JPS6326651A - Silver halide photographic sensitive material - Google Patents
Silver halide photographic sensitive materialInfo
- Publication number
- JPS6326651A JPS6326651A JP17066386A JP17066386A JPS6326651A JP S6326651 A JPS6326651 A JP S6326651A JP 17066386 A JP17066386 A JP 17066386A JP 17066386 A JP17066386 A JP 17066386A JP S6326651 A JPS6326651 A JP S6326651A
- Authority
- JP
- Japan
- Prior art keywords
- silver
- silver halide
- gelatin
- mol
- layer
- 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.)
- Granted
Links
- -1 Silver halide Chemical class 0.000 title claims abstract description 117
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 109
- 239000004332 silver Substances 0.000 title claims abstract description 109
- 239000000463 material Substances 0.000 title claims description 26
- 239000000839 emulsion Substances 0.000 claims abstract description 69
- 229920000159 gelatin Polymers 0.000 claims abstract description 49
- 239000008273 gelatin Substances 0.000 claims abstract description 49
- 108010010803 Gelatin Proteins 0.000 claims abstract description 48
- 235000019322 gelatine Nutrition 0.000 claims abstract description 48
- 235000011852 gelatine desserts Nutrition 0.000 claims abstract description 48
- 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 claims abstract description 20
- 229910021612 Silver iodide Inorganic materials 0.000 claims abstract description 20
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229940045105 silver iodide Drugs 0.000 claims abstract description 20
- 239000013078 crystal Substances 0.000 claims abstract description 19
- 239000004848 polyfunctional curative Substances 0.000 claims abstract description 13
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 claims abstract description 7
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 5
- 150000007524 organic acids Chemical class 0.000 claims abstract description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 32
- 239000002245 particle Substances 0.000 claims description 17
- 239000000126 substance Substances 0.000 claims description 13
- 239000011230 binding agent Substances 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 230000035945 sensitivity Effects 0.000 abstract description 25
- 239000002253 acid Substances 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 8
- 238000000586 desensitisation Methods 0.000 abstract description 5
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 69
- 238000000034 method Methods 0.000 description 50
- 150000001875 compounds Chemical class 0.000 description 31
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 21
- 206010070834 Sensitisation Diseases 0.000 description 19
- 230000008313 sensitization Effects 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 239000007864 aqueous solution Substances 0.000 description 13
- 238000011161 development Methods 0.000 description 12
- 230000018109 developmental process Effects 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 11
- 238000000576 coating method Methods 0.000 description 11
- 230000005070 ripening Effects 0.000 description 10
- 150000003839 salts Chemical class 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 9
- 230000001235 sensitizing effect Effects 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- 239000010931 gold Substances 0.000 description 8
- 229910052737 gold Inorganic materials 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 8
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 7
- 238000007796 conventional method Methods 0.000 description 7
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 7
- 229910052740 iodine Inorganic materials 0.000 description 7
- 239000011630 iodine Substances 0.000 description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 150000004820 halides Chemical class 0.000 description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 6
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- 239000011593 sulfur Substances 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- 150000007513 acids Chemical class 0.000 description 5
- 239000000084 colloidal system Substances 0.000 description 5
- 125000005843 halogen group Chemical group 0.000 description 5
- 229920002554 vinyl polymer Polymers 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 125000000753 cycloalkyl group Chemical group 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 235000021317 phosphate Nutrition 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 229910001961 silver nitrate Inorganic materials 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical class OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 229920003171 Poly (ethylene oxide) Chemical class 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 3
- 229910021607 Silver chloride Inorganic materials 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 229910052783 alkali metal Chemical group 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 238000004061 bleaching Methods 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000004040 coloring Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000011033 desalting Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 229910052741 iridium Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000011241 protective layer Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 229910052711 selenium Inorganic materials 0.000 description 3
- 239000011669 selenium Substances 0.000 description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 3
- HAAYBYDROVFKPU-UHFFFAOYSA-N silver;azane;nitrate Chemical compound N.N.[Ag+].[O-][N+]([O-])=O HAAYBYDROVFKPU-UHFFFAOYSA-N 0.000 description 3
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 3
- 230000000087 stabilizing effect Effects 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 125000003396 thiol group Chemical group [H]S* 0.000 description 3
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- 229920002284 Cellulose triacetate Polymers 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 235000018936 Vitellaria paradoxa Nutrition 0.000 description 2
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001340 alkali metals Chemical group 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- ZOJBYZNEUISWFT-UHFFFAOYSA-N allyl isothiocyanate Chemical compound C=CCN=C=S ZOJBYZNEUISWFT-UHFFFAOYSA-N 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N alpha-ketodiacetal Natural products O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- CJPQIRJHIZUAQP-MRXNPFEDSA-N benalaxyl-M Chemical compound CC=1C=CC=C(C)C=1N([C@H](C)C(=O)OC)C(=O)CC1=CC=CC=C1 CJPQIRJHIZUAQP-MRXNPFEDSA-N 0.000 description 2
- JEHKKBHWRAXMCH-UHFFFAOYSA-N benzenesulfinic acid Chemical compound O[S@@](=O)C1=CC=CC=C1 JEHKKBHWRAXMCH-UHFFFAOYSA-N 0.000 description 2
- 229920002301 cellulose acetate Polymers 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000001493 electron microscopy Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- ALCDAWARCQFJBA-UHFFFAOYSA-N ethylselanylethane Chemical compound CC[Se]CC ALCDAWARCQFJBA-UHFFFAOYSA-N 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical class OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 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
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- JEXVQSWXXUJEMA-UHFFFAOYSA-N pyrazol-3-one Chemical class O=C1C=CN=N1 JEXVQSWXXUJEMA-UHFFFAOYSA-N 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- 229930182490 saponin Natural products 0.000 description 2
- 150000007949 saponins Chemical class 0.000 description 2
- 235000017709 saponins Nutrition 0.000 description 2
- 150000003346 selenoethers Chemical class 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical class OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 description 1
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical class C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 1
- GGZHVNZHFYCSEV-UHFFFAOYSA-N 1-Phenyl-5-mercaptotetrazole Chemical compound SC1=NN=NN1C1=CC=CC=C1 GGZHVNZHFYCSEV-UHFFFAOYSA-N 0.000 description 1
- ADAKRBAJFHTIEW-UHFFFAOYSA-N 1-chloro-4-isocyanatobenzene Chemical compound ClC1=CC=C(N=C=O)C=C1 ADAKRBAJFHTIEW-UHFFFAOYSA-N 0.000 description 1
- GFNKTLQTQSALEJ-UHFFFAOYSA-N 1-isocyanato-4-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(N=C=O)C=C1 GFNKTLQTQSALEJ-UHFFFAOYSA-N 0.000 description 1
- BDQNKCYCTYYMAA-UHFFFAOYSA-N 1-isocyanatonaphthalene Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1 BDQNKCYCTYYMAA-UHFFFAOYSA-N 0.000 description 1
- UZGKAASZIMOAMU-UHFFFAOYSA-N 124177-85-1 Chemical class NP(=O)=O UZGKAASZIMOAMU-UHFFFAOYSA-N 0.000 description 1
- JAAIPIWKKXCNOC-UHFFFAOYSA-N 1h-tetrazol-1-ium-5-thiolate Chemical class SC1=NN=NN1 JAAIPIWKKXCNOC-UHFFFAOYSA-N 0.000 description 1
- NOGFHTGYPKWWRX-UHFFFAOYSA-N 2,2,6,6-tetramethyloxan-4-one Chemical compound CC1(C)CC(=O)CC(C)(C)O1 NOGFHTGYPKWWRX-UHFFFAOYSA-N 0.000 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- PHPYXVIHDRDPDI-UHFFFAOYSA-N 2-bromo-1h-benzimidazole Chemical class C1=CC=C2NC(Br)=NC2=C1 PHPYXVIHDRDPDI-UHFFFAOYSA-N 0.000 description 1
- AYPSHJCKSDNETA-UHFFFAOYSA-N 2-chloro-1h-benzimidazole Chemical class C1=CC=C2NC(Cl)=NC2=C1 AYPSHJCKSDNETA-UHFFFAOYSA-N 0.000 description 1
- KRTDQDCPEZRVGC-UHFFFAOYSA-N 2-nitro-1h-benzimidazole Chemical class C1=CC=C2NC([N+](=O)[O-])=NC2=C1 KRTDQDCPEZRVGC-UHFFFAOYSA-N 0.000 description 1
- JSIAIROWMJGMQZ-UHFFFAOYSA-N 2h-triazol-4-amine Chemical class NC1=CNN=N1 JSIAIROWMJGMQZ-UHFFFAOYSA-N 0.000 description 1
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 description 1
- KSXHZOTTWSNEHY-UHFFFAOYSA-N 3-[3-(2-cyanoethoxy)-2,2-bis(2-cyanoethoxymethyl)propoxy]propanenitrile Chemical group N#CCCOCC(COCCC#N)(COCCC#N)COCCC#N KSXHZOTTWSNEHY-UHFFFAOYSA-N 0.000 description 1
- OWIRCRREDNEXTA-UHFFFAOYSA-N 3-nitro-1h-indazole Chemical class C1=CC=C2C([N+](=O)[O-])=NNC2=C1 OWIRCRREDNEXTA-UHFFFAOYSA-N 0.000 description 1
- MWWNNNAOGWPTQY-UHFFFAOYSA-N 3-nitrobenzenesulfonyl chloride Chemical compound [O-][N+](=O)C1=CC=CC(S(Cl)(=O)=O)=C1 MWWNNNAOGWPTQY-UHFFFAOYSA-N 0.000 description 1
- XRZDIHADHZSFBB-UHFFFAOYSA-N 3-oxo-n,3-diphenylpropanamide Chemical compound C=1C=CC=CC=1NC(=O)CC(=O)C1=CC=CC=C1 XRZDIHADHZSFBB-UHFFFAOYSA-N 0.000 description 1
- OCVLSHAVSIYKLI-UHFFFAOYSA-N 3h-1,3-thiazole-2-thione Chemical class SC1=NC=CS1 OCVLSHAVSIYKLI-UHFFFAOYSA-N 0.000 description 1
- ZLYBFBAHAQEEQQ-UHFFFAOYSA-N 4-chlorobenzenesulfonyl chloride Chemical compound ClC1=CC=C(S(Cl)(=O)=O)C=C1 ZLYBFBAHAQEEQQ-UHFFFAOYSA-N 0.000 description 1
- DTJVECUKADWGMO-UHFFFAOYSA-N 4-methoxybenzenesulfonyl chloride Chemical compound COC1=CC=C(S(Cl)(=O)=O)C=C1 DTJVECUKADWGMO-UHFFFAOYSA-N 0.000 description 1
- UTMDJGPRCLQPBT-UHFFFAOYSA-N 4-nitro-1h-1,2,3-benzotriazole Chemical class [O-][N+](=O)C1=CC=CC2=NNN=C12 UTMDJGPRCLQPBT-UHFFFAOYSA-N 0.000 description 1
- SKDHHIUENRGTHK-UHFFFAOYSA-N 4-nitrobenzoyl chloride Chemical compound [O-][N+](=O)C1=CC=C(C(Cl)=O)C=C1 SKDHHIUENRGTHK-UHFFFAOYSA-N 0.000 description 1
- HLQPFEHFAQQWLW-UHFFFAOYSA-N 5-bromo-2-chlorosulfonylbenzoic acid Chemical compound OC(=O)C1=CC(Br)=CC=C1S(Cl)(=O)=O HLQPFEHFAQQWLW-UHFFFAOYSA-N 0.000 description 1
- GIQKIFWTIQDQMM-UHFFFAOYSA-N 5h-1,3-oxazole-2-thione Chemical compound S=C1OCC=N1 GIQKIFWTIQDQMM-UHFFFAOYSA-N 0.000 description 1
- 244000215068 Acacia senegal Species 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229920001817 Agar Polymers 0.000 description 1
- 102000009027 Albumins Human genes 0.000 description 1
- 108010088751 Albumins Proteins 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 244000099147 Ananas comosus Species 0.000 description 1
- 235000007119 Ananas comosus Nutrition 0.000 description 1
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 1
- KHBQMWCZKVMBLN-UHFFFAOYSA-N Benzenesulfonamide Chemical class NS(=O)(=O)C1=CC=CC=C1 KHBQMWCZKVMBLN-UHFFFAOYSA-N 0.000 description 1
- 244000161488 Berberis lycium Species 0.000 description 1
- 235000008130 Berberis lycium Nutrition 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- 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
- G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
- G03C1/30—Hardeners
-
- 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
- G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
-
- 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
- G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
- G03C2001/03535—Core-shell grains
-
- 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
- G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
- G03C2001/03558—Iodide content
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- Chemical Kinetics & Catalysis (AREA)
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- Crystallography & Structural Chemistry (AREA)
Abstract
Description
[)li業上の利用分野】
本発明はハロゲン化銀写真感光材料に関し、更に詳しく
は、高感度でかぶりの低い沃臭化銀写真感光材料に関す
る。[Field of Industrial Application] The present invention relates to a silver halide photographic material, and more particularly to a silver iodobromide photographic material with high sensitivity and low fog.
