン化銀粒子が懸濁した形態で製造され、また用
いられる。このときの該粒子の群の粒径分布は単分散で
も多分散でも、またこれらを混合してなる分布でもよ
く、用途等に応じて適宜選択することができるが、粒径
分布の変動係数が20％以下の単分散乳剤を得るためには
本発明の製造方法は有効である。The silver halide grains according to the present invention are usually produced and used in a form dispersed in a mother liquor containing a dispersion medium such as gelatin, that is, a form in which silver halide grains called an emulsion are suspended. The particle size distribution of the group of particles at this time may be monodisperse, polydisperse, or a mixture of these, and can be appropriately selected depending on the application etc., but the coefficient of variation of the particle size distribution is The production method of the present invention is effective for obtaining a monodisperse emulsion of 20% or less.
この変動係数は 変動係数（％）＝ として定義され、単分散性を示す尺度である。This coefficient of variation is the coefficient of variation (%) = Is a measure of monodispersity.
本発明に係るハロゲン化銀粒子は外表面に(nn1)面以外
の面、例えば(111)面、(100)面等を含んでも構わないこ
とは前述のとおりである。全表面積に対する(nn1)面の
面積の割合は前記のとおり、少なくとも30％以上であ
り、好ましくは50％以上、更に好ましくは70％以上であ
る。As described above, the silver halide grain according to the present invention may include a surface other than the (nn1) plane, such as the (111) plane and the (100) plane, on the outer surface. As described above, the ratio of the area of the (nn1) plane to the total surface area is at least 30% or more, preferably 50% or more, more preferably 70% or more.
本発明の如く、粒子表面が(nn1)結晶面を有した、実質
的に臭化銀または沃臭化銀からなるハロゲン化銀粒子を
含有したハロゲン化銀乳剤を用いることによって、従来
の(nn1)結晶面を有さない臭化銀乳剤または沃臭化銀乳
剤では得ることのできなかった種々の写真乳剤としての
利点を得ることができるようになった。As in the present invention, by using a silver halide emulsion containing a silver halide grain consisting essentially of silver bromide or silver iodobromide having a (nn1) crystal plane on the grain surface, a conventional (nn1) ) It has become possible to obtain various photographic emulsion advantages which could not be obtained with a silver bromide emulsion or a silver iodobromide emulsion having no crystal plane.
例えば(111)面および／または(100)面および／または
(110)面から外表面が構成されるハロゲン化銀粒子を含
む乳剤（以下、従来の乳剤という）に比べて、カブリを
低く抑えかつ、感度を高くすることができる。For example, (111) plane and / or (100) plane and / or
Compared with an emulsion containing silver halide grains (hereinafter referred to as a conventional emulsion) whose outer surface is composed of the (110) plane, fog can be suppressed low and sensitivity can be increased.
に伴い、従来乳剤に比べ粒状性の優れた写真感光材
料を提供することができる。Accordingly, it is possible to provide a photographic light-sensitive material having more excellent graininess than conventional emulsions.
従来乳剤の中では(110)面を有する乳剤カブリ−感度
関係において優れていることが知られているが、これに
は高温下での保存性が劣るという欠点がある(110)面を
有する乳剤に対し、(nn1)を有する乳剤はカブリ−感度
関係において優れ、なお、かつ高温下での保存性も改善
される。Among the conventional emulsions, emulsions having a (110) plane are known to be excellent in the fog-sensitivity relationship, but this has the disadvantage of poor storage stability at high temperatures. On the other hand, the emulsion having (nn1) is excellent in the fog-sensitivity relationship, and the storage stability at high temperature is also improved.
後述する製造方法において、(nn1)面の発達を促進す
る化合物（以下、結晶制御化合物と称す）として、テト
ラザインデン化合物を用いるため、所望の沃化銀含有率
の沃臭化銀粒子を得ることが比較的容易にできる。In the production method described below, a tetrazaindene compound is used as a compound that accelerates the development of the (nn1) plane (hereinafter referred to as a crystal control compound), and thus silver iodobromide grains having a desired silver iodide content are obtained. Can be done relatively easily.
同製造法は、特に単分散性の高い乳剤を製造すること
ができる。この点において、結晶制御化合物としてメル
カプトアゾール類を用いて製造する(110)面を有する乳
剤より優れている。This production method can produce an emulsion having particularly high monodispersity. In this respect, it is superior to the emulsion having a (110) plane produced by using mercaptoazoles as a crystal controlling compound.
に伴い鮮鋭度の優れた写真感光材料を提供すること
ができる。Accordingly, a photographic light-sensitive material having excellent sharpness can be provided.
前記本発明に係る(nn1)面を有するハロゲン化銀粒子を
含有するハロゲン化銀乳剤は、保護コロイドの存在の下
に、水溶性ハロゲン化物溶液と水溶性銀塩溶液とを混合
してハロゲン化銀粒子を形成する工程を有するハロゲン
化銀乳剤の製造方法に於て、 （イ）ハロゲン化銀粒子の形成に用いる生成ハロゲン化
銀量の少なくとも30モル％が生成される期間はハロゲン
化銀懸濁母液のpAgを7.0〜9.8に制御し、かつ （ロ）該期間にテトラザインデン化合物を該母液中に共
存させ、かつ （ハ）ハロゲン化銀量の生成終了後、ハロゲン化銀粒子
を整え形成する間、pAgを7.0〜9.5に制御して、外表面
はすべて(nn1)面から構成され、しかも明確な稜線を有
する24面体ハロゲン化銀粒子からなることを特徴とする
ハロゲン化銀乳剤の製造方法によって得られる。The silver halide emulsion containing silver halide grains having the (nn1) plane according to the present invention is a halogenated compound obtained by mixing a water-soluble halide solution and a water-soluble silver salt solution in the presence of a protective colloid. In a method for producing a silver halide emulsion having a step of forming silver grains, (a) a silver halide suspension is used during a period in which at least 30 mol% of the amount of silver halide produced for forming silver halide grains is produced. The pAg of the turbid mother liquor is controlled to 7.0 to 9.8, (b) the tetrazaindene compound is allowed to coexist in the mother liquor during the period, and (c) the silver halide grains are prepared after the production of the silver halide amount is completed. During formation, the pAg was controlled to 7.0 to 9.5, the outer surface was composed entirely of (nn1) planes, and was composed of tetrahedral silver halide grains having clear ridges. Obtained by the manufacturing method.
前記「ハロゲン化銀粒子を整え形成する間」とは結晶内
転位、溶解熱平衡、或は結晶表面状態等の粒子物性を実
用的見地から実験的に最適に整えて粒子構成を最終的に
決定する期間であって、本発明に特徴を付すものであ
る。The term "during the formation of the silver halide grains" means that the grain constitution is finally determined experimentally from the practical point of view by adjusting the physical properties of grains such as intra-crystalline dislocation, dissolution thermal equilibrium, and crystal surface state. A period, which characterizes the present invention.
本発明に係わるハロゲン化銀粒子の前記製造方法におい
て、ハロゲン化銀を生成させハロゲン化銀粒子を形成さ
せる工程には、酸性法、中性法、アンモニア法等のいず
れの方法をも用いることができる。また可溶性銀塩と可
溶性ハロゲン塩を反応させる形式としては、一方の液を
他方を母液として注加する片方注加法、母液に両反応液
を注加する同時混合法、それらの組合わせなどのいずれ
を用いてもよいが、同時混合法の一つの形式としてハロ
ゲン化銀の生成される液相中のpAgを一定に保つ方法、
すなわちいわゆるコントロールド・ダブルジエット法を
用いることが好ましい。In the method for producing silver halide grains according to the present invention, any method such as an acidic method, a neutral method or an ammonia method may be used in the step of forming silver halide to form silver halide grains. it can. The method of reacting the soluble silver salt and the soluble halogen salt may be one-side injection method in which one solution is added as the mother liquor, simultaneous mixing method in which both reaction solutions are added to the mother liquor, or a combination thereof. May be used, but as one form of the simultaneous mixing method, a method of keeping pAg constant in the liquid phase in which silver halide is produced,
That is, it is preferable to use the so-called controlled double jet method.
この方法によると、結晶形が規則的で粒子サイズが均一
に近いハロゲン化銀乳剤（単分散乳剤）が得られる。ま
た、ハロゲン化銀溶剤を用いると粒子形成時間を短時間
に行いうるので好ましい。例えばアンモニア、チオエー
テルなど一般によく知られたハロゲン化銀溶剤を用いる
ことができる。According to this method, a silver halide emulsion (monodisperse emulsion) having a regular crystal form and a substantially uniform grain size can be obtained. Further, it is preferable to use a silver halide solvent because the grain formation time can be shortened. For example, a commonly known silver halide solvent such as ammonia or thioether can be used.
また、粒子サイズを均一にするには、英国特許1,535,01
6号、特公昭48-36890号、同52-16364号に記載されてい
るように、硝酸銀やハロゲン化アルカリ水溶液の添加速
度を粒子成長速度に応じて変化させる方法や、米国特許
4,242,445号、特開昭55-158124号に記載されているよう
に水溶液濃度を変化させる方法を用いて臨界飽和度を越
えない範囲において早く成長させることが好ましい。In addition, in order to make the particle size uniform, British Patent 1,535,01
No. 6, JP-B-48-36890 and JP-A-52-16364, a method of changing the addition rate of an aqueous solution of silver nitrate or an alkali halide according to the grain growth rate, and US Pat.
It is preferable to use the method of changing the concentration of the aqueous solution as described in 4,242,445 and JP-A-55-158124 to grow quickly in a range not exceeding the critical saturation.
これらの方法は、核再発生を起こさず、各ハロゲン化銀
粒子が均一に被覆されていくため、ハロゲン化銀組成の
異なった複数の層を有する粒子を形成する場合にも好ま
しく用いられる。These methods are preferably used also when forming grains having a plurality of layers having different silver halide compositions, because each silver halide grain is uniformly coated without regenerating nuclei.
異なったハロゲン化銀組成の層を設ける場合には、ハロ
ゲン置換法を用いることもできる。When providing layers having different silver halide compositions, a halogen substitution method can also be used.
ハロゲン置換法としては、例えば主としてヨード化合物
（好ましくはヨードカリウム）からなる水溶液、好まし
くは濃度10％以下の水溶液を添加することによって行う
ことができる。詳しくは、米国特許2,592,250号、同4,0
75,020号、特開昭55-127549号などに記載された方法に
よって行うことができる。このとき、高沃化銀含有層の
粒子間ヨード分布差を少なくするためには、ヨード化合
物水溶液の濃度を10-2モル／以下にした10分以上かけ
て添加するのが望ましい。The halogen substitution method can be performed, for example, by adding an aqueous solution mainly containing an iodo compound (preferably potassium iodo), preferably an aqueous solution having a concentration of 10% or less. For details, see U.S. Patents 2,592,250 and 4,0
75,020, JP-A-55-127549 and the like. At this time, in order to reduce the difference in iodine distribution between grains in the high silver iodide containing layer, it is desirable to add the iodine compound aqueous solution at a concentration of 10 -2 mol / or less for 10 minutes or more.
ハロゲン化銀組成の異なる層を設ける場合には、途中で
必要に応じて常法に従って脱塩工程を行っても良いし、
脱塩工程を行わずに連続して層の形成を行っても良い。When a layer having a different silver halide composition is provided, a desalting step may be performed according to a conventional method, if necessary, on the way.
The layers may be continuously formed without performing the desalting step.
本発明のハロゲン化銀粒子の製造方法において、最も好
ましい形態の一つは、アンモニアの存在下において、ア
ンモニア性硝酸銀水溶液とハロゲン化物水溶液とをコン
トロールド・ダブルジエット法で添加する方法である。In the method for producing silver halide grains of the present invention, one of the most preferable modes is a method of adding an aqueous ammoniacal silver nitrate solution and an aqueous halide solution by a controlled double jet method in the presence of ammonia.
本発明に係るハロゲン化銀粒子製造方法において、種粒
子を使用し、その表面にハロゲン化銀を生成させて粒子
を成長させてもよい。種粒子を用いる場合、そのハロゲ
ン化銀組成は本発明に係るハロゲン化銀粒子を形成しう
る範囲であればよい。In the method for producing silver halide grains according to the present invention, seed grains may be used, and silver halide may be produced on the surface thereof to grow the grains. When the seed grains are used, the silver halide composition may be within the range capable of forming the silver halide grains according to the present invention.
先記ハロゲン化銀生成量が30モル％に達する期間のpAg
の制御は、ハロゲン化銀が生成する期間内であれば任意
であり、ハロゲン化銀生成工程の初めでも中途でもまた
終りでもよい。また、この期間は連続した期間であるこ
とが好ましいが、本発明の効果を阻害しない範囲で断続
的であってもよい。この期間におけるpAgは7.0〜9.8で
あり、好ましくは7.3〜9.5であり、更に好ましくは7.6
〜9.2である。そしてこの期間、乳剤のpHは７〜10の範
囲に保つことが好ましい。この期間及び先記ハロゲン化
銀粒子を整え形成する期間外のハロゲン化銀のpAgは４
〜11.5の範囲が適当であり、好ましくは６〜11の範囲で
あり、pHは２〜12の範囲が適当であり、好ましくは５〜
11の範囲である。PAg in the period when the amount of silver halide produced reaches 30 mol%
Can be controlled within the period during which silver halide is produced, and may be at the beginning, midway or end of the silver halide producing step. Further, this period is preferably a continuous period, but may be intermittent as long as the effect of the present invention is not impaired. PAg in this period is 7.0 ~ 9.8, preferably 7.3 ~ 9.5, more preferably 7.6.
~ 9.2. During this period, the pH of the emulsion is preferably kept in the range of 7-10. The pAg of silver halide outside this period and the period for forming and forming the silver halide grains is 4
The range of 1 to 11.5 is suitable, the range of 6 to 11 is preferable, and the range of pH is 2 to 12 is preferable, and the range of 5 is preferable.
The range is 11.
本発明に係るハロゲン化銀粒子は、ハロゲン化銀沈澱生
成時、粒子成長時あるいは成長終了後において各種金属
塩あるいは金属錯塩によってドーピングを施してもよ
い。例えば金、白金、パラジウム、イリジウム、ロジウ
ム、ビスマス、カドミウム、銅等の金属塩または錯塩お
よびそれらの組合わせを適用できる。The silver halide grains according to the present invention may be doped with various metal salts or metal complex salts at the time of silver halide precipitation formation, at the time of grain growth or after the growth is finished. For example, metal salts or complex salts of gold, platinum, palladium, iridium, rhodium, bismuth, cadmium, copper and the like and combinations thereof can be applied.
本発明に係るハロゲン化銀粒子は、そのまま使用に供し
ても、また平均粒径の異なる２種以上を粒子形成以後の
任意の時期にブレンドして所定の階調度を得るよう調合
して使用に供してもよい。そのほか本発明以外のハロゲ
ン化銀粒子と混合して用いることができる。The silver halide grains according to the present invention may be used as they are, or may be prepared by blending two or more kinds having different average grain sizes at any time after grain formation to obtain a predetermined gradation. May be offered. In addition, it can be used as a mixture with silver halide grains other than those of the present invention.
本発明に係るテトラザインデン化合物は結晶制御用に供
されるものであって、下記一般式（Ｉ），（II），（II
I），（IV）及び一般式（Ｖ）の繰り返し単位を有する
テトラザインデン化合物が好ましい。The tetrazaindene compound according to the present invention is used for controlling crystals and has the following general formulas (I), (II) and (II
Tetrazaindene compounds having repeating units of I), (IV) and general formula (V) are preferred.
一般式（Ｉ） 一般式（II） 一般式（III） 一般式（IV） 一般式（Ｖ） 式中、Ｒ1,Ｒ2およびＲ3は同じでも異なっていてもよ
く、各々水素原子、ハロゲン原子、アミノ基、アミノ基
の誘導体、アルキル基、アルキル基の誘導体、アリール
基、アリール基の誘導体、シクロアルキル基、シクロア
ルキル基の誘導体、メルカプト基、メルカプト基の誘導
体または -CONH-R4 （Ｒ4は水素原子、アルキル基、アミノ基、アルキル基
の誘導体、アミノ基の誘導体、ハロゲン原子、シクロア
ルキル基、シクロアルキル基の誘導体、アリール基また
はアリール基の誘導体を表わす。）を表わし、Ｒ5は水
素原子またはアルキル基を表わし、Ｒ1とＲ2は結合して
環（例えば、５〜７員の炭素環、複素環）を形成しても
よく、Ｘは一般式（Ｉ），（II），（III）または（I
V）で表わされる化合物から水素原子１箇を除いた一価
の基（例えば前記一般式（Ｉ）ないし（IV）におけるＲ
1〜Ｒ3またはOH部分から水素原子１箇を除いたもの）を
表わし、Ｊは２価の連結基を表わす。General formula (I) General formula (II) General formula (III) General formula (IV) General formula (V) In the formula, R 1 , R 2 and R 3 may be the same or different and each is a hydrogen atom, a halogen atom, an amino group, an amino group derivative, an alkyl group, an alkyl group derivative, an aryl group or an aryl group derivative. , A cycloalkyl group, a cycloalkyl group derivative, a mercapto group, a mercapto group derivative or -CONH-R 4 (R 4 is a hydrogen atom, an alkyl group, an amino group, an alkyl group derivative, an amino group derivative, a halogen atom, A cycloalkyl group, a derivative of a cycloalkyl group, an aryl group or a derivative of an aryl group), R 5 represents a hydrogen atom or an alkyl group, and R 1 and R 2 are bonded to form a ring (for example, 5 to 5). 7-membered carbocycle, heterocycle) may be formed, and X is represented by the general formula (I), (II), (III) or (I
A monovalent group obtained by removing one hydrogen atom from the compound represented by V) (for example, R in the general formulas (I) to (IV)).