近年、写真用のハロゲン化銀乳剤に対する要請はますま
す厳しく、高感度、優れた粒状性、高鮮鋭性、低いかぶ
り濃度および十分高い光学濃度等の写真性能に対してま
すます高水準の要求がなされている。
これらの要請に対して、高感度乳剤としては、沃臭化銀
乳剤で沃素を0〜10モル%含む乳剤が良く知られてい
る。そして、これらの乳剤を調製する方法としては、従
来がらアンモニア法、中性法、酸性法等のpH条件、p
Ag条件を制御する方法、混合法としてはシングルノエ
−/ )法、ダブルジェット法等が知られており、従来
から高感度写真フィルムに遇するハロゲン化銀乳剤とし
て多分散の双晶粒子からなる沃臭化銀乳剤が知られてい
る。
これらの公知技術を基盤にして、更なる高感度化、粒状
性の改良、高鮮鋭性および低かJ、−’)を達成する目
的のためにN級なまでに技術手段が検討され、実用化さ
れてきた1本発明で対象としている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aされた乳剤が研究さ
れてさた。
上に述べてきたような高感度、優れた粒状性、高鮮鋭性
、低いが」rり濃度および十分高いカバリングパワー等
の写真性能を達成するため、ハロゲン化銀の量子効率を
向上させ、がっ、化学熟成において低いが」ζワを保っ
たまま効率よく高感度を達成することを指向した単分散
乳剤が知られており、例えば特開昭58−107530
号、同58−126526号、同59−29243号、
同59−180536号、同59−181:137号等
により粒子外表面が(100)結晶面お上り/または(
111)結晶面からなる立方体、8面体または14面体
の沃臭化銀粒子からなる単分散乳剤により高感度化し得
ることが知られている。
また、特開昭60−222842号には (110)結
晶面を有する沃臭化銀以外により低いが老りを達成しう
るーことが開示されている。
最近、このような従来知られている(100)、(11
1)、(110)面以外の結晶面を有する臭化銀、沃化
銀粒子がvf開昭61−83531号に開示されている
。
この新しい結晶面に関しては、最近の研究によって、(
331)というミラー指数を有する事が日本写真T全昭
和61年度年次大会研究発表講演要旨p、79に報告さ
れた。
我々は、高感度の手段として(331)結晶面を有する
沃臭化銀乳剤について研究を進める過程で、該乳剤は熱
かフリ(感光材料が高温で保存されたときのがjζりの
増大)vf性に問題があることを見出し、更に該乳剤の
パイングーに用いるゼラチンの硬膜剤としてゼラチンと
反応して有機酸または無機酸を放出する有機の硬膜剤を
用いると熱かぶりは減少するが、多層構成(ゼラチンを
バイングーとする塗設層が2層1以上あることをいい、
通常実用されているハロゲン化銀写真感光材料は少なく
とも1層のゼラチン−ハロゲン化銀乳剤層の他にゼラチ
ン保護層を有し多層構成である。)にしたときの減感(
重層減感)が大きい欠5αのあることを見出した。In recent years, demands on silver halide emulsions for photography have become increasingly strict, with increasingly high standards required for photographic performance such as high sensitivity, excellent graininess, high sharpness, low fog density, and sufficiently high optical density. being done. In order to meet these demands, silver iodobromide emulsions containing 0 to 10 mol % of iodine are well known as high-sensitivity emulsions. Methods for preparing these emulsions include conventional methods such as ammonia method, neutral method, acidic method, etc. under pH conditions, p.
Methods for controlling Ag conditions and mixing methods include the single-noe method and the double-jet method. Conventionally, silver halide emulsions used in high-speed photographic films consist of polydisperse twin crystal grains. Silver iodobromide emulsions are known. Based on these known technologies, technological means up to the N level have been studied for the purpose of achieving further high sensitivity, improved graininess, high sharpness, and low sharpness (J, -'), and have been put into practical use. In the silver iodobromide emulsions targeted by the present invention, research has been conducted on emulsions in which not only the crystal habit and grain size distribution but also the iodine concentration distribution within individual silver halide grains are controlled. Sata. In order to achieve the above-mentioned photographic performance such as high sensitivity, excellent graininess, high sharpness, low density and sufficiently high covering power, the quantum efficiency of silver halide has been improved and Monodisperse emulsions are known that are aimed at efficiently achieving high sensitivity while maintaining low ζ in chemical ripening.
No. 58-126526, No. 59-29243,
According to No. 59-180536, No. 59-181:137, etc., the outer surface of the particle is a (100) crystal plane.
111) It is known that high sensitivity can be achieved by using a monodisperse emulsion consisting of cubic, octahedral or tetradecahedral silver iodobromide grains having crystal planes. Furthermore, JP-A No. 60-222842 discloses that silver iodobromide having a (110) crystal face can achieve a lower aging resistance. Recently, such conventionally known (100), (11
1) Silver bromide and silver iodide grains having crystal planes other than the (110) plane are disclosed in VF JP-A-61-83531. Regarding this new crystal plane, recent research has shown that (
331) was reported in the 1986 annual conference of Nippon Photo T, Research Presentation Abstracts, p. 79. In the process of researching silver iodobromide emulsions with (331) crystal planes as a means of high sensitivity, we discovered that the emulsions exhibit heat resistance (increasing of γ when photosensitive materials are stored at high temperatures). It was discovered that there was a problem with VF properties, and furthermore, using an organic hardener that reacts with gelatin to release organic or inorganic acids as a hardener for the gelatin used in the pineapple of the emulsion reduces heat fog, but the heat fog can be reduced. , multilayer structure (meaning that there are two or more coated layers with gelatin as the binder,
A commonly used silver halide photographic light-sensitive material has a multilayer structure including at least one gelatin-silver halide emulsion layer and a gelatin protective layer. ), the desensitization (
It was discovered that there is a lack of 5α with large layer desensitization).
本発明の目的は、高感度で、かつ熱がぶりの少ないハロ
ゲン化銀写真感光材料を提供することである0本発明の
他の目的は、(331)結晶面を有する沃臭化銀乳剤層
を有し、その高感度の特徴を生かし、熱かXりおよび重
°層滅感が少ないハロゲン化銀写真感光材料を提供する
ことである。An object of the present invention is to provide a silver halide photographic material having high sensitivity and low thermal burnout.Another object of the present invention is to provide a silver iodobromide emulsion layer having a (331) crystal plane. It is an object of the present invention to provide a silver halide photographic light-sensitive material which has a high sensitivity and exhibits less thermal x-ray and double layer desensitization.
本発明の目的は、少なくとも粒子表面が沃臭化銀から実
質的になり、(331)結晶面を外表面に有し、粒子表
面より内部の沃臭化銀含有率が高いコア/シェル構造を
有するハロゲン化銀粒子、および結合剤としてゼラチン
を含有し、ゼラチンと反応して有機または無機酸を放出
する有機の硬膜剤によって硬化された少なくとも1層の
ハロゲン化銀乳剤層を有することを特徴とするハロゲン
化銀写真感光材料によって達成される。
以下、本発明について詳述する。
本発明に係わるハロゲン化以粒子はミラー指数(331
)で定義される結晶面を外表面にもち、該粒子の少なく
とも表面が実質的に臭化銀または沃臭化銀からなるもの
である。
該粒子の表面には (331)面のほかに (100)
面、(lit)面(110)面等が存在してもがまわな
いが、全表面積に対する (331) i7i’iの割
合が20%以上であることが好ましく、80%以上であ
ることが特に好ましい。
また(331)面の存在やその割合については、電子顕
微鏡を用いた方法やx#a回折法、色素吸着法によって
知ることができる。
本発明のハロゲン化銀乳剤層には、(331)面を有す
るハロゲン化銀粒子が30重量%以上であることが好ま
しく、50重量%以上であることがより好ましい。
本発明に係わるハロゲン化以粒子の組成において、臭化
銀または沃臭化銀から実質的になるとは、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ことを意味
する。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−1。
本発明に係わるハロゲン化以粒子の沃化銀の比率は好ま
しくは0〜40モル%で、0〜20モル%の範囲が更に
好ましく、0〜15モル%の範囲が特に好ましい。
本発明に係るハロゲン化銀粒子は単一iff成のハロゲ
ン化銀粒子であっても、ハロゲン組成の異なる複数の相
(例えば層)からなるハロゲン化銀粒子(例えばコア/
シェル型粒子)であってもよい。
ハロゲン化銀粒子がハロゲン化銀組成において単一組成
でない場合、粒子内部のハロゲン、llr&は塩化銀、
塩臭化銀などであってもよい。
また、各相内のハロゲン組成は均一であっても、連続的
に変化するものであってもよい。
最も好ましい形態のひとつは粒子内部に高沃度植を有す
るものである。すなわち、粒子表面の沃素含有率より沃
素含有率の大きい相(複数でもよい)を粒子内部に有す
るハロゲン化銀粒子である。
本発明に係る(331)面を有するこのような粒子内部
高沃化銀タイプのコア/シェル乳剤について詳しくは特
開昭61−88235号に記載さhている。このような
コア/ンエル乳剤の場合、フ7のハロゲン化銀mraは
沃化銀を3〜40モル%含む事が好ましく、シェルのハ
ロゲン化銀1■成は沃化銀を0〜10モル%含有するハ
ロゲン化銀である事が好ましく、シェルとコアの沃化銀
含有率の差が2〜30モル%である事が好ましい、コア
/シェルとの境界における沃化銀含有率の変化は、連続
的、段階的等任意である。 本発明に係るハロゲン化銀
粒子の粒径は特に制約はな(、好ましくは0.1〜3.
0μ国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
等しい豆方体の一辺の長さをいう。
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
媒に分散された形態、すなわち乳剤と称される形態で製
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
さる。
本発明に係る (331)面を有するハロゲン化銀粒子
を製造するには、特開昭61−83531号に開示され
る方法を用いることができろ。
すなわち、(331)面を有する臭化服あるいは沃臭化
銀粒子を製造する方法として、保護コロイドの存在下で
水溶性系塩溶液と水溶性ハロゲン化物溶液とを混合して
ハロゲン化銀粒子を形成させる工程において、全ハロゲ
ン化銀の少なくとも30モル%が生成する期間、乳剤の
9AIFを8.0〜9.5の範囲に制御し、かつ、この
期間に結晶制御化合物として下記一般式([)、(■)
、(III)または(■)で表わされる化合物および下
記一般式(V)で表わされる繰り返し単位を有する化合
物から選ばれる少なくとも1種の化合物を上記乳剤中に
含有させることを特徴とする方法が示されている。
一般式(1) 一般式(fl)一般
式(ill) 一般式(IV)一般式(
V)
I5
−(−CI+、−C+−
■
式中、R11、R12およびI’l)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7基
、アミ7基の誘導体、フルキル基、アルキル基の誘導体
、アリール基、了り−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−CONII−R,,(R,、は水
素原子、アルキル基、アミ7基、アルキル基の誘導体、
アミ7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、アリール基または了り−ル
基の誘導体を表わす。)を表わし、RtSは水素原子ま
たはアルキル基を表わし、R11と1曵、□は結合して
環(例えば、5〜7貝の炭素環、複索環)を形成しても
よく、Xは一般式(1)、(II)、(1)または (
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(例えば前記一般式(1)ないし (IV)にお
けるR1−R13または011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。
結晶制御化合物(1)〜 (V)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lO1〜2 X 10””モルの範囲
が好ましい、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敗をもって、添加量とする。
結晶制御化合物(1)〜 (V)の添加方法としては予
め保護コロイド溶液中に添加しておく方法、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
せて行なう方法等がある。
本発明に係るハロゲン化銀粒子の製造方法において、種
粒子を使用し、その表面にハロゲン化凱を生I&させて
粒子を成長させてもよい。
本発明に係るハロゲン化銀粒子の製造方法において、ハ
ロゲン化銀を生成させハロゲン化ff1粒子を形成させ
ろ工程は、7ンモニ7の存在下にt3いて、アンモニア
性硝酸銀水溶渡とハライド水溶液とをダブルノエット法
で添加することが好ましい。
また、この粒子r&艮過程において、新たな結晶核が発
生しないように銀およびハライド溶液を添加することが
好ましい。
この製造方法の特徴は、vf聞昭61−83531号明
細書内で述べられているように、単分散性のすぐれたハ
ロゲン化銀乳剤を供給し得ることにある。
以上、本発明に係る (331)面を有するハロゲン化
銀粒子の製造方法の概略を述べたが、詳細は、特開昭6
1−83531号明#I書により知ることがでさる。
本発明に係わる (331)面を有するハロゲン化銀粒
子は、ハロゲン化銀粒子形成または物理熟成の過程にお
いて、カドミウム塩、亜鉛塩、鉛塩、タリウム塩、イリ
ノウム塩またはその錯塩、ロジウム塩またはその錯塩、
鉄塩またはその錯塩、金塩またはその錯塩などを共存さ
せてもよい。
沈澱形成後あるいは物理熟成後の乳剤から可溶性塩類を
除去するためにはゼラチンをゲル化させて行なうヌーデ
ル水洗法を用いてもよく、また無機塩類、アニオン性界
面活性剤、アニオン性ポリマ (たとえばポリスチレン
スルホン酸)、あるいはゼラチン講導体(たとえばアシ
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(70キユレージラン法)を用いテモヨい。
本発明に係るハロゲン化銀粒子は化学増感される。
化学熟成即ち、化学増感の工程の条件、例えばpH、C
IAIF、温度、時間および添加剤等に特に制限はなく
、当業界で一般に行なわれている条件で行うことができ
る。
化学増感のためには、銀イオンと反応し得る硫黄を含む
化合物や活性ゼラチンを用いる硫黄増感法、セレン化合
物を用いるセレン増感法、還元性物質を用いる還元増感
法、金その他の貴金属化合物を用いる貴金属増感法など
を単独または紙合せて用いることができる。
硫黄増感剤としては公知のものを用いる二とができる0
例えば、チオ硫酸塩、アリルチオ〃ルパミド、チオ尿素
、アリルイソチオシアネート、シスチン、9−)ルエン
チオスルホン酸塩、ローゲニンなどが挙げられる。その
他、米国特許1 、574 。
944号、同2.411)、689号、同2,278,
947号、同2,728゜668号、同3,501.3
13号、同3 、656 、955号、西独出顧公聞(
OLS) 1,422,869号、特開昭58−249
37号、同55−45016号等に記載されている硫黄
増感剤も用いることができる。m黄増感剤の添加量は、
乳剤の感度を効果的に増大させるに十分な量でよい。
この量は、含窒素複葉環化合物の添加量、pl+、温度
、ハロゲン化銀粒子の大きさなど種々の条件の下で相当
の範囲にわたって変化するが、目安としては、ハロゲン
化ia1モル当り約10−1モル−約to−’モル程度
が好ましい。
硫黄増感剤の代わりにセレン増感剤を用いることができ
るが、セレン増感剤としては、アリルイソセレノシアネ
ートの如き脂肪族イ類モレ/シアネート類、セレノ尿素
類、セレノケトン類、モレ/アミド類、セレノカルボン
酸類及びエステル類、セレノホスフェート類、ジエチル
セレナイド、ジエチルセレナイド等のセレナイド類など
を用いることができ、それらの具体例は、米国特許1.