1 to R 3 or an OH moiety from which one hydrogen atom has been removed), and J represents a divalent linking group.
前記一般式（Ｉ）〜（Ｖ）において、Ｒ1〜Ｒ4で表わさ
れるアルキル基としては、例えばメチル基、エチル基、
プロピル基、ペンチル基、ヘキシル基、オクチル基、イ
ソプロピル基、sec−ブチル基、t−ブチル基等が挙げら
れ、アルキル基の誘導体としては、例えば芳香族残基で
置換された（２価の連結基、例えば−NHCO−等を介して
もよい）アルキル基（例えばベンジル基、フェネチル
基、ベンズヒドリル基、１−ナフチルメチル基、３−フ
ェニルブチル基、ベンゾイルアミノエチル基等）、アル
コキシ基で置換されたアルキル基（例えばメトキシメチ
ル基、２−メトキシエチル基、３−エトキシプロピル
基、４−メトキシブチル基等）、ハロゲン原子、ヒドロ
キシ基、カルボキシ基、メルカプト基、アルコキシカル
ボニル基または置換もしくは非置換のアミノ基で置換さ
れたアルキル基（例えばモノクロロメチル基、ヒドロキ
シメチル基、３−ヒドロキシブチル基、カルボキシメチ
ル基、２−カルボキシエチル基、２−（メトキシカルボ
ニル）エチル基、アミノメチル基、ジエチルアミノメチ
ル基等）、シクロルアルキル基で置換されたアルキル基
（例えばシクロペンチルメチル基等）、上記一般式
（Ｉ）〜（IV）で表わされる化合物から水素原子１箇を
除いた１価の基で置換されたアルキル基等が挙げられ
る。In the general formulas (I) to (V), examples of the alkyl group represented by R 1 to R 4 include a methyl group, an ethyl group,
Examples thereof include a propyl group, a pentyl group, a hexyl group, an octyl group, an isopropyl group, a sec-butyl group, a t-butyl group, and the like. Examples of the alkyl group derivative are substituted with an aromatic residue (divalent linking A group such as -NHCO- or the like) alkyl group (e.g., benzyl group, phenethyl group, benzhydryl group, 1-naphthylmethyl group, 3-phenylbutyl group, benzoylaminoethyl group, etc.), alkoxy group Alkyl group (eg, methoxymethyl group, 2-methoxyethyl group, 3-ethoxypropyl group, 4-methoxybutyl group, etc.), halogen atom, hydroxy group, carboxy group, mercapto group, alkoxycarbonyl group or substituted or unsubstituted Alkyl groups substituted with amino groups (eg monochloromethyl group, hydroxymethyl group, 3-hydro) Cibutyl group, carboxymethyl group, 2-carboxyethyl group, 2- (methoxycarbonyl) ethyl group, aminomethyl group, diethylaminomethyl group, etc.), an alkyl group substituted with a cyclolalkyl group (eg, cyclopentylmethyl group, etc.), Examples thereof include alkyl groups substituted with a monovalent group obtained by removing one hydrogen atom from the compounds represented by the above general formulas (I) to (IV).
Ｒ1〜Ｒ4で表わされるアリール基としては、例えばフェ
ニル基、１−ナフチル基等が挙げられ、アリール基の誘
導体としては、例えばp−トリル基、m−エチルフェニル
基、m−クメニル基、メシチル基、２，３−キシリル
基、p−クロロフェニル基、o−プロモフェニル基、p−
ヒドロキシフェニル基、１−ヒドロキシ−２−ナフチル
基、m−メトキシフェニル基、p−エトキシフェニル基、
p−カルボキシフェニル基、o−（メトキシカルボニル）
フェニル基、m−（エトキシカルボニル）フェニル基、
４−カルボキシ−１−ナフチル基等が挙げられる。Examples of the aryl group represented by R 1 to R 4 include a phenyl group and a 1-naphthyl group, and examples of the derivative of the aryl group include a p-tolyl group, m-ethylphenyl group, m-cumenyl group, Mesityl group, 2,3-xylyl group, p-chlorophenyl group, o-promophenyl group, p-
Hydroxyphenyl group, 1-hydroxy-2-naphthyl group, m-methoxyphenyl group, p-ethoxyphenyl group,
p-carboxyphenyl group, o- (methoxycarbonyl)
Phenyl group, m- (ethoxycarbonyl) phenyl group,
4-carboxy-1-naphthyl group and the like can be mentioned.
Ｒ1〜Ｒ4で表わされるシクロアルキル基としては、例え
ばシクロヘプチル基、シクロペンチル基、シクロヘキシ
ル基等が挙げられ、シクロアルキル基の誘導体として
は、例えばメチルシクロヘキシル基等が挙げられる。Ｒ
1〜Ｒ4で表わされるハロゲン原子としては、例えば弗
素、塩素、臭素、沃素等、Ｒ1〜Ｒ4で表わされるアミノ
基の誘導体としては、例えばブチルアミノ基、ジエチル
アミノ基、アニリノ基等が挙げられる。Ｒ1〜Ｒ3として
表わされるメルカプト基の誘導体としては、例えばメチ
ルチオ基、エチルチオ基、フェニルチオ基等が挙げられ
る。Examples of the cycloalkyl group represented by R 1 to R 4 include a cycloheptyl group, a cyclopentyl group and a cyclohexyl group, and examples of the derivative of the cycloalkyl group include a methylcyclohexyl group. R
Examples of the halogen atom represented by 1 to R 4 include fluorine, chlorine, bromine and iodine, and examples of the derivative of the amino group represented by R 1 to R 4 include butylamino group, diethylamino group and anilino group. To be Examples of the mercapto group derivative represented by R 1 to R 3 include a methylthio group, an ethylthio group, and a phenylthio group.
Ｒ5で表わされるアルキル基は、好ましくは炭素数１〜
６であり、例えばメチル基、エチル基等が挙げられる。Alkyl group represented by R 5 is preferably 1 to carbon atoms
6 and examples thereof include a methyl group and an ethyl group.
Ｒ5としては特に水素原子およびメチル基が好ましい。R 5 is particularly preferably a hydrogen atom or a methyl group.
Ｊは２価の連結基であるが、総炭素数が１〜20であるこ
とが好ましい。そのような連結基の中でも次の式（Ｊ−
Ｉ）または（Ｊ−II）で表わされるものが好ましい。J is a divalent linking group, and preferably has a total carbon number of 1 to 20. Among such linking groups, the following formula (J-
Those represented by I) or (J-II) are preferable.
（Ｊ−Ｉ） （Ｊ−II） 式中、Ｙは−Ｏ−または （ここではＲ6は水素原子または炭素数１〜６のアルキ
ル基）を表わす。(JI) (J-II) In the formula, Y is -O- or (Here, R 6 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms).
Ｚはアルキレン基（好ましくは炭素数10までのもの。ア
ルキレン基の中間にはアミド結合、エステル結合、若し
くはエーテル結合が介在していてもよい。例えばメチレ
ン基、エチレン基、プロピレン基、−CH2OCH2−，−CH2
CONHCH2−，−CH2CH2COOCH2−，−CH2CH2OCOCH2−，−C
H2NHCOCH2−等）−Ｏ−アルキレン基、−CONH−アルキ
レン基、−COO−アルキレン等、−OCO−アルキレン基も
しくは−NHCO−アルキレン基（これらのアルキレン基は
好ましくは炭素数10までのもの）またはアリーレン基
（好ましくは炭素数６〜12のもの。例えばp−フェニレ
ン基など）を表わす。Z is an alkylene group (preferably having up to 10 carbon atoms. An amide bond, an ester bond, or an ether bond may be interposed between the alkylene groups. For example, methylene group, ethylene group, propylene group, -CH 2 OCH 2 −, −CH 2
CONHCH 2 -, - CH 2 CH 2 COOCH 2 -, - CH 2 CH 2 OCOCH 2 -, - C
H 2 NHCOCH 2 — etc.) —O-alkylene group, —CONH-alkylene group, —COO-alkylene group, —OCO-alkylene group or —NHCO-alkylene group (these alkylene groups preferably have up to 10 carbon atoms. ) Or an arylene group (preferably having 6 to 12 carbon atoms, such as a p-phenylene group).
Ｊとして特に好ましい２価の連結基としては、次のもの
が挙げられる。Particularly preferable divalent linking groups as J include the following.
−CONHCH2−，−CONHCH2CH2−，−CONHCH2OCOCH2−，−
CONHCH2CH2CH2OCOCH2−，−COOCH2−，−COOCH2CH2−，
−COOCH2CH2OCOCH2−，−COOCH2CH2CH2OCOCH2−， 一般式（Ｖ）で表わされる単位を有する化合物は、ホモ
ポリマーであっても、コポリマーであってもよく、コポ
リマーとしては、例えば、アクリルアミド、メタクリル
アミド、アクリルエステル、メタクリルエステル等が挙
げられる。−CONHCH 2 −, −CONHCH 2 CH 2 −, −CONHCH 2 OCOCH 2 −, −
CONHCH 2 CH 2 CH 2 OCOCH 2 -, - COOCH 2 -, - COOCH 2 CH 2 -,
-COOCH 2 CH 2 OCOCH 2 -, - COOCH 2 CH 2 CH 2 OCOCH 2 -, The compound having the unit represented by the general formula (V) may be a homopolymer or a copolymer, and examples of the copolymer include acrylamide, methacrylamide, acrylic ester, methacrylic ester and the like.
次に前記一般式（Ｉ），（II），（III）もしくは（I
V）で表わされる化合物または前記一般式（Ｖ）で表わ
される繰り返し単位を有する化合物（以下、本発明に用
いられるテトラザインデン化合物という）の代表的具体
例を示す。Next, the general formula (I), (II), (III) or (I
Representative specific examples of the compound represented by V) or the compound having the repeating unit represented by the general formula (V) (hereinafter referred to as tetrazaindene compound used in the present invention) are shown.
（１） （２） （３） （４） （５） （６） （７） （８） （９） （10） （11） （12） （13） （14） （15） （16） （17） （18） （19） （20） （21） （22） （23） （24） （25） （26） （27） （28） （29） （30） （31） （32） y：５〜50モル％である共重合物 （33） y：５〜50モル％である共重合物 （34） y：５〜50モル％である共重合物 （35） y：５〜50モル％である共重合物 （36） y：５〜50モル％である共重合物 本発明のハロゲン化銀粒子の製造に用いられるテトラザ
インデン化合物の添加量は、所望のハロゲン化銀粒径、
乳剤の温度、pH、pAg、沃化銀含有率等の製造条件によ
って異なるが、生成する全ハロゲン化銀１モル当り10-5
〜２×10-1モルの範囲が好ましい。(1) (2) (3) (4) (5) (6) (7) (8) (9) (Ten) (11) (12) (13) (14) (15) (16) (17) (18) (19) (20) (twenty one) (twenty two) (twenty three) (twenty four) (twenty five) (26) (27) (28) (29) (30) (31) (32) y: Copolymer of 5 to 50 mol% (33) y: Copolymer of 5 to 50 mol% (34) y: Copolymer of 5 to 50 mol% (35) y: Copolymer of 5 to 50 mol% (36) y: 5 to 50 mol% of copolymer The addition amount of the tetrazaindene compound used in the production of the silver halide grains of the present invention is the desired silver halide grain size,
It depends on the production conditions such as the temperature of emulsion, pH, pAg, and silver iodide content, but it is 10 -5 per mol of total silver halide produced.
It is preferably in the range of 2 × 10 -1 mol.
尚、テトラザインデン化合物が一般式（Ｖ）で表わされ
る単位を有する化合物である場合には、テトラザインデ
ン部分のモル数をもって、添加量とする。When the tetrazaindene compound is a compound having a unit represented by the general formula (V), the number of moles of the tetrazaindene portion is the addition amount.
更に好ましい添加量は粒径に対して表−１の通りであ
る。表−１に記載されている粒径以外の粒径に対する添
加量は、添加量を粒径に反比例させて外挿法、または内
挿法で求めることができる。The more preferable addition amount is as shown in Table 1 with respect to the particle size. The addition amount with respect to the particle size other than the particle size listed in Table 1 can be obtained by extrapolation or interpolation by making the addition amount inversely proportional to the particle size.
また、更に好ましい添加量はpAgおよび沃化銀含有率に
対して表−２の通りである。 Further, the more preferable addition amount is as shown in Table 2 with respect to pAg and silver iodide content.
テトラザインデン化合物の添加方法としては予め保護コ
ロイド溶液中に添加したおく方法、ハロゲン化銀粒子の
成長につれて徐々に添加する方法、これらを合わせて行
う方法等がある。 The tetrazaindene compound may be added in advance in a protective colloid solution, gradually added as the silver halide grains grow, or a combination thereof.
本発明のハロゲン化銀乳剤の通常の使用形態において
は、ハロゲン化銀粒子の調製時に生ずる過剰ハロゲン化
合物あるいは副生するまたは不要となった硝酸塩、アン
モニア等の塩類、化合物類は該粒子の分散媒から除去
（脱塩工程）されるべきである。除去の方法は一般乳剤
において常用されるヌーデル水洗法、透析法あるいは無
機塩類、アニオン性界面活性剤、アニオン性ポリマー
（例えばポリスチレンスルホン酸）あるいはゼラチン誘
導体（例えばアシル化ゼラチン、カルバモイル化ゼラチ
ンなど）を利用した沈降法、凝析沈澱法（フロキュレー
ション）等を適宜用いることができる。In a usual use form of the silver halide emulsion of the present invention, an excess halogen compound generated during the preparation of silver halide grains, salts by-produced or no longer needed, salts such as ammonia, and compounds are a dispersion medium of the grains. Should be removed (desalting step). The removal method is a Nudel water washing method, a dialysis method or an inorganic salt, an anionic surfactant, an anionic polymer (for example, polystyrene sulfonic acid) or a gelatin derivative (for example, acylated gelatin, carbamoylated gelatin, etc.) commonly used in general emulsions. The sedimentation method and coagulation sedimentation method (flocculation) used can be appropriately used.
ハロゲン化銀粒子形成工程においてハロゲン化銀粒子を
整え形成して所望のハロゲン化銀粒子を得るまでの即
ち、上記脱塩工程に入る時点まで、母液のpAgは7.0〜9.
5の範囲に制御されなくてはならない。この間好ましく
はpAgは7.4〜9.2であり、さらに好ましくは7.8〜9.0で
ある。pHは５〜８が好ましく、さらに好ましくは５〜７
である。In the step of forming silver halide grains, the pAg of the mother liquor is 7.0 to 9.until the silver halide grains are formed to form the desired silver halide grains, that is, until the desalting step is started.
It must be controlled to a range of 5. During this period, pAg is preferably 7.4 to 9.2, and more preferably 7.8 to 9.0. The pH is preferably 5-8, more preferably 5-7.
Is.
ハロゲン化銀生成工程終了から、脱塩工程開始までの時
間は好ましくは30分以内、更に好ましくは20分以内であ
る。The time from the end of the silver halide forming step to the start of the desalting step is preferably within 30 minutes, more preferably within 20 minutes.
また本発明に係るハロゲン化銀粒子は一般乳剤に対して
施される各種の化学増感法を施すことができる。即ち、
活性ゼラチン；水溶性金塩、水溶性白金塩、水溶性パラ
ジウム塩、水溶性ロジウム塩、水溶性イリジウム塩等の
貴金属増感剤；硫黄増感剤；セレン増感剤；還元増感剤
等の化学増感剤等により単独にあるいは併用して化学増
感することができる。Further, the silver halide grains according to the present invention can be subjected to various chemical sensitization methods applied to general emulsions. That is,
Active gelatin; water-soluble gold salts, water-soluble platinum salts, water-soluble palladium salts, water-soluble rhodium salts, water-soluble iridium salts and other precious metal sensitizers; sulfur sensitizers; selenium sensitizers; reduction sensitizers, etc. Chemical sensitization can be carried out individually or in combination with a chemical sensitizer.
前記還元増感は低pAg条件下に乳剤を攪拌する即ち銀熟
成によってもよいし、塩化スズ、ジメチルアミンボラ
ン、ヒドラジン、二酸化チオ尿素のような適当な還元剤
を用いてもよい。The reduction sensitization may be carried out by stirring the emulsion under a low pAg condition, that is, by aging the silver, or using a suitable reducing agent such as tin chloride, dimethylamine borane, hydrazine and thiourea dioxide.
更にこのハロゲン化銀は所望の波長域に光学的に増感す
ることができる。本発明の乳剤の光学増感方法には特に
制限はなく、例えばゼロメチン色素、モノメチン色素、
ジメチン色素、トリメチン色素等のシアニン色素あるい
はメロシアニン色素等の光学増感剤を単独あるいは併用
して（例えば超色増感）光学的に増感することができ
る。これらの技術については米国特許2,688,545号、同
2,912,329号、同3,397,060号、同3,615,635号、同3,62
8,964号、米国特許1,195,302号、同1,242,588号、同1,2
93,862号、西独特許(OLS)2,030,326号、同2,121,780
号、特公昭43−4936号、同44−14030号等にも記載され
ている。その選択は増感すべき波長域、感度等、感光材
料の目的、用途に応じて任意に定めることが可能であ
る。Further, this silver halide can be optically sensitized to a desired wavelength range. The optical sensitization method of the emulsion of the present invention is not particularly limited, and examples thereof include a zero methine dye, a monomethine dye,
An optical sensitizer such as a cyanine dye such as a dimethine dye or a trimethine dye or an optical sensitizer such as a merocyanine dye may be used alone or in combination (for example, supersensitization) to perform optical sensitization. Regarding these technologies, U.S. Pat.