574,944号、同1,602,592号、同1,6
23.499号に記載されている。
添加量は硫黄増感剤と同様に広い範囲にわたって変化す
るが、目安としては、ハロゲン化銀1モル当り約10−
1モルから10−1モル程度が好ましい。
本発明において、金増感剤としては金の価数が+1価で
も+3価でもよく多種の金化合物が用いられる1代表的
な例としては塩化金酸塩、カリウムクロロオーレート、
オーリックトリクロライY。
カリウムオーリックチオシアネート、カリウムヨードオ
ーレート、テトラシアノオーリックアシド、アンモニウ
ムオーロチオシアネート、ピリジルトリクロロゴールド
などが挙げられる。
金増感剤の添加量は種々の条件に上り異なるが目安とし
てはハロゲン化銀1モル当り約10−7モルから10−
’モルまでの範囲が好ましい。
金−ゼラチナートより金イオンを離脱させ、かつハロゲ
ン化銀粒子への含イオン吸着を促進する化合物としては
好ましいものは、R2MX、、R3M’X。
またはM’X、(式中、Rは水素原子、アンモニウム基
、アルカリ金属原子を表わし、MはptまたはPdを、
M′はIrまたはRbを表わす、またXはハロゲン原子
を表わす、)で示されるRh%Pd、 Ir、 pt¥
?の錯塩が効果的である。
具体的化合物としては(NH4)zPLcL、(旧+、
)、PdCf4、に31rBrss (旧1.)、R
hCe6−1211.0等が挙げられるが、特に好まし
いのはテトクロロパラジウム(II)酸アンモニウム(
NIl、)、PdC14である。
添加量は金増感剤に対し化学量論比(モル比)で10〜
100倍の範囲が好ましい。
添加時期は、化学熟成開始時、熟成進行中、熟成終了後
の何れの工程でもよいが、好ましくは化学熟成進行中で
あり、特に好ましくは金増感剤の添加と同時あるいはそ
の前後である。
本発明においては更に還元増感を併用することも可能で
ある。還元剤としては特に制限はないが、公知の塩化第
一錫、二酸化子オ尿素、ヒドラノン誘導体、ポリアミン
等が挙げられる。
還元増感を行う時期はハロゲン化11粒子のrR艮中に
行うが、カルコデン増感、金増感およびRh、Pd、
Ir、pt等の貴金属化合物の中から選ばれる化合物に
よる増感の終了後に行うことが好ましい。
本発明におけるコア/シェル型ハロゲン化銀粒子は沃化
銀含有率の異なる少なくとも2層から構成されている粒
子構造を有し、かつ該2層以上の層のうちの粒子表面に
おける沃化銀含有率が内部に比べて低いことが好ましい
。
上記コア/シェル型ハロゲン化銀粒子においては、沃化
銀含有率の高い層から含有率の低い層への含有率の差に
よる傾斜は、シャープな境界を有するものでもよく、ま
た、境界の必ずしも明白でない連続して変化するもので
あってもよい。
また、特願昭60−86659号に記載されるような複
数のNよりなる内部高沃化銀型コア/シェル乳剤が好ま
しい、コアはその一部(例えば製造における種粒子に相
当する部分等)に沃化銀含有率が小さい、あるいはOの
部分があっても差支えない、シェルの厚さはコアの好ま
しい素質を隠蔽せぬ厚さであり、かつ逆にフ7の好まし
からざる効果、素質を隠蔽するに足る厚みであることが
好ましい。
上記のコア/シェル型ハロゲン化銀粒子における沃化銀
の分布状態は、各種の物理的測定法によって検知するこ
とができ、例えば、日本写真学会、昭和56年度年次大
会講演要要旨上記載されているような低温でのルミネッ
センスを測定することによっても調べることができる。
上記のコア/シェル型ハロゲン化銀粒子を有するハロゲ
ン化銀乳剤は、単分散性のハロゲン化銀粒子をコアとし
て、これにシェルを被覆することによってSt造するこ
とが好ましい。
前記フ7の単分散性のハロゲン化銀粒子を製造するには
、pAgを一定に保ちながらグプルジェット法により所
望の大きさの粒子を得ることができ、例えば、単分散性
のハロゲン化銀乳剤は、特開昭54−48521号公報
に記載されている方法を適用することができる0例えば
、沃臭化カリウムーゼラチン水溶液とアンモニア性硝酸
銀水溶液とをハロデン化ffi種粒子を含むゼラチン水
溶液中に添加速度を粒子表面積の関数として時間を変化
させて添加する方法によって製造する。この際、添加速
度の時間関数、pH、pAg、温度等を適宜に選択する
ことにより、高度の単分散性のハロゲン化銀粒子を得る
ことができる。
上記のコア/シェル型ハロゲン化銀粒子の製造方法につ
いては、例えば、西独特許1,169,290号、英国
特許1,027,146号、特開昭57−154232
号、特公昭51−1417号等の記載を参照できる。
本発明に係るハロゲン化銀粒子は所望の波長域に光学的
に増感することができる。そ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、ツ
メチン色素、トリノ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3,397,080号、
同3,615.635号、同3,828゜964号、英
国特許1,195,302号、同1,242.588号
、同1,293.862号、西独特許(OLS) 2,
030,326号、同2,121.780号、特公昭4
3−4936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
6
本発明に係るハロゲン化銀粒子を含むハロゲン化銀乳剤
層のハロゲン化銀乳剤には、その製造工程、保存中ある
いは現像処理中のがXつの発生を防止し、あるいは写真
性能を安定化させる目的で化学熟成の終了時に種々の化
合物を含有させてもよい。
例えばアゾール類、例えばベンゾチアゾリウム塩、ニト
ロインダゾール類、ニトロベンズイミダゾール類、クロ
ロベンズイミダゾール類、ブロモベンズイミダゾール類
、メルカプトチアゾール類、メルカプトベンズイミダゾ
ール類、アミノトリアゾール類、ベンゾトリアゾール類
、ニトロベンゾトリ7ゾール類、メルカプトテトラゾー
ル類 (特に1−フェニル−5−メルカプトテトラゾー
ルなど、またメルカプトとリミノン類、メルカプトトリ
アノン類、例えばオキサゾリンチオンのようなチオケト
化合物、更には、ベンゼンチオスルフィン酸、ベンゼン
スルフィン酸、ベンゼンスルホン酸アミド、ハイドロキ
ノン誘導体、7ミ/7工ノール誘導体、没食子酸誘導体
、アスコルビン酸誘導体等のようなカブリ防止剤または
安定剤として知られた多くの化合物を加えることができ
る.これらの化合物は化学熟成時或いは塗布前に添加す
るのが好ましい。
本発明のハロゲン化銀乳剤層がバインダとして含有する
ゼラチンとしては通常の写真用ゼラチンが好ましいが、
ゼラチンのみならず誘導体ゼラチンも包含され、誘導体
ゼラチンとしては、ゼラチン酸無水物との反応生成物、
ゼラチンとイソシアネートとの反応生成物、或いはゼラ
チンと活性ハロゲン原子を有する化合物との反応生成物
等が包含される.ここにゼラチンとの反応に用いられる
酸無水物としては、例えば無水マレイン酸、無水7タル
酸、無水安息香酸、無水酢酸、無水イサト酸、無水フハ
ク酸等が含まれ、インシアネート化合物としては、例え
ばフェニルイソシアネート、p−ブロモフェニルイソン
アネート、p−クロロフェニルイソシアネー)、p−)
リルイソシアネート、p−ニトロフェニルイソシアネー
ト、ナフチルイソシアネート等を挙げることができる。
更に活性ハロゲン原子を有する化合物としては、例えば
ベンゼンスルホニルクロライド、p−メトキシベンゼン
スルホニルクロライド、p−7エ/キシベンゼンスルホ
ニルクロライド、p 7’ロモベンゼンスルホニルク
ロライド、p−トルエンスルホニルクロライド、m−二
トロベンゼンスルホニルクロライト、臆−スルホベンゾ
イルノクロライト、ナフタレン−β−スルボニルクロラ
イド、p−クロロベンゼンスルホニルクロライド、3−
二)O−4−7ミノベンゼンスルホニルクロライド、2
−カルボキシ−4−ブロモベンゼンスルホニルクロライ
ド、−一カルポキンベンゼンスルホニルクロライド、2
−アミ/−5−メチルベンゼンスルホニルクロライド、
7タリルクロライド、p−ニトロベンゾイルクコライド
、ペンゾイルクロライド、エチルクロロカーボネート、
70イルクロライド等が包含される。
本発明のハロゲン化銀乳剤層のバインダとして本発明の
効果を阻害しない範囲でゼラチン以外の親水性コロイド
例えばコロイド状アルブミン、寒天、アラビアゴム、デ
キストラン、アルギン酸、例えばアセチル含量19〜2
6%にまで加水分解されたセルロースアセテートの如き
セルロース誘導体、ポリアクリルアミド、イミド化ポリ
アクリル7ミド、カゼイン、例えばビニルアルコール−
ビニルシア/アセテートコポリマの如きウレタンカルボ
ン酸基またはシア/7セチル基を含むビニルアルコール
ポリマ、ポリビニルアルコール−ポリビニルピロリドン
、加水分解ポリビニルアセテート、蛋白質または飽和ア
シル化蛋白質とビニル基を有する七ツマとの重合で得ら
れるポリマ、ポリビニルビリノン、ポリビニルアミン、
ポリアミ/エチルメタクリレート、ポリエチレンイミン
等を使用することもできる。
本発明のハロゲン化銀乳剤層に使用するゼラチン硬膜剤
は、ゼラチンと反応して9A橋を起し、硬膜作用を呈す
る際副産物として、有機または無機の酸を発生すもので
ある。例元ばハロゲン化水素酸を放出する2、3−ノへ
ロデ/マレアルデヒド酸類(米国特許2,080,01
9号)、2,4−フクロローS−トリフノンX1t(米
国特許3,325.287号)、クロロトリ7ノン誘導
体(英国特許1,193,290号)、クロロトリ7ノ
ン環を側鎖に含むポリマー類(米国特許3,362゜8
27号、西独国特許公1ml、921,363号)、フ
クロ0フオスフオアマイド誘導体(英国特許974.7
23号、同1 、004 、658号)、ハロメチル誘
導体(英国特許990゜275号)7オス7オニトリル
クロライド誘導体(米国特許3,186,848号)、
或いは石炭酸誘導体を放出する2−7二ノキシー3−ハ
ロデノーマレアルデヒド酸の誘導体(英国特許1,19
2,775号)等であって、特に好ましくは下記一般式
(Vl)で表わされる化合物である。
以下余白
一般式(Vl)
N
式中、1土アルカリ金属原子を表わす。
これらゼラチン硬膜剤は、水、メタ/−ル、ツメチルフ
ォルムアミドその池水と混り合い、写真乳剤に害を与え
ない溶媒に溶かして、乳剤に塗布する前の任意−の段階
で添加する。これらの硬膜剤はゼラチンを含む塗布液中
のゼラチンの乾燥重量1−2に対し、好ましくは1〜1
00.程度添加することにより、適当な硬膜効果を与え
ることができ、更に5〜60gの範囲が最適である。
上記の硬膜剤の具体例としては次の如きものが挙げられ
る。
Ca) C/−C−COOI+C!−C−CI
IO
(1+) Br112Cco N11−CI!2−
CI!2Nil−COCll□Dr本発明のハロゲン化
銀乳剤層は上記硬膜剤と共に本発明の効果を阻害しない
範囲でその他の硬膜剤を併用することができる。その他
の硬膜剤としては、例えばホルムアルデヒド、グリオキ
ザール、グルタルアルデヒドの如きアルデヒド系化合物
、およびそれらの7セタールあるいは重亜硫酸ナトリウ
ム付加物のような誘導体化合物、メタンスルホン酸エス
テル系化合物、エポキシ系化合物、アジリジン系化合物
、マレイン酸イミド系化合物、活性ビニル系化合物、カ
ルボッイミド系化合物、インオキサゾール系化合物、N
−ノチロール系化合物、インシアネート系化合物、ある
いはクロム明ばん、硫酸ジルコニウム等の5![硬膜剤
を挙げることができる。
本発明のハロゲン化銀乳剤層には、塗布助剤、帯電防止
、スベリ性改良、乳化分散、接着防止及び写真性改良(
例えば現像促進、硬調化、増感)など種々の目的で種々
の公知の界面活性剤を含んでもよい。
すなわち、米国特許2,240.472号、同2,83
1,768号、同3,158.484号、同3,210
,191号、同3 、294 。
540号、同3,507,860号、英国特許1,01
2,495号、同1,022,878号、同1,179
,290号、同1,198,450号、米国特許2,7
39.891号、同2,823,123号、同1,17
9゜290号、同1,198.450号、同2,739
.891号、同2,823゜123号、同3,068.
101号、同3,415,649号、同3,866゜4
78号、同3,756,828号、英国特許1,397
.218号、同3,113,816号、同3,411.
413号、同3,473.174号、同3,345.9
74号、同3,726,683号、同3,843.36
8号、ベルイー特許731,126号、英国特許1,1
38.514号、同1,159,825号、同1,37
4,780号、米国特許2,271゜623号、同2,
288.226号、同2,944,900号、同3,2
35゜919号、同3,671,247号、同3,77
2,012号、同3,589゜906号、同3,686
.478号、同3,754,924号、西独出願公開(
OLS) 1,961,683号及び特開昭50−11
7414号、同50−59025号、特公昭40−37
8号、同40−379号、同43・13822号に記載
されている例えばサポニン(ステロイドP、)、アルキ
レンオキサイド誘導体(例えばポリエチレングリコール
、ポリエチレングリコール/ポリプロピレングリフール
縮合物、ポリエチレングリコールフルキルまたはフルキ
ルアリ・−ルエーテル類、ポリエチレングリフールエス
テル類、ポリエチレングリフールソルビタンエステル類
、ポリアルキレングリコールフルキルアミンまたはアミ
ド類、シリコーンのポリエチレンオキサイド付加物類)
、グリシドール誘導体(例えばフルケニルフハク酸ポリ
グリセリド、アルキルフェノールポリグリセリド)、多
価アルコールの脂肪酸エステル類、糖のフルキルエステ
ル類、同じくウレタン頚またはエーテル類などの非イオ
ン性界面活性剤、トリテルベメイド系サポニン、フルキ
ルカルボン酸塩、7ルキルベンゼンスルホンキル硫酸エ
ステル類、フルキルリン酸エステル類、N−7シルーN
−フルキルタウリン類、スルホコハク酸エステル類、ス
ルホフルキルポリオキシエチレンフルキルフェニルエー
テル類、ポリオキシエチレンフルキルリン酸エステル類
などのようなカルボキシ基、スルホ基、ホスホ基、硫酸
エステル基、リン酸エステル基等の酸性基を含むアニオ
ン界面活性剤、アミlpHM,7ミノフルキルスルホン
酸類、アミノアルキル硫酸またはリン酸エステル類、フ
ルキルベタイン類、アミンイミド類、アミンオキシド類
などの両性界面活性剤、フルキルアミン塩類、脂肪族或
いは芳香族第4級アンモニウム塩類、ピリジウム、イミ
ダゾリウムなどの複素環tjS4級アンモニウム塩類及
び脂肪族または複素環を含むスルホニウムまたはスルホ
ニウム塩類などのカチオン界面活性剤を用いることがで
きる。
本発明のハロゲン化銀乳剤層には、現像促進剤として、
前記の界面活性剤の他に西独出願公開(OLS) 2,
002,871号、同2,445,611号、同2,3
60,878号、英国特許1,352.196号などに
記載されているイミダゾール類、チオエーテル類、セレ
ノエーテル類などを含有してもよい。
また本発明をカラー用の感光材料に適用するには、本発
明に係わる赤感性、緑感性及び青感性の各ハロゲン化銀
乳剤層にシアン、マゼンタ及びイエローカプラなそれぞ
れ組合わ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く、カプラは分子中に
バラスト基とよばれる疎水基を有する非拡散性のものが
望ましい、カプラは銀イオンに対し4当量性あるいは2
当量性のどちらでもよい、また色補正の効果をもつカラ
ードカプラ、或いは現像にともなって現像抑制剤を放出
するカプラ (いわゆるDIRカプラ)を含んでもよい
、更にカプラはカップリング反応の生成物が無色である
ようなカプラでもよい。
黄色発色カプラとしては公知のIJ1111ケトメチレ
ン系カプラ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パロイルアセトアニリド系
化合物は有利である。用い得る黄色発色カプラの具体例
は米国特許2 、875 、057号、同3゜265.
506号、同3,408,194号、同3,551,1
55号、同3゜582.322号、同3,725,07
2号、同3,891,445号、西独特許1,547,
868号、西独出願公開(OLS) 2,213゜46
1号、同2,219.917号、同2.261,361
号、同2,414゜006号、同2,263,875号
などに記載されたものである。
マゼンタ発色カプラとしてはピラゾロン系化合物、イン
グゾロン呆化合物、シアノアセチル化合物などを用いる
ことができ、特にピラゾロン系化合物は有利である。用
い得るマゼンタ発色カプラの具体例は、米国特許2,6
00,788号、同2,983,608号、同3,06
2,653号、同3,127,269号、同39314
.476号、同3,419,391号、同3,519,
429号、同3,558.319号、同3,582.3
22号、同3,615.506号、同3,834゜90
8号3,891,445号、西独特許1,810.46
4号、西独出IEI 公II (QLS) 2−46
8,665+、同2,417.945号、同2,418
,959号、同2,424,467号、特公昭40−6
031号などに記載のものである。
シアン発色カプラとしてはフェノール系化合物、カブト
ール糸化合物などを泪いることができる。
その具体例は米国特許2,369,929号、同2,4
34,272号、同2,474,293号、同2,52
1.908号、同2,895.826号、同3,034
,892号、同3.3LL、476号、同3 、458
1315号、同3,476.563号、同3,583.
971号、同3,591゜383号、同3,767.4
11%、[L出願公開(OLS) 2゜414 、83
0号、同2,454,329号、特開昭4111−59
838号などに記載されたものである。
カラードカプラとしては例えば米国特許3.476゜5
60号、同2,521,908号、同3,034,89
2号、特公昭44−2016号、同38−22335号
、同42−11304号、同44−32461号、特願
昭49−98469号、同50−118029号、西独
出願公開(OLS) 2.418.959号に記載のも
のを使用できる。
[)IRカブラとしては、例えば米国特許3,227゜
554号、同3,817,291号、同3,701.7
83号、同3,790゜384号、同3,632,34
5号、西独出願公開(OLS)2.414,006号、
同2,454,301号、同2,454,329号、英
国特許953,454号、特願昭50−146570号
に記載されたものが使用でさる。
DIRカプラ以外に、現像にともなって現像抑制剤を放
出する化合物を、感光材料中i二含んでもよく、例えば
米国特許3,297,445号、同3,379,529
号、西独出願公開(OLS) 2,417,914号に
記載のものが使用できる。その他特閤昭55−8554
9号、同5フー94752号、同56−65134号、
同5B−135841号、同54−130716号、同
56−133734号、同56−135841号、米国
特許4.310.618号、英国特許2,083,64
0号、リサーチ・ディスクローツヤ18360 (19
79年)、14850 (1980年)、19033
(1980年)、19146 (1980年)、205
25(19旧年)、21728 (1982年)に記載
されたカプラも使用することができる。
上記のカプラは同一層に二種以上含むこともでさる。ま
た同一の化合物を異なる2つ以上の層に含んでもよい。
カプラをハロゲン化銀乳剤層に導入するには、公知の方
法例えば米国特許2,322,027号に記載の方法な
どが用いられる1例えば7タール酸フルキルエステル(
ジプチル7タレー)、ノオクチル7タレートなど)、リ
ン酸エステル(ジフェニルホス7z−)、)リフェニル
ホス7エート、トリフレノルホスフェート、ノオクチル
ブチルホス7エ−) )、クエン酸 エステル(例えば
7セチルクエン酸トリブチル)、安息香酸エステル(例
えば安息香酸オクチル)、アルキルアミド (例えばジ
エナルラウリルアミド)など、または沸点約30℃乃至
150°Cの有機溶媒、例えば酢酸エチル、酢酸ブチル
の如き低級アルキルアセテート、プロピオン酸エナル、
2級ブチルアルコール、メチルイソブチルケトン、β−
エトキシエチルアルキレンアセテート、メチルセロソル
ブアセテート等に溶解したのち、親水性コロイドに分散
される。上記の高沸点有磯溶牒と低沸点有機溶媒とを混
合して用いてもよい。
カブラがカルボン酸、スルホン酸の如き酸基を有する場
合には、アルカリ性水溶液として親水性コロイド中に導
入させる。
これらのカプラは、一般にノ10デン化銀乳剤層中の銀
1モル当り2X10−’モル乃至5X10一’モル、好
ましくはlXl0−2乃至5X10−’モル添加される
。
本発明に係る感光材料は色かぶり防止剤として、ハイド
ロキノン誘導体、アミ/フェノール講導体、没食子酸誘
導体、7スコルビン酸誘導体などを含有してもよ(、そ
の具体例は米国特許2,360.290号、同2 、3
36 、327、同2,403,721号、同2,41
8,613号、2,675,314号、同2,701,
197号、同2,704,713号、同、2 、728
、659号、同2,732,300号、同2.735
.765号、特開昭50,92988号、同50−92
989号、同50−93928号、同50−11033
7号、特公昭50−23813号等に記載されている。
4i′!電防止剤としてはノアセチルセルロース、スチ
レンーパーフルオロアルキルソノウムマレエ−F共重合
体、スチレン−無水マレイン酸共重合体と9−7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アクリル酸メチル、ポリ
スチレン及びアルカル可溶性ポリマーなどが挙げられる
。また更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Wとt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、グリフール系化合物
を挙げることができ、増結剤としてはスチレン−マレイ
ン酸ナトリウム共重合体、アルキルビニルエーテル−マ
レインa 共m 6体等が挙げられる。
本発明に係る感光材料の支持体としては、例乏ばバライ
タ紙、ポリエチレン被覆紙、ポリプロピレン合成紙、ガ
ラス板、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ィルム、
ポリスチレン等がありこれらの支持体はそれぞれの感光
材料の使用目的に応じて適宜選択される。
これらの支持体は必要に応じて下引加工がmされる。
本発明に係る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。
黒白現像液は、ヒドロキンベンゼン類、アミ77エ/−
ル類、アミ/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、臭化物及び沃化物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〃現像液で現像し、次いで白色露光を与えるか、或
いはカプ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イ?い
必要に応じてさらに水洗、安定処理を行う方式を適用す
ることができる。
本発明に係る感光材料は多くの用途に適用できる6例え
ば白黒一般用、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
用途に供し得る。
また多層カラー感光材料に適用する場合には、当該分野
でよく知られている種々の層hm成、すなわち順層、逆
層その池あらゆるNJ構成に適用できる。
r実施例]
以下、実施例を挙げて本発明を具体的に説明する。
実施例 1
下記の方法で比較用の8面体沃臭化銀乳剤EM−1およ
び(3:11)面を有する沃臭化銀7L削EM−2、な
らびに本発明の(331)面を有するコア/シエル型沃
臭化1a?lJllEM−3ヲ3sl L m。
(EM−1)
特開昭60−145440号記載の方法により単分散8
面体沃臭化銀乳剤を作成した。すなわち、40℃におい
てゼラチンと4−ヒドロキン−6−7チル−1.3.3
a、7−チトラザインデンの存在下で0.15μ噛の沃
央化銀種礼剤(沃化銀含有率4モル%)を含む溶液にア
ンモニア性硝酸銀水溶液と臭化カリウム沃化カリウムの
混合水溶液をコントロールドグプルジェット法により小
粒子発生のない最小時間を要して添加することにより製
造した。この添加の間、I)Agを9から10へ連続的
に変化させた。まrこ、添加硝酸銀に対する沃化カリウ
ムのモル比は8%とした。
次に、常法により脱塩した後、ゼラチンを加えて再溶解
した。電子顕微鏡観察の結果、EM−1は(111)結
晶面からなるほぼ完全な8面体粒子を含むものであった
。
(EM−2>
平均粒径0.40μ鋤の沃臭化銀粒子(沃化銀含有率4
モル%)0.29モルを含む乳剤を蒸留水1000m1
00O%アンモニア 30m1を含む)に分散させてか
ら、4−ヒドロキシ−6−メチル−1,3,3m、7−
チトラザインデンの存在下で、50°C1:おいて0.
47モル/lの硝酸銀水溶filooomZと必要十分
な臭化カリウムと沃化カリツムの混合水溶!(8モル%
の沃化カリウムを含む)とをコントロールダブルジェッ
ト法で特開昭61−83531号に記載される方法に従
って製造した。
次に、常法により脱塩したのち、ゼラチンを加えて再溶
解した。電子顕微tft観察の結果、EM−2は(:+
31)結晶面からなるほぼ完全な24面体を含むもので
あった。
(EM−3)
次に本発明のコア/シェル乳剤を特開昭61−8823
5号に示される方法に準じて製造した平均粒径0゜40
μ鴫の正8面体臭化銀粒子0.29モルを含む乳剤を蒸
留水1000m100O%アンモニア30m1を含む)
に分散させてから、4−ヒドロキシ−6−メチル−1,
3,3a17−チトラザインデンの存在下に、50℃に
おいて0.47モル/lの硝酸銀水溶液500纏lと必
要な臭化カリウムと沃化カリウムの混合水溶液(15モ
ル%の沃化カリツムを含む)とをコントロールダブルジ
ェット法で添加し、これにつづけて、0.47モル/l
の硝酸銀水溶9500I61と必要な臭化カリウムと沃
化カリウムの混合水?8液(2モル%の沃化カリウムを
含む)とをフントロールグプルノエット法で添加するこ
とにより作製した。
次に、常法に上り脱塩したのち、ゼラチンを加えて再溶
解した。こうして+111造したEM−3は内部に高沃
度殻をもつコア/シェル乳剤であり、電子顕微鏡観察の
結果、(:+31)結晶面から成るほぼ完全な菱形12
面体粒子を含むものであった。
上記EM−1〜EM−3の各々に対し常法に従って化学
増感を施し、更に後記増感色素■お上り■をハロゲン化
銀1モル当たり各々1,5X IF5および1、OX
10−Sモル添加して緑感性に分光増感した。
これらの乳剤に4−ヒrロキシ−6−メチル−1゜3.