2,912,329, 3,397,060, 3,615,635, 3,62
8,964, U.S. Patents 1,195,302, 1,242,588, 1,2
93,862, West German Patent (OLS) 2,030,326, 2,121,780
No. 4, Japanese Patent Publication Nos. 43-4936 and 44-14030. The selection can be arbitrarily determined depending on the wavelength region to be sensitized, sensitivity, etc., according to the purpose and application of the light-sensitive material.
本発明に係るハロゲン化銀のバインダー、または該粒子
の製造に用いられる分散媒としては、通常ハロゲン化銀
乳剤に用いられる親水性コロイドが用いられる。親水性
コロイドとしては、ゼラチン、（石灰処理または酸処理
いずれでもよい）のみならず、ゼラチン誘導体、例えば
米国特許2,614,928号に記載されているようなゼラチン
と芳香族塩化スルフォニル、酸塩化物、酸無水物、イソ
シアネート、１，４−ジケント類との反応により作られ
るゼラチン誘導体、米国特許3,118,766号に記載されて
いるゼラチンとトリメリット酸無水物との反応により作
られるゼラチン誘導体、特公昭39-5514号に記載された
活性ハロゲンを有する有機酸とゼラチンとの反応による
ゼラチン誘導体、特公昭42-26845号に記載された芳香族
グリシジルエーテルとゼラチンとの反応によるゼラチン
誘導体、米国特許3,186,846号に記載されたマレイミ
ド、マレアミン酸、不飽和脂肪族ジアミド等とゼラチン
との反応によるゼラチン誘導体、米国特許第1,033,189
号に記載されたスルフォアルキル化ゼラチン、米国特許
3,312,553号に記載されたゼラチンのポリオキシアルキ
レン誘導体など；ゼラチンの高分子グラフト化物、例え
ばアクリル酸、メタアクリル酸、それらの一価または多
価アルコールとのエステル、同じくアミド、アクリル
（またはメタアクリル）エトリル、スチレンその他のビ
ニル系モノマーの単独または組合せをゼラチンにグラフ
ト化させたもの；合成親水性高分子物質、例えばビニル
アルコール、Ｎ−ビニルピロリドン、ヒドロキシアルキ
ル（メタ）アクリレート、（メタ）アクリルアミド、Ｎ
置換（メタ）アクリルアミド、Ｎ置換（メタ）アクリル
アミド等の単量体を成分とするホモポリマーもしくはこ
れら相互の共重合体、これらと（メタ）アクリル酸エス
テル、酢酸ビニル、スチレンなどとの共重合体、上記の
いずれかと無水マレイン酸、マレアミン酸などとの共重
合体など；ゼラチン以外の天然親水性高分子物質、例え
ばカゼイン、寒天、アルギン酸多糖類等も単独もしくは
混合して用いることができる。As the binder of the silver halide according to the present invention or the dispersion medium used for the production of the grains, a hydrophilic colloid usually used in silver halide emulsions is used. Examples of the hydrophilic colloid include not only gelatin (which may be lime-treated or acid-treated) but also gelatin derivatives such as gelatin and aromatic sulfonyl chlorides, acid chlorides, acid anhydrides as described in US Pat. No. 2,614,928. Derivatives produced by the reaction of a dimer, an isocyanate, and 1,4-dikents, a gelatin derivative described in US Pat. No. 3,118,766, which is produced by the reaction of gelatin with trimellitic anhydride, and JP-B-39-5514. Gelatin derivatives obtained by reacting an organic acid having active halogen with gelatin described in JP-A-42-26845, Gelatin derivatives obtained by reaction between aromatic glycidyl ether described in JP-B No. 42-26845 and gelatin, described in US Pat. No. 3,186,846. Gelatin derivatives by the reaction of maleimide, maleamic acid, unsaturated aliphatic diamide, etc. with gelatin, Country. No. 1,033,189
Sulfoalkylated Gelatin, US Patent
Polyoxyalkylene derivatives of gelatin described in 3,312,553; polymer graft products of gelatin, such as acrylic acid, methacrylic acid, esters thereof with mono- or polyhydric alcohols, also amides, acrylics (or methacrylics) Grafting of ethryl, styrene and other vinyl monomers alone or in combination with gelatin; synthetic hydrophilic polymer substances such as vinyl alcohol, N-vinylpyrrolidone, hydroxyalkyl (meth) acrylate, (meth) acrylamide, N
Homopolymers containing monomers such as substituted (meth) acrylamides and N-substituted (meth) acrylamides or copolymers thereof, and copolymers of these with (meth) acrylic acid esters, vinyl acetate, styrene, etc. Copolymers of any of the above with maleic anhydride, maleamic acid, etc .; natural hydrophilic polymer substances other than gelatin, such as casein, agar, alginic acid polysaccharides, etc., can be used alone or in combination.
本発明に係るハロゲン化銀粒子を含む乳剤は、目的に応
じて通常用いられる種々の添加剤を含むことができる。
例えばアザインデン類、トリアゾール類、テトラゾール
類、イミダゾリウム塩、テトラゾリウム塩、ポリヒドロ
キシ化合物等の安定剤やカブリ防止剤；アルデヒド系、
アジリジン系、イノオキサゾール系、ビニルスルホン
系、アクリロイル系、アルポジイミド系、マレイミド
系、メタンスルホン酸エステル系、トリアジン系等の硬
膜剤；ベンジルアルコール、ポリオキシエチレン系化合
物等の現像促進剤；クロマン系、クラマン系、ビスフェ
ノール系、亜リン酸エステル系の画像安定剤；ワック
ス、高級脂肪酸のグリセライド、高級脂肪酸の高級アル
コールエステル等の潤滑剤等がある。また、界面活性剤
として塗布助剤、処理液等に対する浸透性の改良剤、消
泡剤あるいは感光材料の種々の物理的性質のコントロー
ルのための素材として、アニオン型、カチオン型、非イ
オン型あるいは両性の各種のものが使用できる。帯電防
止剤としてはジアセチルセルローズ、スチレンパーフル
オロアルキルリジウムマレエート共重合体、スチレン−
無水マレイン酸共重合体とp−アミノベンゼンスルホン
酸との反応物のアルカリ塩等が有効である。マット剤と
してはポリメタクリル酸メチル、ポリスチレン及びアル
カリ可溶性ポリマー等が挙げられる。またさらにコロイ
ド状酸化珪素の使用も可能である。また膜物性を向上す
るために添加するラテックスとしてはアクリル酸エステ
ル、ビニルエステル等と他のエチレン基を持つ単量体と
の共重合体を挙げることができる。ゼラチン可塑剤とし
てはグリセリン、グリコール系化合物等を挙げることが
でき、増粘剤としてはスチレン−マレイン酸ソーダ共重
合体、アルキルビニルエーテル−マレイン酸共重合体等
が挙げられる。The emulsion containing silver halide grains according to the present invention can contain various additives usually used depending on the purpose.
For example, stabilizers and antifoggants such as azaindenes, triazoles, tetrazoles, imidazolium salts, tetrazolium salts, polyhydroxy compounds; aldehyde-based agents,
Hardeners such as aziridine type, inoxazole type, vinyl sulfone type, acryloyl type, arpegimide type, maleimide type, methanesulfonic acid ester type, triazine type, etc .; development accelerators such as benzyl alcohol, polyoxyethylene type compound, etc .; chroman type. , Claman-based, bisphenol-based, phosphite-based image stabilizers; waxes, glycerides of higher fatty acids, and lubricants such as higher alcohol esters of higher fatty acids. Further, a coating aid as a surfactant, an agent for improving the permeability to a processing liquid, a defoaming agent, or a material for controlling various physical properties of a light-sensitive material is used as an anion type, a cation type, a nonionic type or Various amphoteric substances can be used. As antistatic agents, diacetyl cellulose, styrene perfluoroalkylridium maleate copolymer, styrene-
Alkaline salts of a reaction product of a maleic anhydride copolymer and p-aminobenzenesulfonic acid are effective. Examples of the matting agent include polymethyl methacrylate, polystyrene and alkali-soluble polymers. It is also possible to use colloidal silicon oxide. Examples of the latex added to improve the physical properties of the film include copolymers of acrylic acid ester, vinyl ester and the like with other monomers having an ethylene group. Examples of the gelatin plasticizer include glycerin and glycol compounds, and examples of the thickener include styrene-sodium maleate copolymer and alkyl vinyl ether-maleic acid copolymer.
本発明に係るハロゲン化銀粒子は、白黒一般用、Ｘレイ
用、カラー用、赤外用、マイクロ用、銀色素漂白法用、
反転用、拡散転写法用等の種々の用途の写真感光材料に
有効に適用することができる。The silver halide grain according to the present invention is used for general black and white, X ray, color, infrared, micro, silver dye bleaching method,
It can be effectively applied to photographic light-sensitive materials for various purposes such as reversal and diffusion transfer method.
本発明のハロゲン化銀粒子を有する乳剤は、少くとも２
種の平均粒径が異なるが感度の異なる乳剤を混合するこ
とによって、あるいは複層塗布することによって豊かな
ラチチュードを有することができる。Emulsions having silver halide grains of the present invention are at least 2
Rich latitude can be obtained by mixing emulsions having different average grain sizes of seeds but different sensitivities, or by multilayer coating.