3a、7−チトラザインデンをハロゲン化銀1モル当り
9,4X 10−’モルおよび1−フェニル−5−メル
カプテトラゾールをハロゲン化J!t1モル当り1.6
×10−4モル加乏て安定化した。
各試料は下引加工したセルローストリアセテート支持体
上に下記の各層を銀量が15TofI/d+o”になる
ように塗設した。
なお試料の各層の記載における成分の量は1m2当りの
量を示す。
第1層:
上記ハロゲン化凧乳削1.8g並びに0.20gの下記
マゼンタカプラMB−1および0,04!hの下記カラ
ードマゼンタカプラCM−1をi8Mした。(1,06
,のDNI’(ノターンヤリー/ニル7エ/−ル)分散
物を含有する高感度緑感性乳剤層。
ff≦2ノ(り:
0、15gの黄色コロイド銀、0.2yの汚染防止層を
溶解した。、tiyのDIIP(ノブチルテレフタレー
ト)分散物及び1.52のゼラチンを含有するイエロフ
ィルタ層。
B−1
I
M−1
Cσ
Ct’
上記第1NJおよび第271には上記添加剤の他に下記
硬膜剤H1および112を表1の通り添加した。添加量
はゼラチン1g当り111は8−g、+12は12Bで
ある。
l篭1
[(C112= CH30□CH2)3CC112SO
□CLCLI□NCHaCHzSOJ各試料は常法に従
いウェッジ露光し、下記処理工程で処理した。なお、熱
かぶりの測定試料はウェッジ露光の前に試料を65°C
1相対温度20%の条件で3日間保存した。
処理工程:
発色現像 3分15秒
漂白 6分30秒水洗
3分15秒定着
6分30秒水洗 3分15秒
安定化 1分30秒
乾燥
各処理工程において使用した処理液組成を下記に示す。
発色現像液
4−7ミノー3−メチル−N−(β−ヒドロキシエチル
)−アニリン・硫酸塩 4.75゜無水亜硫酸ナ
トリウム 4,259ヒドロキシルアミン
1/2硫酸塩 2.02無水炭酸カリウム
37.5゜臭化カリウム
1.3gニトリロトリ酢酸・3ナトリウム塩(1
水塩)2.52
水酸化カリウム t、og水を加え
て11とする。
漂白液
エチレンノアミンチトラ酢酸鉄アンモニウム塩100.
09
エチレンノアミンチトラ酢PI12アンモニウム塩10
.0g
臭化アンモニウム 150.0g水水酸
酸 10.O+aZ水を加え
て11とし、アンモニア水を用いてpH6,0に調整す
る。
定着液
チオ硫酸アンモニウム 175.0g無水亜
硫酸アンモニウム 8.697り亜硫酸ナト
リウム 2.3g水を加えてliとし、酢
酸を用いてpl(6,0):1層gする。
安定化液
ホk v ’J ン(37%水溶l) 1.
5@1コニダフクス(小西六写真工業株式会社製)7.
5+1
水を加えて11とする。
現像した試料はグリーン党を用いて感度およびかJ:r
)を測定した。
感度は特性曲線上でカプリ+0.1の点の感度であり、
試料No、 1の感度を100とする相対値で示した。
結果を表1に示す1表1において、熱かぷり:(前記の
高温保存を施した試料のが、JS’))−(前記の高温
保存をしない試料のかぶり)である、 、以下倉、百
++。
表1
表1から明らかなように、本発明に係る試料は比較試料
と比べて度が高く、かつ熱かぶりが少ない。
実施例2
前記EM−L〜εM−3に常法に従い化学増感を施し、
以下の様にして、青色感光層、緑色感光層および赤色感
光層の3種類の感光層を有する11層からなるカラー感
光材料を作製した。化学増感を施したEM−1〜EM−
3の乳剤は、緑感性高感度層(第5層)にのみおいて変
化させた。他の感光性層は各試料において全(共通の乳
剤を用いた。
下引き加工したセルローストリアセテートフィルム支持
体上に、下記のようなm成の各層からなる多層式カラー
感光材料を作製した。
Pt51層:ハレーション防止層
黒色コロイド銀を含むゼラチン層。
第2屑:中間層
2.5−L−オクチルハイドロキノンの乳化分散物を含
むゼラチン層。
第3層:低感度赤感性ハロゲン化銀乳剤層平均粒径(i
)0.30μ箇、八gl 6モル%を含むΔg[1r
lからなる単分散乳剤(乳剤り・・・・・・銀塗布量
1.897m2
増感色素! ・・・・・・銀1モルに対して 6X 1
0−’モル増患色索■ ・・・・・・ /#
1.0X10−’モルシアンカプラ(C−1)・
・・・・・
銀1モルに対して 0.06モル
カラードシアンカブラ(CC−1)・・・・・・銀1モ
ルに対して 0.003モル
DIR化合物(D−1)・・・・・・
銀II!!ルに対して 0.0015モル(D−2)・
・・・・・
銀1モルに対して 0.002モル
fi4層:高感度赤感性ハロゲン化銀乳剤層平均粒径(
”)0.5μm、八917.0モル%を含む八gUr
lからなる
単分散乳剤(乳剤■)・・・・・・銀塗布Jl 1.
3y/m”増感色素 I・・・・・・銀1モルに対して
3X 10−’モル■・・・・・・
1.OX 10”モルシアンカプラ(C−1)・・・
・・・
銀1モルに対して 0.03モル
1)IR化合物([1−2)・・・・・・銀1モルに対
して o−ooiモル
第5層:中間層((、L、)
第2層と同じゼラチン層。
16層:低感度緑感性ハロゲン化銀?LM層乳削 I
・・・・・・塗布銀量 1.5g/m”増感
色素■・・・・・・!Il1モルに対して2.5X 1
0−’モル■・・・・・・ 1.2
X 10−5モルマゼンタカプラ(M[1−1)・・・
・・・銀1モルに対して 0.045モル
カラードマゼンタカプラ(CM−1)・・・・・・銀1
モルに対して 0.009モル
[1[R化合物(El−1)・・・・・・銀1モルに対
して 0.0010モル
(D−3)・・・・・・
銀1モルに対して Q、QQ30モル
FA7層:高感度緑感性ハロゲン化銀乳剤層乳剤(EN
−1−EM−3)−・・・・−銀塗布i1 1,4y/
m”増感色素 ■・・・・・・銀1モルに対して1.5
X 10−’モル■・・・・・・ 1
.OX 10−’モルマゼンタカブラ(M[1−1)・
・・・・・銀1モルに対して0.030モル
DIR化合物(D−3)・・・ s O,
0010モル第8層:イエローフィルタ層
黄色コロイド銀と2.5−ノーt−オクチルハイドr:
Iキ/ンの乳化分散物とを含むゼラチン層。
第9M:低感度青感性ハロゲン化銀乳剤層平均粒径0.
48μs、Apl 6モル%を含む八28「lからな
る単分散乳剤(乳剤■)・・・・・・銀塗布量
0.9y/+o”
増感色素 V・・・・・・銀1モルに対して1.:lX
10−’モルイエローカプラ(Y−1)・・・・・・
銀1モルに対して 0.29モル
第10wJ:高感度青感性乳剤層
平均粒径0.8μI、^y115モル%を含む^yBr
lからなる単分散乳剤(乳剤■)・・・・・・銀塗布
量 0.597輸2
増感色素 ■・・・・・・銀1モルに対して1.OX
10−’モルイエローカプラ(Y−1)・・・・・・銀
1モルに対して 0.08モル
DIR化合物(D−2)・・・ 0.0
15モル第11層:第1保護層
沃央化m<N1モル%、平均粒径0,07μm)銀塗布
fl O,59/醜2紫外線吸収剤 uv−
1,UV−2を含むゼラチン層。
第1UI:第2保護層
ポリメチルクリレート粒子(直径1.5μ、)及びホル
マリンスカベンジャ(IIS−1>を含むゼラチン層。
尚各層には上記組成物の他に、ゼラチン硬膜剤(1!1
または112)および界面活性剤を添加した。
ゼラチン硬膜剤H1はゼラチン1g当たり8aAg、t
12の場合は12IIg添加した。
増感色素 I:アンヒドロー5.5′−フクロロー9−
エチル−3,3′−ノ(3−スルホプロピル)チアカル
ポジ7ニンヒドロキ
シド
増感色素 ■:7ンヒドロー9−エチルー3.3′−ジ
クロロ(3−スルホプロピル)−4,5゜4’、5’−
ノベンゾチアカルポシアニンヒドロキシド
■:アンヒドロー5,5′−ノフェニル−9−エチル−
3,3′−ノ(3−スルホプロピル)オキサカルボシア
ニンヒドロ
キシド
■:アンヒドロー9−3.3’−ノ(3−スルホプロピ
ル) −5,6,5’、6’−ジベンゾオキサカルボシ
アニンヒドロキンド
■:7ンヒドロ−3,3′−ノ(3−スルホプロピル)
−4,5−ベンゾ−5′−メトキシチアシアニン
以下余白
C−1:
n■
CC−1:
0(I
Y−1:
I
uv−i :
11V−2:
Its−1:
、n
I
D−1=
nl+
D−2=
D−3:
このようにした作製した多層式カラー惑尤材料誌料につ
いて実施例1と同様に熱がぶつの測定のための高温保存
を施し、常法に従い白色ウェッジ露光し、実施例1と同
様に緑色光を用いて感度、かよりおよび熱かよりを測定
した。結果を表2に示す。
以下余−°菖
表 2
表2から、多層式カラー写真感光材料においても、本発
明に係る試料は比較試料と比べて高感度でかつ熱かぶり
が少ないことがわかる。
【発明の効果1
本発明により、(331)結晶面を有する沃臭化銀乳剤
層を有するハロゲン化銀写真感光材料の熱がぶりおよび
重層減感が改良される。
従って、本発明に係るハロゲン化銀写真感光材料は高感
度でかつ熱かぶりが低い。The object of the present invention is to have a core/shell structure in which at least the grain surface is substantially made of silver iodobromide, has a (331) crystal face on the outer surface, and has a higher silver iodobromide content inside than the grain surface. and at least one silver halide emulsion layer containing gelatin as a binder and hardened with an organic hardener that reacts with the gelatin to release an organic or inorganic acid. This can be achieved using a silver halide photographic material. The present invention will be explained in detail below. The halogenated particles related to the present invention have a Miller index (331
) on the outer surface, and at least the surface of the grain consists essentially of silver bromide or silver iodobromide. In addition to the (331) surface, the particle has a (100) surface.
It is acceptable for planes, (lit) planes, (110) planes, etc. to exist, but it is preferable that the ratio of (331) i7i'i to the total surface area is 20% or more, particularly 80% or more. preferable. Furthermore, the presence of (331) planes and their proportion can be determined by a method using an electron microscope, an x#a diffraction method, or a dye adsorption method. The silver halide emulsion layer of the present invention preferably contains silver halide grains having (331) planes in an amount of 30% by weight or more, more preferably 50% by weight or more. In the composition of the halogenated grains according to the present invention, "consisting essentially of silver bromide or silver iodobromide" means silver halides other than silver bromide and silver iodobromide, as long as the effects of the present invention are not impaired. , meaning that it may contain, for example, silver chloride. Specifically, in the case of silver chloride, the ratio is preferably 5 mol% or less, more preferably 1 mol% or less -1. The proportion of silver iodide in the subhalogenated grains according to the present invention is preferably 0 to 40 mol%, more preferably 0 to 20 mol%, and particularly preferably 0 to 15 mol%. Even if the silver halide grains according to the present invention are silver halide grains of a single IF structure, they may be silver halide grains composed of a plurality of phases (for example, layers) having different halogen compositions (for example, core/
shell-type particles). When silver halide grains do not have a single silver halide composition, halogen inside the grain, llr& is silver chloride,
Silver chlorobromide or the like may also be used. Furthermore, the halogen composition within each phase may be uniform or may vary continuously. One of the most preferred forms is one with high iodine content inside the grains. That is, it is a silver halide grain having within the grain a phase (or phases) having a higher iodine content than the iodine content on the grain surface. Details of such a core/shell emulsion of the grain internal high silver iodide type having the (331) plane according to the present invention are described in JP-A-61-88235. In the case of such a core/el emulsion, the silver halide mra of the shell 7 preferably contains 3 to 40 mol % of silver iodide, and the silver halide mra of the shell 1 contains 0 to 10 mol % of silver iodide. The difference in silver iodide content between the shell and core is preferably 2 to 30 mol%.The change in silver iodide content at the core/shell boundary is as follows: It can be continuous, stepwise, etc. There are no particular restrictions on the grain size of the silver halide grains according to the present invention (preferably 0.1-3.
The present invention is at least effective within the range of 0μ countries. In addition,
In this specification, the grain size of silver halide refers to the length of one side of a parallelepiped that is equal to its volume. The silver halide grains according to the present invention are usually produced and used in a form dispersed in a dispersion medium such as gelatin, that is, in a form called an emulsion. 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. In order to produce silver halide grains having (331) planes according to the present invention, the method disclosed in JP-A-61-83531 can be used. That is, as a method for producing bromide grains or silver iodobromide grains having (331) planes, silver halide grains are produced by mixing a water-soluble salt solution and a water-soluble halide solution in the presence of a protective colloid. In the forming step, the 9AIF of the emulsion is controlled within the range of 8.0 to 9.5 during a period in which at least 30 mol% of the total silver halide is formed, and during this period, the following general formula ([ ), (■)
, (III) or (■) and a compound having a repeating unit represented by the following general formula (V). has been done. General formula (1) General formula (fl) General formula (ill) General formula (IV) General formula (
V) I5 -(-CI+, -C+- ■ In the formula, R11, R12 and I'l) may be the same or different, and each represents a hydrogen atom, a halogen atom, an ami7 group, a derivative of an ami7 group, a furkyl group, alkyl group derivative, aryl group, aryl group derivative, cycloalkyl group, cycloalkyl group derivative, mercapto group, mercapto group derivative or -CONII-R,, (R, is a hydrogen atom, Alkyl group, amide 7 group, alkyl group derivative,
Ami7 derivative, halogen atom, cycloalkyl group,
It represents a derivative of a cycloalkyl group, an aryl group, or an aryl group. ), RtS represents a hydrogen atom or an alkyl group; Formula (1), (II), (1) or (
1 obtained by removing one hydrogen atom from the compound represented by IV)
It represents a valent group (for example, one hydrogen atom removed from the R1-R13 or 011 moiety in the above general formulas (1) to (IV)), and J represents a divalent linking group. The amount of the crystal control compounds (1) to (V) to be added varies depending on the production conditions such as the desired silver halide grain size, emulsion temperature, pH, pAg, and silver iodide content. A range of 1 to 2 x 10"" moles of lO per mole is preferred. It should be noted that the tetrazaindene compound has the general formula (V
), the amount to be added is determined by the molar loss of the tetrazaindene moiety. Methods for adding the crystal control compounds (1) to (V) include a method in which they are added in advance to a protective colloid solution, a method in which they are added gradually as silver halide grains grow, and a method in which these are added in combination. In the method for producing silver halide grains according to the present invention, grains may be grown by using seed grains and growing phosphorus halide on their surfaces. In the method for producing silver halide grains according to the present invention, the step of producing silver halide to form halide ff1 grains is carried out at t3 in the presence of 7 ammonium 7, and double-noeting an ammoniacal silver nitrate aqueous solution and a halide aqueous solution. Preferably, it is added by a method. Further, in this particle r&dispersion process, it is preferable to add a silver and halide solution so that new crystal nuclei are not generated. The feature of this manufacturing method is that it can provide a silver halide emulsion with excellent monodispersity, as described in VF Bunsho No. 61-83531. The outline of the method for producing silver halide grains having (331) planes according to the present invention has been described above.
You can know this from book No. 1-83531 #I. The silver halide grains having (331) planes according to the present invention are produced by cadmium salts, zinc salts, lead salts, thallium salts, ilinium salts or their complex salts, rhodium salts or their complex salts, in the process of silver halide grain formation or physical ripening. complex salt,
Iron salts or complex salts thereof, gold salts or complex salts thereof, etc. may also be present. In order to remove soluble salts from the emulsion after precipitation or physical ripening, a nude water washing method in which gelatin is gelatinized may be used. sulfonic acid) or gelatin conductor (eg, acylated gelatin, carbamoylated gelatin, etc.) using a precipitation method (70 curage run method). Silver halide grains according to the invention are chemically sensitized. The conditions of the chemical ripening or chemical sensitization process, such as pH, C
There are no particular restrictions on IAIF, temperature, time, additives, etc., and it can be carried out under conditions commonly used in the industry. For chemical sensitization, sulfur sensitization method uses sulfur-containing compounds that can react with silver ions or active gelatin, selenium sensitization method uses selenium compounds, reduction sensitization method uses reducing substances, gold and other A noble metal sensitization method using a noble metal compound can be used alone or in combination. As the sulfur sensitizer, known ones can be used.
Examples include thiosulfate, allylthiolupamide, thiourea, allyl isothiocyanate, cystine, 9-)luenethiosulfonate, logenine, and the like. Others, U.S. Pat. No. 1,574. No. 944, No. 2.411), No. 689, No. 2,278,
No. 947, No. 2,728゜668, No. 3,501.3
No. 13, No. 3, No. 656, No. 955, West German Survey Publication (
OLS) No. 1,422,869, JP-A-58-249
Sulfur sensitizers described in No. 37, No. 55-45016, etc. can also be used. The amount of yellow sensitizer added is
The amount may be sufficient to effectively increase the sensitivity of the emulsion. This amount varies over a considerable range under various conditions such as the amount of nitrogen-containing bicyclic compound added, pl+, temperature, and the size of silver halide grains, but as a guide, it is approximately 10% per mole of ia halide. -1 mol to about to-' mol is preferred. Selenium sensitizers can be used instead of sulfur sensitizers, but examples of selenium sensitizers include aliphatic mole/cyanates such as allyl isoselenocyanate, selenoureas, selenoketones, mole/amides, etc. selenocarboxylic acids and esters, selenophosphates, diethylselenide, selenides such as diethylselenide, and the like can be used, and specific examples thereof can be found in US Pat.
No. 574,944, No. 1,602,592, No. 1,6
23.499. As with the sulfur sensitizer, the amount added varies over a wide range, but as a guide, approximately 10-
The amount is preferably about 1 mol to 10 −1 mol. In the present invention, as the gold sensitizer, various gold compounds can be used, whether the gold has a valence of +1 or +3. Typical examples include chloraurate, potassium chloroaurate,
Auric Trichlorai Y. Potassium auric thiocyanate, potassium iodoaurate, tetracyano auric acid, ammonium aurothiocyanate, pyridyl trichlorogold, and the like. The amount of gold sensitizer added varies depending on various conditions, but as a guide, it is about 10-7 to 10-7 mol per mol of silver halide.
Ranges up to 'molar are preferred. Preferred compounds that release gold ions from gold-gelatinate and promote ion-containing adsorption onto silver halide grains include R2MX and R3M'X. or M'X, (wherein R represents a hydrogen atom, ammonium group, or alkali metal atom, M represents pt or Pd,
M′ represents Ir or Rb, and X represents a halogen atom) Rh%Pd, Ir, pt¥
? complex salts are effective. Specific compounds include (NH4)zPLcL, (old +,
), PdCf4, 31rBrss (old 1.), R
hCe6-1211.0, etc., but particularly preferred is ammonium tetrachloropalladate (II) (
NIl, ), PdC14. The amount added is 10 to 10 in stoichiometric ratio (mole ratio) to the gold sensitizer.
A range of 100 times is preferred. The timing of addition may be at the start of chemical ripening, during ripening, or after the end of ripening, but preferably during chemical ripening, and particularly preferably at the same time as or before or after the addition of the gold sensitizer. In the present invention, reduction sensitization can also be used in combination. There are no particular limitations on the reducing agent, but known examples include stannous chloride, urea dioxide, hydranone derivatives, and polyamines. Reduction sensitization is performed during rR sensitization of halogenated 11 particles, but chalcodene sensitization, gold sensitization, Rh, Pd,
It is preferable to carry out the sensitization after completion of sensitization with a compound selected from noble metal compounds such as Ir and pt. The core/shell type silver halide grains in the present invention have a grain structure composed of at least two layers having different silver iodide contents, and the silver iodide content is present on the grain surface of the two or more layers. It is preferable that the rate is lower than that inside. In the above-mentioned core/shell type silver halide grains, the gradient due to the difference in content from a layer with a high silver iodide content to a layer with a low silver iodide content may have a sharp boundary, and the boundary may not necessarily be It may be something that changes continuously and is not obvious. In addition, an internal high silver iodide type core/shell emulsion consisting of a plurality of nitrogen atoms as described in Japanese Patent Application No. 60-86659 is preferable, and the core is a part of the emulsion (for example, a part corresponding to a seed grain in production). There is no problem even if the silver iodide content is small or there is an O part, and the thickness of the shell is such that it does not hide the favorable qualities of the core, and conversely, the unfavorable effects and qualities of the core are suppressed. It is preferable that the thickness is sufficient to hide it. The distribution state of silver iodide in the above-mentioned core/shell type silver halide grains can be detected by various physical measurement methods. This can also be investigated by measuring luminescence at low temperatures. The silver halide emulsion having the above-mentioned core/shell type silver halide grains is preferably manufactured by forming a monodisperse silver halide grain into a core by coating the core with a shell. In order to produce the monodisperse silver halide grains of F7 above, grains of a desired size can be obtained by the gupurujet method while keeping the pAg constant. For example, the monodisperse silver halide emulsion is For example, a potassium iodobromide-gelatin aqueous solution and an ammoniacal silver nitrate aqueous solution are added to a gelatin aqueous solution containing halide ffi seed particles. Produced by a method of varying rate of addition over time as a function of particle surface area. At this time, highly monodisperse silver halide grains can be obtained by appropriately selecting the time function of addition rate, pH, pAg, temperature, etc. Regarding the method for producing the above-mentioned core/shell type silver halide grains, for example, West German Patent No. 1,169,290, British Patent No. 1,027,146, and Japanese Patent Application Laid-open No. 154232/1989
Reference can be made to the descriptions in Japanese Patent Publication No. 51-1417, etc. The silver halide grains according to the present invention can be optically sensitized to a desired wavelength range. The optical sensitization method is not particularly limited, and for example, an optical sensitizer such as a cyanine dye such as a zeromethine dye, a monomethine dye, a tumetine dye, or a trinotine dye or an optical sensitizer such as a merocyanine dye is used alone or in combination (for example, supersensitization). Can be optically sensitized. Regarding these technologies, see U.S. Patent No. 2,688.545, U.S. Pat.
No. 3,615.635, No. 3,828°964, British Patent No. 1,195,302, No. 1,242.588, No. 1,293.862, West German Patent (OLS) 2,
No. 030,326, No. 2,121.780, Special Publication No. 4
It is also described in No. 3-4936, No. 44-14030, etc. The selection can be arbitrarily determined depending on the wavelength range to be sensitized, sensitivity, etc., and the purpose and use of the light-sensitive material.6 Silver halide of the silver halide emulsion layer containing silver halide grains according to the present invention. The emulsion may contain various compounds at the end of chemical ripening for the purpose of preventing the occurrence of X during its manufacturing process, storage or development, or for stabilizing photographic performance. For example, azoles such as benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzimidazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles, etc. 7zoles, mercaptotetrazoles (particularly 1-phenyl-5-mercaptotetrazole, etc.); also mercapto and liminones, mercaptotrianones, thioketo compounds such as oxazolinthione, and also benzenethiosulfinic acid, benzenesulfinic acid, Many compounds known as antifoggants or stabilizers can be added, such as benzenesulfonic acid amides, hydroquinone derivatives, 7-mi/7-ethanol derivatives, gallic acid derivatives, ascorbic acid derivatives, etc. These compounds It is preferable to add it during chemical ripening or before coating.As the gelatin contained as a binder in the silver halide emulsion layer of the present invention, ordinary photographic gelatin is preferable.
Not only gelatin but also derivative gelatin is included, and derivative gelatin includes reaction products with gelatin acid anhydride,
Included are reaction products between gelatin and isocyanate, or reaction products between gelatin and a compound having an active halogen atom. The acid anhydrides used in the reaction with gelatin include, for example, maleic anhydride, 7-talic anhydride, benzoic anhydride, acetic anhydride, isatoic anhydride, succinic anhydride, etc., and the incyanate compounds include: For example phenyl isocyanate, p-bromophenylisonanate, p-chlorophenylisocyanate), p-)
Examples include lylisocyanate, p-nitrophenyl isocyanate, naphthylisocyanate, and the like. Furthermore, examples of compounds having active halogen atoms include benzenesulfonyl chloride, p-methoxybenzenesulfonyl chloride, p-7e/xybenzenesulfonyl chloride, p7'lomobenzenesulfonyl chloride, p-toluenesulfonyl chloride, m-nitrobenzenesulfonyl chloride, Benzenesulfonyl chlorite, p-sulfobenzoylnochlorite, naphthalene-β-sulfonyl chloride, p-chlorobenzenesulfonyl chloride, 3-
2) O-4-7 minobenzenesulfonyl chloride, 2
-carboxy-4-bromobenzenesulfonyl chloride, -carpoquinbenzenesulfonyl chloride, 2
-ami/-5-methylbenzenesulfonyl chloride,
7thalyl chloride, p-nitrobenzoyl chloride, penzoyl chloride, ethyl chlorocarbonate,
70yl chloride and the like are included. As a binder for the silver halide emulsion layer of the present invention, hydrophilic colloids other than gelatin, such as colloidal albumin, agar, gum arabic, dextran, alginic acid, such as acetyl content of 19 to 2, within a range that does not impair the effects of the present invention.
Cellulose derivatives such as cellulose acetate hydrolyzed to 6%, polyacrylamide, imidized polyacryl 7mide, casein, e.g. vinyl alcohol-
Vinyl alcohol polymers containing urethane carboxylic acid groups or shea/7 cetyl groups such as vinyl shea/acetate copolymers, polyvinyl alcohol-polyvinylpyrrolidone, hydrolyzed polyvinyl acetate, polymerization of proteins or saturated acylated proteins with vinyl group-containing The resulting polymer, polyvinylbilinone, polyvinylamine,
Polyamide/ethyl methacrylate, polyethyleneimine, etc. can also be used. The gelatin hardener used in the silver halide emulsion layer of the present invention reacts with gelatin to form a 9A bridge and generates an organic or inorganic acid as a by-product when exhibiting a hardening effect. Examples include 2,3-noherode/malaldehyde acids that release hydrohalic acids (U.S. Pat. No. 2,080,01
No. 9), 2,4-fuchloroS-trifunone (U.S. Patent 3,362゜8
No. 27, West German Patent Publication 1ml, No. 921,363), Fukuro 0 Phosphoamide Derivative (British Patent No. 974.7)
23, 1,004, 658), halomethyl derivatives (British Patent No. 990°275), 7-male 7-onitrile chloride derivatives (US Pat. No. 3,186,848),
Alternatively, derivatives of 2-7dinoxy-3-halodenormalaldehyde acids releasing carbolic acid derivatives (UK Patent No. 1,19
No. 2,775), and particularly preferred are compounds represented by the following general formula (Vl). The blank space below represents the general formula (Vl) N where 1 represents an alkali metal atom. These gelatin hardeners can be mixed with water, methanol, trimethylformamide, or water, dissolved in a solvent that does not harm the photographic emulsion, and added at any stage before coating the emulsion. . These hardeners are preferably used in an amount of 1-1 to 1-2 dry weight of gelatin in the gelatin-containing coating solution.