本発明に係るハロゲン化銀粒子をカラー用の感光材料に
適用するには、赤感性、緑感性及び青感性に調節された
本発明に係るハロゲン化銀粒子を含む乳剤にシアン、マ
ゼンタ及びイエローカプラーを組合せて含有せしめる等
カラー用感光材料に使用される手法及び素材を充当すれ
ばよい。In order to apply the silver halide grains according to the present invention to a color light-sensitive material, a cyan, magenta and yellow coupler can be added to an emulsion containing the silver halide grains according to the present invention which are adjusted to have red-sensitivity, green-sensitivity and blue-sensitivity. The methods and materials used for the color light-sensitive material may be applied such that they are contained in combination.
イエローカプラーとしては開鎖ケトメチレン系カプラー
を用いることができる。これらのうちベンゾイルアセト
アニリド系及びピバロイルアセトアニリド系化合物が有
用である。マゼンタカプラーとしてはピラゾロン系化合
物、イソダゾロン系化合物、シアノアセチル化合物、シ
アンカプラーとしてはフェノール系化合物、ナフトール
系化合物などを用いることができる。An open chain ketomethylene type coupler can be used as the yellow coupler. Among these, benzoylacetanilide compounds and pivaloylacetanilide compounds are useful. A pyrazolone compound, an isodazolone compound, a cyanoacetyl compound can be used as the magenta coupler, and a phenol compound and a naphthol compound can be used as the cyan coupler.
本発明に係るハロゲン化銀写真感光材料においては、赤
感性乳剤層、緑感性乳剤層および青感性乳剤層はそれぞ
れ２層以上から成っていてもよく、例えばカラーネガ写
真感光材料においては、通常２層あるいは３層が好まし
く用いられる。該各乳剤層の塗設位置は使用目的に応じ
て任意に定めることができる。同一感色層を複数用いる
場合、それぞれを分離して塗設することができる。In the silver halide photographic light-sensitive material according to the present invention, each of the red-sensitive emulsion layer, the green-sensitive emulsion layer and the blue-sensitive emulsion layer may be composed of two or more layers. For example, in a color negative photographic light-sensitive material, it is usually two layers. Alternatively, three layers are preferably used. The coating position of each emulsion layer can be arbitrarily determined according to the purpose of use. When a plurality of the same color-sensitive layers are used, they can be separately applied.
本発明に係るハロゲン化銀粒子を含む乳剤層は、これら
の感光性層の任意の層に適用することができる。なお、
各感色性層が感度の異なる２層以上からなるとき、より
高感度の層へ適用する方がより低感度の層へ適用するよ
りも本発明の効果が大きい。The emulsion layer containing silver halide grains according to the present invention can be applied to any of these photosensitive layers. In addition,
When each color-sensitive layer is composed of two or more layers having different sensitivities, the effect of the present invention is greater when applied to a layer having higher sensitivity than when applied to a layer having lower sensitivity.
写真感光材料の支持体としては、例えば、バライタ紙、
ポリエチレン被覆紙、ポリプロピレン合成紙、ガラス、
セルロースアセテート、セルロースナイトレート、ポリ
ビニルアセタール、ポリプロピレン、例えばポリエチレ
ンテレフタレート等のポリエステルフイルム、ポリスチ
レン等の通常用いられるものをそれぞれ写真感光材料の
使用目的に応じて適宜選択することができる。Examples of the support for the photographic light-sensitive material include baryta paper and
Polyethylene coated paper, polypropylene synthetic paper, glass,
A commonly used one such as cellulose acetate, cellulose nitrate, polyvinyl acetal, polypropylene, polyester film such as polyethylene terephthalate, polystyrene or the like can be appropriately selected depending on the intended use of the photographic light-sensitive material.
これらの支持体は必要に応じて下引加工が施される。These supports are subjected to a subbing process, if necessary.
本発明に係るハロゲン化銀粒子を有する写真感光材料は
露光後通常用いられる公知の方法により現像処理するこ
とができる。The photographic light-sensitive material having silver halide grains according to the present invention can be subjected to development processing after exposure by a known method usually used.
黒白現像液は、ヒドロキシベンゼン類、アミノフェノー
ル類、アミノベンゼン類等の現像主薬を含むアルカリ溶
液であり、その他アルカリ金属塩の亜硫酸塩、炭酸塩、
重亜硫酸塩、臭化物及び沃臭物等を含むことができる。
また該感光材料がカラー用の場合には通常用いられる発
色現像法で発色現像することができる。反転法ではまず
黒白ネガ現像液で現像し、次いで白色露光を与えるか、
或いはカブリ剤を含有する浴で処理し、更に発色現像主
薬を含むアルカリ現像液で発色現像する。処理方法につ
いては特に制限はなくあらゆる処理方法が適用できる
が、例えばその代表的なものとしては、発色現像後、漂
白定着処理を行い必要に応じ、さらに水洗、安定処理を
行う方式あるいは発色現像後、漂白と定着を分離して行
い必要に応じ、さらに水洗、安定処理を行う方式を適用
することができる。The black-and-white developing solution is an alkaline solution containing a developing agent such as hydroxybenzenes, aminophenols, aminobenzenes, and other alkali metal sulfites, carbonates,
A bisulfite, a bromide, an iodo odor, etc. can be included.
When the light-sensitive material is for color, color development can be performed by a commonly used color development method. In the reversal method, first develop with a black and white negative developer and then give a white exposure, or
Alternatively, it is processed in a bath containing a fogging agent, and then color development is performed with an alkaline developer containing a color developing agent. There are no particular restrictions on the processing method, and any processing method can be applied. For example, as a typical example, after color development, bleach-fixing processing is performed, and if necessary, further washing with water, stabilization processing or after color development. A method in which bleaching and fixing are separately performed and, if necessary, further washing with water and stabilizing treatment can be applied.
次に実施例を挙げて本発明を具体的に説明するが、本発
明はこれらによって限定されるものではない。Next, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.
実施例−１ 以下に示す５種類の溶液を用いて、臭化銀乳剤ＥＭ１及
びＥＭ２を作成した。種乳剤には平均粒径0.25μm、粒
径分布の変動係数10％の単分散臭化銀乳剤を用いた。Example-1 Silver bromide emulsions EM1 and EM2 were prepared using the following five kinds of solutions. As the seed emulsion, a monodisperse silver bromide emulsion having an average grain size of 0.25 μm and a variation coefficient of grain size distribution of 10% was used.
（溶液Ａ−１） （溶液Ｂ−１） （溶液Ｃ−１） （溶液Ｄ−１） 50％ＫＢｒ水溶液で pAg調整必要量 （溶液Ｅ−１） 56％酢酸水溶液 pH調整必要量 40℃において特開昭57-92523号および同57-92524号に示
される混合撹拌機を用いて（溶液Ａ−１）に（溶液Ｃ−
１）と（溶液Ｂ−１）とを同時混合法によって途中小粒
子発生のない最少時間を要して添加した。同時混合中の
pAgは8.6とし、pHおよび（溶液Ｃ−１）の添加速度は表
−３に示すように制御した。pAgおよびpHの制御は流量
可変のローラーチューブポンプにより（溶液Ｄ−１）、
（溶液Ｅ−１）および（溶液Ｂ−１）の流量を変えなが
ら行った。(Solution A-1) (Solution B-1) (Solution C-1) (Solution D-1) pAg adjustment required amount with 50% KBr aqueous solution (Solution E-1) 56% acetic acid aqueous solution pH adjustment required amount At 40 ° C., mixing and stirring shown in JP-A-57-92523 and 57-92524. (Solution A-1) to (Solution C-
1) and (Solution B-1) were added by the simultaneous mixing method so as to require a minimum time during which no small particles were generated on the way. During simultaneous mixing
The pAg was 8.6, and the pH and addition rate of (Solution C-1) were controlled as shown in Table 3. The pAg and pH are controlled by a roller tube pump with variable flow rate (solution D-1).
This was performed while changing the flow rates of (Solution E-1) and (Solution B-1).
ＥＭ１では（溶液Ｃ−１）の添加終了１分後に（溶液Ｅ
−１）によってpHを6.0に調整した。In EM1, 1 minute after the addition of (Solution C-1) was completed, (Solution E)
The pH was adjusted to 6.0 by -1).
ＥＭ２では（溶液Ｃ−１）の添加終了１分後に（溶液Ｄ
−１）によってpAgを9.9に調整し、更に３分後（溶液Ｅ
−１）によってpHを6.0に調整した。In EM2, 1 minute after the addition of (Solution C-1) was completed, (Solution D)
-1) adjusted pAg to 9.9 and after 3 minutes (Solution E)
The pH was adjusted to 6.0 by -1).