00. An appropriate hardening effect can be provided by adding a certain amount, and the optimum amount is in the range of 5 to 60 g. Specific examples of the above-mentioned hardening agents include the following. Ca) C/-C-COOI+C! -C-CI
IO (1+) Br112Cco N11-CI! 2-
CI! 2Nil-COCll□Dr In the silver halide emulsion layer of the present invention, other hardeners may be used in combination with the above-mentioned hardener to the extent that the effects of the present invention are not impaired. Other hardening agents include aldehyde compounds such as formaldehyde, glyoxal, and glutaraldehyde, derivative compounds thereof such as 7-cetal or sodium bisulfite adducts, methanesulfonic acid ester compounds, epoxy compounds, and aziridine. type compounds, maleic acid imide type compounds, active vinyl type compounds, carboimide type compounds, inoxazole type compounds, N
-Notyrol compounds, incyanate compounds, chromium alum, zirconium sulfate, etc. 5! [Hardening agents can be mentioned.] The silver halide emulsion layer of the present invention contains coating aids, antistatic properties, smoothness improvement, emulsification dispersion, adhesion prevention, and photographic properties improvement (
For example, various known surfactants may be included for various purposes such as development acceleration, contrast enhancement, and sensitization. That is, U.S. Patent Nos. 2,240.472 and 2,83
No. 1,768, No. 3,158.484, No. 3,210
, No. 191, 3, 294. No. 540, No. 3,507,860, British Patent No. 1,01
No. 2,495, No. 1,022,878, No. 1,179
, No. 290, No. 1,198,450, U.S. Patent No. 2,7
39.891, 2,823,123, 1,17
9゜290, 1,198.450, 2,739
.. No. 891, No. 2,823゜123, No. 3,068.
No. 101, No. 3,415,649, No. 3,866゜4
No. 78, No. 3,756,828, British Patent No. 1,397
.. No. 218, No. 3,113,816, No. 3,411.
No. 413, No. 3,473.174, No. 3,345.9
No. 74, No. 3,726,683, No. 3,843.36
No. 8, Belly Patent No. 731,126, British Patent No. 1,1
38.514, 1,159,825, 1,37
No. 4,780, U.S. Patent No. 2,271゜623, No. 2,
No. 288.226, No. 2,944,900, No. 3,2
35゜919, 3,671,247, 3,77
No. 2,012, No. 3,589゜906, No. 3,686
.. No. 478, No. 3,754,924, West German Application Publication (
OLS) No. 1,961,683 and Japanese Unexamined Patent Publication No. 1983-11
No. 7414, No. 50-59025, Special Publication No. 40-37
8, No. 40-379, and No. 43.13822, such as saponin (steroid P), alkylene oxide derivatives (e.g., polyethylene glycol, polyethylene glycol/polypropylene glycol condensate, polyethylene glycol furkyl or furkylar). - ethers, polyethylene glyfur esters, polyethylene glyfur sorbitan esters, polyalkylene glycol furkylamines or amides, polyethylene oxide adducts of silicone)
, glycidol derivatives (e.g. flukenylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, furkyl esters of sugars, nonionic surfactants such as urethane necks or ethers, triterbemade saponins, Furkyl carboxylate, 7-rukylbenzenesulfonyl sulfate, furkyl phosphate ester, N-7silu-N
- Carboxy groups, sulfo groups, phospho groups, sulfate ester groups, phosphorus, such as furkyltaurines, sulfosuccinates, sulfofurkyl polyoxyethylene furkylphenyl ethers, polyoxyethylene furkyl phosphates, etc. Anionic surfactants containing acidic groups such as acid ester groups, amphoteric surfactants such as amylpHM, 7-minofurkylsulfonic acids, aminoalkyl sulfates or phosphoric acid esters, furkyl betaines, amine imides, and amine oxides. , furkylamine salts, aliphatic or aromatic quaternary ammonium salts, heterocyclic tjS quaternary ammonium salts such as pyridium, imidazolium, and sulfonium or sulfonium salts containing aliphatic or heterocyclic rings can be used. . In the silver halide emulsion layer of the present invention, as a development accelerator,
In addition to the surfactants mentioned above, OLS 2,
No. 002,871, No. 2,445,611, No. 2,3
It may also contain imidazoles, thioethers, selenoethers, etc., which are described in No. 60,878 and British Patent No. 1,352.196. In addition, in order to apply the present invention to a color photographic material, a combination of cyan, magenta and yellow couplers may be contained in each red-sensitive, green-sensitive and blue-sensitive silver halide emulsion layer according to the present invention. The method and materials used for photosensitive materials may be used; it is desirable that the coupler has a hydrophobic group called a ballast group in its molecule and is non-diffusive.
It may be either equivalence, or it may contain a colored coupler that has a color correction effect, or a coupler that releases a development inhibitor during development (so-called DIR coupler). A coupler such as . As the yellow coloring coupler, a known IJ1111 ketomethylene coupler can be used. Among these, benzoylacetanilide and piparoylacetanilide compounds are advantageous. Specific examples of yellow couplers that can be used are U.S. Pat.
No. 506, No. 3,408,194, No. 3,551,1
No. 55, No. 3゜582.322, No. 3,725,07
No. 2, No. 3,891,445, West German Patent No. 1,547,
No. 868, West German Publication (OLS) 2,213°46
No. 1, No. 2,219.917, No. 2.261,361
No. 2,414°006, No. 2,263,875, etc. As the magenta color-forming coupler, pyrazolone compounds, ingzolone compounds, cyanoacetyl compounds, etc. can be used, and pyrazolone compounds are particularly advantageous. Specific examples of magenta coloring couplers that can be used include U.S. Pat.
No. 00,788, No. 2,983,608, No. 3,06
No. 2,653, No. 3,127,269, No. 39314
.. No. 476, No. 3,419,391, No. 3,519,
No. 429, No. 3,558.319, No. 3,582.3
No. 22, No. 3,615.506, No. 3,834゜90
8 No. 3,891,445, West German Patent No. 1,810.46
No. 4, West German IEI Public II (QLS) 2-46
8,665+, 2,417.945, 2,418
, No. 959, No. 2,424,467, Special Publication No. 1977-6
This is described in No. 031, etc. As cyan coloring couplers, phenolic compounds, Kabutol thread compounds, etc. can be used. Specific examples include U.S. Patent Nos. 2,369,929 and 2,4.
No. 34,272, No. 2,474,293, No. 2,52
No. 1.908, No. 2,895.826, No. 3,034
, No. 892, No. 3.3LL, No. 476, No. 3, 458
No. 1315, No. 3,476.563, No. 3,583.
No. 971, No. 3,591゜383, No. 3,767.4
11%, [Publication of L Application (OLS) 2゜414, 83
No. 0, No. 2,454,329, JP-A-4111-59
This is described in No. 838, etc. As a colored coupler, for example, U.S. Patent No. 3.476゜5
No. 60, No. 2,521,908, No. 3,034,89
No. 2, Japanese Patent Publication No. 44-2016, Japanese Patent Publication No. 38-22335, Japanese Patent Publication No. 42-11304, Japanese Patent Application No. 44-32461, Japanese Patent Application No. 49-98469, Japanese Patent Application No. 50-118029, West German Publication (OLS) 2. 418.959 can be used. [) As the IR cover, for example, U.S. Pat. No. 3,227.554, U.S. Pat.
No. 83, No. 3,790°384, No. 3,632,34
No. 5, OLS No. 2.414,006,
Those described in Japanese Patent No. 2,454,301, Japanese Patent No. 2,454,329, British Patent No. 953,454, and Japanese Patent Application No. 146,570/1988 can be used. In addition to the DIR coupler, the light-sensitive material may also contain a compound that releases a development inhibitor upon development; for example, U.S. Pat.
No. 2,417,914 can be used. Other Tokuko Showa 55-8554
No. 9, No. 5 Hu 94752, No. 56-65134,
No. 5B-135841, No. 54-130716, No. 56-133734, No. 56-135841, U.S. Patent No. 4.310.618, British Patent No. 2,083,64
No. 0, Research Disclosure 18360 (19
79), 14850 (1980), 19033
(1980), 19146 (1980), 205
25 (19th year), 21728 (1982) can also be used. Two or more of the above couplers may be contained in the same layer. Further, the same compound may be contained in two or more different layers. To introduce the coupler into the silver halide emulsion layer, known methods such as those described in U.S. Pat. No. 2,322,027 can be used.
phosphoric acid esters (diphenylphos 7z-),) liphenyl phosphate 7ate, trifrenol phosphate, nooctyl 7-thale), citric acid esters (e.g. 7-cetyl tributyl citrate) , benzoic acid esters (e.g. octyl benzoate), alkylamides (e.g. dienal laurylamide), etc., or organic solvents with a boiling point of about 30°C to 150°C, such as lower alkyl acetates such as ethyl acetate, butyl acetate, enal propionate. ,
Secondary butyl alcohol, methyl isobutyl ketone, β-
After being dissolved in ethoxyethyl alkylene acetate, methyl cellosolve acetate, etc., it is dispersed in a hydrophilic colloid. The above-mentioned high boiling point organic solvent may be mixed with a low boiling point organic solvent. When Kabra has an acid group such as carboxylic acid or sulfonic acid, it is introduced into the hydrophilic colloid as an alkaline aqueous solution. These couplers are generally added in an amount of 2.times.10@-' moles to 5.times.10@-' moles, preferably 1.times.10@-2 to 5.times.10@-' moles per mole of silver in the silver dendenide emulsion layer. The light-sensitive material according to the present invention may contain a hydroquinone derivative, an ami/phenol conductor, a gallic acid derivative, a 7-scorbic acid derivative, etc. as a color cast preventive agent (specific examples thereof can be found in U.S. Pat. No. 2,360,290). No. 2, 3
36, 327, No. 2,403,721, No. 2,41
No. 8,613, No. 2,675,314, No. 2,701,
No. 197, No. 2,704,713, No. 2, 728
, No. 659, No. 2,732,300, No. 2.735
.. No. 765, JP-A No. 50,92988, JP-A No. 50-92
No. 989, No. 50-93928, No. 50-11033
No. 7, Japanese Patent Publication No. 50-23813, etc. 4i'! Effective antistatic agents include noacetylcellulose, styrene-perfluoroalkylsonium maleate-F copolymer, and alkali salts of reaction products of styrene-maleic anhydride copolymer and 9-7 minobenzenesulfonic acid. It is. Examples of matting agents include polymethyl methacrylate, polystyrene, and alkali-soluble polymers. Furthermore, it is also possible to use colloidal silicon oxide. The latex added to improve the physical properties of the film may include a copolymer of acrylic acid ester, vinyl ester W, and a monomer having an ethylene group (t). Examples of the gelatin plasticizer include glycerin and glyfur compounds, and examples of the binder include styrene-sodium maleate copolymer, alkyl vinyl ether-maleic a co-m6, and the like. Supports for the photosensitive material according to the present invention include, for example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper, glass plates, cellulose acetate, cellulose nitrate, polyvinyl acetal, polypropylene, polyester films such as polyethylene terephthalate, etc.
There are polystyrene and the like, and these supports are appropriately selected depending on the intended use of each photosensitive material. These supports are subjected to undercoat processing if necessary. After exposure, the photosensitive material according to the present invention can be developed by a commonly used known method. The black and white developer is hydroquinebenzene, Ami77E/-
It is an alkaline solution containing developing agents such as metals, aminos/benzenes, and other alkali metal salts such as sulfites, carbonates,
May include bisulfites, bromides and iodides. Further, when the light-sensitive material is for color use, color development can be carried out by a commonly used color development method. In the reversal method, the image is first developed with a black-and-white developer, then exposed to white light or treated with a bath containing a capri agent, and then color developed 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, typical methods include a method in which bleach-fixing is performed after color development, followed by further washing and stabilization treatment if necessary, or a method in which bleaching and fixing are separated after color development. If necessary, a method of further washing with water and stabilizing treatment can be applied. The photosensitive material according to the present invention can be applied to many uses, such as black and white general use, X-ray use, color use, infrared use, micro use, silver dye bleaching method, reversal use, diffusion transfer method use, etc. It can be used for Further, when applied to multilayer color light-sensitive materials, the present invention can be applied to various layer configurations well known in the art, ie, normal layer, reverse layer, and any NJ configuration. rExample] The present invention will be specifically described below with reference to Examples. Example 1 Comparative octahedral silver iodobromide emulsions EM-1 and silver iodobromide 7L polished EM-2 having a (3:11) plane, and a core having a (331) plane of the present invention were prepared by the following method. / Shell type iodobromide 1a? lJllEM-3wo3sl L m. (EM-1) Monodispersed 8 by the method described in JP-A-60-145440
A hedral silver iodobromide emulsion was prepared. That is, gelatin and 4-hydroquine-6-7thyl-1.3.3 at 40°C.
a. In the presence of 7-chitrazaindene, a mixed aqueous solution of ammoniacal silver nitrate and potassium bromide potassium iodide was added to a solution containing 0.15 micron grains of silver iodide seed (silver iodide content: 4 mol%). It was manufactured by adding using a controlled dog pull jet method, requiring a minimum amount of time without generating small particles. During this addition, I) Ag was changed continuously from 9 to 10. The molar ratio of potassium iodide to added silver nitrate was 8%. Next, after desalting by a conventional method, gelatin was added and redissolved. As a result of electron microscopic observation, EM-1 contained almost perfect octahedral grains consisting of (111) crystal faces. (EM-2> Silver iodobromide grains with an average grain size of 0.40μ (silver iodide content 4
The emulsion containing 0.29 mol (mol%) was added to 1000 ml of distilled water.