次に常法により脱塩水洗を行い、オセインゼラチン56.3
gを含む水溶液に分散したのち、蒸留水で総量を1500m
に調製し、さらに（溶液Ｄ−１）及び（溶液Ｅ−１）を
用いて40℃においてpAg8.5、pH5.8に調製した。Next, deionized water was washed by a conventional method, and ossein gelatin 56.3
After dispersing in an aqueous solution containing g, add distilled water to bring the total volume to 1500 m.
Then, (solution D-1) and (solution E-1) were used to prepare pAg8.5 and pH 5.8 at 40 ° C.
電子顕微鏡観察の結果、ＥＭ１，２とも平均粒径1.0μ
m、粒径分布の変動係数が10％という高度な単分散乳剤
であることがわかった。As a result of electron microscope observation, both EM1 and EM have an average particle size of 1.0 μ
It was found to be a highly monodisperse emulsion with a coefficient of variation of m and grain size distribution of 10%.
ＥＭ１の臭化銀粒子は第１図のような形態をしており、
外表面はすべて(nn1)面から構成される24面体粒子で稜
線ｃ（第１図）が明瞭に観察された。これに対し、ＥＭ
２では稜線ｃが不明瞭であった。The silver bromide grains of EM1 have the form shown in FIG.
Ridge lines c (Fig. 1) were clearly observed on the outer surface of a tetrahedral grain composed of (nn1) planes. In contrast, EM
In 2, the ridge line c was unclear.
実施例−２ 実施例-1における（溶液Ａ−１）、（溶液Ｂ−１）をそ
れぞれ下記（溶液Ａ−２）、（溶液Ｂ−２）に換え、ま
た種乳剤を平均粒径0.25μm、変動係数11％、沃化銀４
モル％の沃臭化銀とし、更に同時混合中のpAg、pHおよ
び（溶液Ｃ−１）の添加速度を表−４に示す制御に変更
したほかは、実施例１、ＥＭ１の製法と同様にしてＥＭ
３を、ＥＭ２の製法と同様にしてＥＭ４を作成した。Ｅ
Ｍ３及びＥＭ４は４モル％沃化銀を含む、沃臭化銀乳剤
である。 Example-2 (Solution A-1) and (Solution B-1) in Example-1 were replaced with the following (Solution A-2) and (Solution B-2), and the seed emulsion had an average grain size of 0.25 μm. , Coefficient of variation 11%, silver iodide 4
Mol% silver iodobromide was used, and pAg, pH and the addition rate of (solution C-1) during the simultaneous mixing were changed to the control shown in Table-4, except that the production method of Example 1 and EM1 was changed. EM
EM4 was prepared in the same manner as in EM2. E
M3 and EM4 are silver iodobromide emulsions containing 4 mol% silver iodide.
（溶液Ａ−２） （溶液Ｂ−２） 電子顕微鏡観察の結果、ＥＭ３，４とも平均粒径1.0μm
の単分散乳剤であり、ＥＭ３の変動係数が11％、ＥＭ４
が12％という高度な単分散乳剤であることがわかった。(Solution A-2) (Solution B-2) As a result of electron microscope observation, EM3 and 4 both have an average particle size of 1.0 μm.
Is a monodisperse emulsion of EM3, the coefficient of variation of EM3 is 11%, EM4
It was found to be a highly monodisperse emulsion having a ratio of 12%.
ＥＭ３の沃臭化銀粒子は第１図のような形態をしてお
り、外表面はすべて(nn1)面から構成される24面体粒子
で稜線ｃが明瞭に観察された。これに対し、ＥＭ４では
稜線ｃが不明瞭であった。The silver iodobromide grains of EM3 have a morphology as shown in FIG. 1, and the outer surface is a dodecahedral grain composed entirely of (nn1) faces, and the ridge line c is clearly observed. On the other hand, in EM4, the ridge line c was unclear.
実施例−３ 実施例２における（溶液Ａ−２）、（溶液Ｂ−２）をそ
れぞれ下記（溶液Ａ−３）（溶液Ｂ−３）に換え、また
同時混合中のpAg、pHおよび表−３（溶液Ｃ−１）の添
加速度を表−５に示す制御に変更したほかは、実施例
２、ＥＭ３の製法と同様にしてＥＭ５を、ＥＭ４の製法
と同様にしてＥＭ６を作成した。ＥＭ５、ＥＭ６は14.8
モル％沃化銀を含む、沃臭化銀乳剤である。Example-3 (Solution A-2) and (Solution B-2) in Example 2 were replaced with the following (Solution A-3) and (Solution B-3), respectively, and pAg, pH and table during simultaneous mixing were changed. EM5 and EM6 were prepared in the same manner as in the production method of Example 2 and EM3, except that the addition rate of 3 (solution C-1) was changed to the control shown in Table-5. 14.8 for EM5 and EM6
A silver iodobromide emulsion containing mol% silver iodide.
（溶液Ａ−３） （溶液Ｂ−３） 電子顕微鏡観察の結果、ＥＭ５，６とも平均粒径1.0μm
の単分散乳剤であり、ＥＭ５の変動係数が13％、ＥＭ６
が14％という高度な単分散乳剤であることがわかった。(Solution A-3) (Solution B-3) As a result of electron microscope observation, the average particle size of both EM5 and 6 is 1.0 μm.
Is a monodisperse emulsion of EM5, the coefficient of variation of EM5 is 13%, EM6
Was found to be a highly monodisperse emulsion having a ratio of 14%.
ＥＭ５の沃臭化銀粒子は第１図のような形態をしてお
り、外表面はすべて(nn1)面から構成される24面体粒子
で稜線ｃが明瞭に観察された。これに対し、ＥＭ６では
稜線ｃが不明瞭であった。The silver iodobromide grains of EM5 have the morphology as shown in FIG. 1, and the outer surface is a dodecahedral grain composed entirely of (nn1) faces, and the ridge line c is clearly observed. On the other hand, in EM6, the ridge line c was unclear.
実施例−４ 以下に示す７種類の溶液を用いて、沃臭化銀コア／シェ
ル乳剤ＥＭ７、ＥＭ８を作成した。種乳剤には平均粒径
0.25μm粒径分布の変動係数11％、沃化銀含有率４モル
％の沃臭化銀乳剤を用いた。Example-4 Silver iodobromide core / shell emulsions EM7 and EM8 were prepared using the following seven kinds of solutions. Average grain size for seed emulsion
A silver iodobromide emulsion having a variation coefficient of 11% in a 0.25 μm grain size distribution and a silver iodide content of 4 mol% was used.
（溶液Ａ−４） （溶液Ｂ−４） （溶液Ｂ−５） （溶液Ｂ−６） （溶液Ｃ−４） （溶液Ｄ−４） 50％ＫＢｒ水溶液で pAg調整必要量 （溶液Ｅ−４） 56％酢酸水溶液 pH調整必要量 50℃において特開昭57-92523号および同57-92524号に記
される混合撹拌機を用いて（溶液Ａ−４）に（溶液Ｃ−
４）と（溶液Ｂ−４）とを同時混合法によって途中小粒
子発生のない最少時間を要して添加した。同時混合中の
pAgは8.6とし、pHおよび（溶液Ｃ−４）の添加速度は表
−６に示すように制御した。(Solution A-4) (Solution B-4) (Solution B-5) (Solution B-6) (Solution C-4) (Solution D-4) Necessary amount of pAg adjustment with 50% KBr aqueous solution (Solution E-4) Necessary amount of pH adjustment with 56% acetic acid aqueous solution At 50 ° C, the mixing described in JP-A-57-92523 and 57-92524. Using a stirrer, add (Solution A-4) to (Solution C-
4) and (Solution B-4) were added by the simultaneous mixing method so that the minimum time during which no small particles were generated was required. During simultaneous mixing
The pAg was 8.6, and the pH and addition rate of (Solution C-4) were controlled as shown in Table-6.
pAgおよびpHの制御は流量可変のローラーチューブポン
プにより（溶液Ｄ−４）、（溶液Ｅ−４）の流量を変え
ながら行った。The pAg and pH were controlled by changing the flow rates of (Solution D-4) and (Solution E-4) with a roller tube pump having a variable flow rate.
ハロゲン化銀粒子の平均粒径（同体積の立方体の辺長）
が計算上0.65μmに達したところで（溶液Ｂ−４）を
（溶液Ｂ−５）に切り換え、更に平均粒径が計算上0.80
μmに達したところで（溶液Ｂ−５）を（溶液Ｂ−６）
に切り換えた。（溶液Ｂ−４）、（Ｂ−５）、（Ｂ−
６）はそれぞれ沃化物イオン濃度が、全ハロゲン化物イ
オン濃度に対して15モル％、５モル％、0.3モル％とし
て調整してある。Average grain size of silver halide grains (side length of cube of the same volume)
Is calculated to reach 0.65 μm, (Solution B-4) is switched to (Solution B-5), and the average particle size is calculated to be 0.80.
When the solution reaches μm, add (Solution B-5) to (Solution B-6)
I switched to. (Solution B-4), (B-5), (B-
In 6), the iodide ion concentration is adjusted to 15 mol%, 5 mol% and 0.3 mol% with respect to the total halide ion concentration.
ＥＭ７では（溶液Ｃ−４）の添加終了１分後に（溶液Ｅ
−４）によってpHを6.0に調整した。In EM7, 1 minute after the addition of (Solution C-4) was completed, (Solution E)
The pH was adjusted to 6.0 by -4).
ＥＭ８では（溶液Ｃ−４）の添加終了１分後に（溶液Ｄ
−４）によってpAgを9.9に調整し、更に３分後（溶液Ｅ
−４）によってpHを6.0に調整した。In EM8, 1 minute after the addition of (Solution C-4) was completed, (Solution D)
-4) adjusted pAg to 9.9 and after 3 minutes (Solution E)
The pH was adjusted to 6.0 by -4).
次に常法により脱塩水洗を行い、オセインゼラチン63.3
gを含む水溶液に分散したのち、蒸留水で総量を1500m
に調製し、さらに（溶液Ｄ−４）、（Ｅ−４）を用いて
40℃においてpAg8.5、pH5.8の調製した。Next, deionized water was washed by a conventional method, and ossein gelatin 63.3
After dispersing in an aqueous solution containing g, add distilled water to bring the total volume to 1500 m.
To (Solution D-4) and (E-4)
At 40 ° C, pAg 8.5 and pH 5.8 were prepared.
電子顕微鏡観察の結果、ＥＭ７，８とも平均粒径1.0μm
単分散乳剤であり、粒径分布の変動係数は、ＥＭ７が13
％、ＥＭ８が15％であることがわかった。ＥＭ７．８と
も粒子内部に高沃化銀含有相を有するコア／シェル型沃
臭化銀乳剤である。As a result of electron microscope observation, both EM7 and EM have an average particle size of 1.0 μm.
It is a monodisperse emulsion, and the coefficient of variation of grain size distribution is 13 for EM7.
%, EM8 was found to be 15%. EM7.8 is a core / shell type silver iodobromide emulsion having a high silver iodide content phase inside the grain.
ＥＭ７の沃臭化銀粒子は第１図のような形態をしてお
り、外表面はすべて(nn1)面から構成される24面体粒子
で稜線ｃが明瞭に観察された。これに対し、ＥＭ８では
稜線ｃが不明瞭であった。The silver iodobromide grains of EM7 had the morphology shown in FIG. 1, and the outer surface was a tetrahedral grain composed entirely of (nn1) faces, and the ridge line c was clearly observed. On the other hand, in EM8, the ridge line c was unclear.
〔発明の効果〕 本発明によって従来用いられた(100)面、(110)面及び(1
11)面を有するハロゲン化銀粒子とは全く異なる面(nn1)
結晶面を明確に有するハロゲン化銀粒子が再現性よく得
られ、この面のＡｇ＋イオン、Ｘ−の配列及び転位線の
表れ方等、従来の面とは異なることは明らかであり、既
に得られている写真特性上への好効果を更に改善する素
地を与えた。 (Effects of the Invention) (100) plane, (110) plane and (1
11) Surface completely different from silver halide grains (nn1)
It is clear that a silver halide grain having a clear crystal plane can be obtained with good reproducibility, and Ag + ions, X − arrangement and dislocation line appearance on this plane are different from the conventional plane, and it has already been obtained. It has provided the basis for further improving the positive effects on the photographic properties that are being considered.
第１図、第２図及び第３図は本発明に係る(nn1)面の図
式的な説明図である。 第４図は(nn1)面を有するハロゲン化銀粒子の電子顕微
鏡写真である。 １…(nn1)面 ２…(110)面 ３…(111)面 ４…(100)面 ａ及びｂ…頂点 ｃ…(110)面に重なる２つの(nn1)面の交線のなす稜線FIG. 1, FIG. 2 and FIG. 3 are schematic explanatory views of the (nn1) plane according to the present invention. FIG. 4 is an electron micrograph of silver halide grains having a (nn1) plane. 1 ... (nn1) face 2 ... (110) face 3 ... (111) face 4 ... (100) face a and b ... Vertex c ... Ridge line formed by intersecting lines of two (nn1) faces overlapping the (110) face
Claims (1)
ン化物溶液と水溶性銀塩溶液とを混合してハロゲン化銀
粒子を形成する工程を有するハロゲン化銀乳剤の製造方
法に於て、 （イ）ハロゲン化銀粒子の形成に用いる生成ハロゲン化
銀量の少なくとも30モル％が生成される期間はハロゲン
化銀懸濁母液のpAgを7.0〜9.8に制御し、かつ （ロ）該期間にテトラザインデン化合物を該母液中に共
存させ、かつ （ハ）ハロゲン化銀量の生成終了後、ハロゲン化銀粒子
を整え形成する間、pAgを7.0〜9.5に制御して、外表面
はすべて（ｎｎ１）面から構成され、しかも明確な稜線
を有する２４面体ハロゲン化銀粒子からなることを特徴
とするハロゲン化銀乳剤の製造方法。 但し、ｎは２以上の自然数を表す。1. A method for producing a silver halide emulsion, comprising the step of forming a silver halide grain by mixing a water-soluble halide solution and a water-soluble silver salt solution in the presence of a protective colloid. (A) The pAg of the silver halide suspension mother liquor is controlled to 7.0 to 9.8 during the period in which at least 30 mol% of the amount of silver halide produced for forming silver halide grains is produced, and (b) during that period. A tetrazaindene compound is allowed to coexist in the mother liquor, and (c) after the production of the silver halide amount is finished, pAg is controlled to 7.0 to 9.5 during the formation and formation of silver halide grains, and the outer surface is entirely ( A process for producing a silver halide emulsion, characterized by comprising a tetrahedral silver halide grain having a ridge (n1) plane and having clear ridges. However, n represents a natural number of 2 or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61020593A JPH0640201B2 (en) | 1986-01-31 | 1986-01-31 | Method for producing silver halide emulsion |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61020593A JPH0640201B2 (en) | 1986-01-31 | 1986-01-31 | Method for producing silver halide emulsion |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62178237A JPS62178237A (en) | 1987-08-05 |
| JPH0640201B2 true JPH0640201B2 (en) | 1994-05-25 |
Family
ID=12031552
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61020593A Expired - Lifetime JPH0640201B2 (en) | 1986-01-31 | 1986-01-31 | Method for producing silver halide emulsion |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0640201B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07101288B2 (en) * | 1988-01-25 | 1995-11-01 | 富士写真フイルム株式会社 | Method for producing silver halide photographic emulsion |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60122935A (en) * | 1983-12-07 | 1985-07-01 | Konishiroku Photo Ind Co Ltd | Preparation of silver halide emulsion |
| JPS60247237A (en) * | 1984-05-22 | 1985-12-06 | Konishiroku Photo Ind Co Ltd | Silver halide photosensitive material |
| JPS6114630A (en) * | 1984-06-29 | 1986-01-22 | Konishiroku Photo Ind Co Ltd | Preparation of silver halide emulsion |
-
1986
- 1986-01-31 JP JP61020593A patent/JPH0640201B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62178237A (en) | 1987-08-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4514491A (en) | Photosensitive silver halide emulsion | |
| JPH0352845B2 (en) | ||
| JPS58106532A (en) | Silver halide emulsion and its preparation | |
| JPH0466011B2 (en) | ||
| US4769315A (en) | Silver halide grain and light-sensitive photographic material containing said silver halide grain | |
| JPH07113739B2 (en) | Silver halide photographic light-sensitive material | |
| JPH0640201B2 (en) | Method for producing silver halide emulsion | |
| JPS62212640A (en) | Silver halide photographic sensitive material | |
| JPH03120528A (en) | Silver halide emulsion high in sensitivity and improved in fog and graininess and manufacture of the same | |
| JPS62229128A (en) | Silver halide particle and silver halide photographic sensitive material containing same | |
| JPH055094B2 (en) | ||
| JPH0431378B2 (en) | ||
| JPH0789202B2 (en) | Silver halide photographic light-sensitive material with improved spectral sensitization sensitivity | |
| JP2603189B2 (en) | Photosensitive silver halide emulsion | |
| JPH07113740B2 (en) | Silver halide photographic light-sensitive material | |
| JPS59148049A (en) | Silver halide emulsion | |
| JPS62217238A (en) | Silver halide photosensitive material sensitized in presence of thiocyanate | |
| JPS62223748A (en) | (nn1) face having silver halide photographic sensitive material using sensitizing dye | |
| JPH0664309B2 (en) | Silver halide photosensitive material sensitized in the presence of silver halide solvent | |
| JPS59152438A (en) | Silver halide emulsion | |
| JP3041377B2 (en) | Silver halide emulsion and light-sensitive material containing the emulsion | |
| JP2907964B2 (en) | Silver halide emulsion with high sensitivity and good developability | |
| JPS61232445A (en) | Method for producing silver halide photographic emulsion | |
| JPS6135440A (en) | Silver halide grain, its preparation and photosensitive material containing same | |
| JPH058812B2 (en) |