4-hydroxy-6-methyl-1,3,3m,7-
In the presence of citrazaindene, at 50°C 1:0.
A mixed aqueous solution of 47 mol/l silver nitrate aqueous solution filooomZ and necessary and sufficient potassium bromide and potassium iodide! (8 mol%
(containing potassium iodide) was produced by a controlled double jet method according to the method described in JP-A-61-83531. Next, after desalting by a conventional method, gelatin was added and redissolved. As a result of electron microscopy TFT observation, EM-2 is (:+
31) It contained an almost perfect icosahedron consisting of crystal planes. (EM-3) Next, the core/shell emulsion of the present invention was prepared in JP-A-61-8823.
Average particle size 0°40 manufactured according to the method shown in No. 5
An emulsion containing 0.29 mol of μ-octahedral silver bromide grains (1000 ml of distilled water, 1000% ammonia (containing 30 ml))
4-hydroxy-6-methyl-1,
In the presence of 3,3a17-chitrazaindene, 500 liters of a 0.47 mol/l silver nitrate aqueous solution and the necessary mixed aqueous solution of potassium bromide and potassium iodide (containing 15 mol% potassium iodide) at 50°C. was added by controlled double jet method, followed by addition of 0.47 mol/l.
Aqueous solution of silver nitrate 9500I61 and the necessary potassium bromide and potassium iodide mixed water? 8 liquid (containing 2 mol % potassium iodide) was added by the Funtrorugpurnoet method. Next, after desalting in a conventional manner, gelatin was added and redissolved. EM-3 created in this way is a core/shell emulsion with a high iodine shell inside, and as a result of electron microscopy observation, it has an almost perfect rhombic shape consisting of (:+31) crystal planes.
It contained facepiece particles. Chemical sensitization was applied to each of the above EM-1 to EM-3 in accordance with a conventional method, and the sensitizing dye (as described below) was added at 1,5X IF5 and 1,OX, respectively, per mole of silver halide.
Spectral sensitization to green sensitivity was achieved by adding 10-S mol. These emulsions contain 4-hydroxy-6-methyl-1°3.
3a,7-thitrazaindene at 9,4X 10-' mole per mole of silver halide and 1-phenyl-5-mercaptetrazole at J! 1.6 per mole of t
It was stabilized by adding 10-4 mol. Each sample was coated with the following layers on a subbed cellulose triacetate support so that the silver amount was 15 TofI/d+o''.The amounts of components in the description of each layer of the sample indicate the amounts per 1 m2. 1st layer: 1.8 g of the above halogenated kite milk, 0.20 g of the following magenta coupler MB-1, and 0.04!h of the following colored magenta coupler CM-1 were subjected to i8M. (1,06
, a high-sensitivity green-sensitive emulsion layer containing a DNI' (Notan Yary/Nil 7 E/L) dispersion. ff≦2 (ri: 0, 15g of yellow colloidal silver, 0.2y of anti-fouling layer dissolved. Yellow filter layer containing TIy of DIIP (butyl terephthalate) dispersion and 1.52g of gelatin. B-1 I M-1 Cσ Ct' In addition to the above additives, hardening agents H1 and 112 below were added to the above No. 1 NJ and No. 271 as shown in Table 1. The amount of 111 added was 8-g per 1 g of gelatin. , +12 is 12B. l basket 1 [(C112= CH30□CH2)3CC112SO
□CLCLI□NCHaCHzSOJ Each sample was subjected to wedge exposure according to a conventional method and processed through the following processing steps. For the measurement of heat fog, the sample was heated to 65°C before wedge exposure.
It was stored for 3 days under conditions of 1 relative temperature and 20%. Processing steps: Color development, bleaching for 3 minutes and 15 seconds, washing with water for 6 minutes and 30 seconds
Fixed for 3 minutes and 15 seconds
Washing with water for 6 minutes and 30 seconds Stabilization for 3 minutes and 15 seconds Drying for 1 minute and 30 seconds The composition of the treatment liquid used in each treatment step is shown below. Color developer 4-7 Minnow 3-methyl-N-(β-hydroxyethyl)-aniline sulfate 4.75° Anhydrous sodium sulfite 4,259 Hydroxylamine 1/2 sulfate 2.02 Anhydrous potassium carbonate
37.5゜Potassium Bromide
1.3g nitrilotriacetic acid trisodium salt (1
Water salt) 2.52 Potassium hydroxide Add t, og water to make 11. Bleach solution ethylenenoamine titraacetic acid iron ammonium salt 100.
09 Ethylenenoamine chitra vinegar PI12 ammonium salt 10
.. 0g Ammonium bromide 150.0g Hydroxylic acid 10. The pH was adjusted to 11 by adding O+aZ water, and the pH was adjusted to 6.0 using ammonia water. Fixer Ammonium thiosulfate 175.0g Anhydrous ammonium sulfite 8.697 Sodium sulfite 2.3g Water was added to make li, and acetic acid was used to prepare 1 layer of pl(6,0). Stabilizing liquid k v 'J (37% aqueous solution) 1.
5@1 Konidafukusu (manufactured by Konishiroku Photo Industry Co., Ltd.) 7.
5+1 Add water to make 11. The developed samples were tested for sensitivity and
) was measured. Sensitivity is the sensitivity at the point of Capri +0.1 on the characteristic curve,
The sensitivity is expressed as a relative value with the sensitivity of sample No. 1 as 100. The results are shown in Table 1. In Table 1, thermal fog: (JS' for the sample subjected to the above-mentioned high-temperature preservation) - (fogging for the sample not subjected to the above-mentioned high-temperature preservation). One hundred++. Table 1 As is clear from Table 1, the samples according to the present invention have a higher degree of heat generation and less heat fog than the comparative samples. Example 2 The EM-L to εM-3 were subjected to chemical sensitization according to a conventional method,
A color photosensitive material consisting of 11 layers having three types of photosensitive layers: a blue photosensitive layer, a green photosensitive layer, and a red photosensitive layer was prepared in the following manner. EM-1 to EM- subjected to chemical sensitization
Emulsion No. 3 was changed only in the green-sensitive high-speed layer (fifth layer). All of the other photosensitive layers in each sample were the same (a common emulsion was used). A multilayer color photosensitive material consisting of each layer of the following composition was prepared on a subbed cellulose triacetate film support. Pt51 Layer: Antihalation layer Gelatin layer containing black colloidal silver.Second scrap: Intermediate layer gelatin layer containing an emulsified dispersion of 2.5-L-octylhydroquinone.Third layer: Low-sensitivity red-sensitive silver halide emulsion layer average Particle size (i
)0.30μ, 8gl 6mol% Δg[1r
Monodispersed emulsion (emulsion...silver coating amount) consisting of
1.897m2 Sensitizing dye!・・・・・・6X 1 for 1 mole of silver
0-'molar increase in color cord■ ・・・・・・/#
1.0X10-'Morsian coupler (C-1)・
... 0.06 mol per mol of silver Colored cyankabra (CC-1) 0.003 mol DIR compound (D-1) per 1 mol of silver ... Silver II! ! 0.0015 mol (D-2)・
... 0.002 mol per mol of silver fi4 layer: high sensitivity red-sensitive silver halide emulsion layer average grain size (
”) 0.5μm, 8gUr containing 8917.0 mol%
Monodispersed emulsion (emulsion ■) consisting of L... Silver coating Jl 1.
3y/m" Sensitizing dye I...3X 10-' mol per 1 mol of silver■...
1. OX 10” Morcian coupler (C-1)...
... 0.03 mol per mol of silver 1) IR compound ([1-2) ... o-ooi mol per mol of silver 5th layer: Intermediate layer ((, L, ) Gelatin layer same as 2nd layer. 16th layer: Low sensitivity green sensitive silver halide?LM layer milking I
...Amount of coated silver 1.5g/m" Sensitizing dye ■...!2.5X 1 per mole of Il
0-'mol ■・・・・・・ 1.2
X 10-5 mole magenta coupler (M[1-1)...
...0.045 mol colored magenta coupler (CM-1) for 1 mol of silver...1 silver
Per mole 0.009 mol [1[R compound (El-1)...... per 1 mol of silver 0.0010 mol (D-3)...... per 1 mol of silver Q, QQ30 mol FA7 layer: high sensitivity green sensitive silver halide emulsion layer emulsion (EN
-1-EM-3) --- Silver coating i1 1,4y/
m” sensitizing dye ■・・・・・・1.5 per mole of silver
X 10-'mol ■・・・・・・ 1
.. OX 10-'Mor Magenta Cabra (M[1-1)・
...0.030 mol DIR compound (D-3) per 1 mol of silver... s O,
0010 mol 8th layer: yellow filter layer yellow colloidal silver and 2.5-note t-octylhydride r:
A gelatin layer comprising an emulsified dispersion of I/Kin. 9th M: Low-speed blue-sensitive silver halide emulsion layer average grain size 0.
48 μs, monodispersed emulsion (emulsion ■) consisting of 828 liters containing 6 mol% of Apl... Silver coating amount
0.9y/+o” Sensitizing dye V...1.:lX per mole of silver
10-' mole yellow coupler (Y-1)...
0.29 mol per mol of silver 10th wJ: High sensitivity blue-sensitive emulsion layer average grain size 0.8 μI, containing 115 mol % of Br
Monodispersed emulsion (emulsion ■) consisting of 1. Silver coating amount 0.597 x 2 Sensitizing dye ■...1. OX
10-' mol Yellow coupler (Y-1)...0.08 mol per 1 mol of silver DIR compound (D-2)... 0.0
15 mol 11th layer: 1st protective layer iodine m<N1 mol%, average particle size 0.07 μm) Silver coating fl O, 59/Ugly 2 UV absorber uv-
1. Gelatin layer containing UV-2. 1st UI: second protective layer gelatin layer containing polymethyl acrylate particles (diameter 1.5μ) and formalin scavenger (IIS-1>).In addition to the above composition, each layer also contains a gelatin hardener (1.5 μm in diameter). !1
or 112) and a surfactant were added. Gelatin hardener H1 contains 8aAg per gram of gelatin, t
In the case of 12, 12IIg was added. Sensitizing dye I: Anhydro 5.5'-Fucloro 9-
Ethyl-3,3'-no(3-sulfopropyl)thiacarposi7ine hydroxide sensitizing dye '−
Nobenzothiacarpocyanine hydroxide ■: Anhydro 5,5'-nophenyl-9-ethyl-
3,3'-no(3-sulfopropyl)oxacarbocyanine hydroxide■: Anhydro9-3,3'-no(3-sulfopropyl)-5,6,5',6'-dibenzoxacarbocyanine hydroxide 7-hydro-3,3'-no(3-sulfopropyl)
-4,5-benzo-5'-methoxythiacyanine Below margin C-1: n CC-1: 0 (I Y-1: I uv-i: 11V-2: Its-1: , n I D- 1=nl+D-2=D-3: The thus produced multilayer color speculative material was stored at a high temperature for measurement of heat in the same manner as in Example 1, and a white wedge was prepared according to a conventional method. The sensitivity, brightness, and thermal brightness were measured using green light in the same manner as in Example 1. The results are shown in Table 2. It can also be seen that the sample according to the present invention has higher sensitivity and less thermal fog than the comparative sample. Thermal fog and multilayer desensitization of the silver halide photographic light-sensitive material are improved. Therefore, the silver halide photographic light-sensitive material according to the present invention has high sensitivity and low heat fog.
Claims (1)
になり、(331)結晶面を外表面に有し、粒子表面よ
り内部の沃化銀含有率が高いコア/シェル構造を有する
ハロゲン化銀粒子、および結合剤としてゼラチンを含有
し、ゼラチンと反応して有機または無機酸を放出する有
機の硬膜剤によって硬化された少なくとも1層のハロゲ
ン化銀乳剤層を有することを特徴とするハロゲン化銀写
真感光材料。At least the grain surface consists essentially of silver bromide or silver iodobromide, has a (331) crystal plane on the outer surface, and has a core/shell structure with a higher silver iodide content inside than the grain surface. A halogen containing silver particles and at least one silver halide emulsion layer containing gelatin as a binder and hardened with an organic hardener that reacts with the gelatin to release an organic or inorganic acid. Silver chemical photographic material.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP17066386A JPH0719040B2 (en) | 1986-07-18 | 1986-07-18 | Silver halide photographic light-sensitive material |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP17066386A JPH0719040B2 (en) | 1986-07-18 | 1986-07-18 | Silver halide photographic light-sensitive material |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS6326651A true JPS6326651A (en) | 1988-02-04 |
JPH0719040B2 JPH0719040B2 (en) | 1995-03-06 |
Family
ID=15909065
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP17066386A Expired - Lifetime JPH0719040B2 (en) | 1986-07-18 | 1986-07-18 | Silver halide photographic light-sensitive material |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0719040B2 (en) |
-
1986
- 1986-07-18 JP JP17066386A patent/JPH0719040B2/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
JPH0719040B2 (en) | 1995-03-06 |
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