JPS63249142A - Silver halide photographic sensitive material with reduced uneven development - Google Patents
Silver halide photographic sensitive material with reduced uneven developmentInfo
- Publication number
- JPS63249142A JPS63249142A JP8351787A JP8351787A JPS63249142A JP S63249142 A JPS63249142 A JP S63249142A JP 8351787 A JP8351787 A JP 8351787A JP 8351787 A JP8351787 A JP 8351787A JP S63249142 A JPS63249142 A JP S63249142A
- Authority
- JP
- Japan
- Prior art keywords
- group
- silver halide
- atom
- layer
- general formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000463 material Substances 0.000 title claims abstract description 36
- -1 Silver halide Chemical class 0.000 title claims description 79
- 229910052709 silver Inorganic materials 0.000 title claims description 49
- 239000004332 silver Substances 0.000 title claims description 49
- 238000011161 development Methods 0.000 title description 35
- 239000000839 emulsion Substances 0.000 claims abstract description 29
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 10
- 125000003396 thiol group Chemical group [H]S* 0.000 claims abstract description 6
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 5
- 125000004430 oxygen atom Chemical group O* 0.000 claims abstract description 5
- 125000003277 amino group Chemical group 0.000 claims abstract description 4
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 3
- 150000001875 compounds Chemical class 0.000 claims description 23
- 239000000084 colloidal system Substances 0.000 claims description 17
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 3
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 3
- 125000004448 alkyl carbonyl group Chemical group 0.000 claims description 2
- 125000000304 alkynyl group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 claims description 2
- 239000002253 acid Substances 0.000 abstract description 10
- 125000000129 anionic group Chemical group 0.000 abstract description 3
- 229910052736 halogen Inorganic materials 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract 1
- 150000001721 carbon Chemical group 0.000 abstract 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 53
- 238000000034 method Methods 0.000 description 22
- 150000001450 anions Chemical class 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 9
- 108010010803 Gelatin Proteins 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- 229920000159 gelatin Polymers 0.000 description 8
- 239000008273 gelatin Substances 0.000 description 8
- 235000019322 gelatine Nutrition 0.000 description 8
- 235000011852 gelatine desserts Nutrition 0.000 description 8
- 239000011241 protective layer Substances 0.000 description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- SJOOOZPMQAWAOP-UHFFFAOYSA-N [Ag].BrCl Chemical compound [Ag].BrCl SJOOOZPMQAWAOP-UHFFFAOYSA-N 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 125000003831 tetrazolyl group Chemical group 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- WSGURAYTCUVDQL-UHFFFAOYSA-N 5-nitro-1h-indazole Chemical compound [O-][N+](=O)C1=CC=C2NN=CC2=C1 WSGURAYTCUVDQL-UHFFFAOYSA-N 0.000 description 3
- ORZRMRUXSPNQQL-UHFFFAOYSA-N 6-nitro-1h-indazole Chemical compound [O-][N+](=O)C1=CC=C2C=NNC2=C1 ORZRMRUXSPNQQL-UHFFFAOYSA-N 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 150000002334 glycols Chemical class 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical compound C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 description 2
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 2
- MXWSQZWVKUTEEI-UHFFFAOYSA-N 1h-indazole-5-sulfonic acid Chemical compound OS(=O)(=O)C1=CC=C2NN=CC2=C1 MXWSQZWVKUTEEI-UHFFFAOYSA-N 0.000 description 2
- LLOAINVMNYBDNR-UHFFFAOYSA-N 2-sulfanylidene-1,3-dihydrobenzimidazole-5-sulfonic acid Chemical compound OS(=O)(=O)C1=CC=C2NC(=S)NC2=C1 LLOAINVMNYBDNR-UHFFFAOYSA-N 0.000 description 2
- CIULAVLZOPPVFP-UHFFFAOYSA-N 2H-benzotriazole-5-thiol Chemical compound SC1=CC=C2NN=NC2=C1 CIULAVLZOPPVFP-UHFFFAOYSA-N 0.000 description 2
- XSFHICWNEBCMNN-UHFFFAOYSA-N 2h-benzotriazol-5-amine Chemical compound NC1=CC=C2NN=NC2=C1 XSFHICWNEBCMNN-UHFFFAOYSA-N 0.000 description 2
- KFJDQPJLANOOOB-UHFFFAOYSA-N 2h-benzotriazole-4-carboxylic acid Chemical compound OC(=O)C1=CC=CC2=NNN=C12 KFJDQPJLANOOOB-UHFFFAOYSA-N 0.000 description 2
- OEBMOZBCDOBXAN-UHFFFAOYSA-N 2h-benzotriazole-5-carbonitrile Chemical compound C1=C(C#N)C=CC2=NNN=C21 OEBMOZBCDOBXAN-UHFFFAOYSA-N 0.000 description 2
- PZBQVZFITSVHAW-UHFFFAOYSA-N 5-chloro-2h-benzotriazole Chemical compound C1=C(Cl)C=CC2=NNN=C21 PZBQVZFITSVHAW-UHFFFAOYSA-N 0.000 description 2
- YTSAIZQULMWART-UHFFFAOYSA-N 5-ethoxy-2h-benzotriazole Chemical compound C1=C(OCC)C=CC2=NNN=C21 YTSAIZQULMWART-UHFFFAOYSA-N 0.000 description 2
- ZWTWLIOPZJFEOO-UHFFFAOYSA-N 5-ethyl-2h-benzotriazole Chemical compound C1=C(CC)C=CC2=NNN=C21 ZWTWLIOPZJFEOO-UHFFFAOYSA-N 0.000 description 2
- SUPSFAUIWDRKKZ-UHFFFAOYSA-N 5-methoxy-2h-benzotriazole Chemical compound C1=C(OC)C=CC2=NNN=C21 SUPSFAUIWDRKKZ-UHFFFAOYSA-N 0.000 description 2
- AOCDQWRMYHJTMY-UHFFFAOYSA-N 5-nitro-2h-benzotriazole Chemical compound C1=C([N+](=O)[O-])C=CC2=NNN=C21 AOCDQWRMYHJTMY-UHFFFAOYSA-N 0.000 description 2
- NKLOLMQJDLMZRE-UHFFFAOYSA-N 6-chloro-1h-benzimidazole Chemical compound ClC1=CC=C2N=CNC2=C1 NKLOLMQJDLMZRE-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000012964 benzotriazole Substances 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- 150000007522 mineralic acids Chemical group 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000003755 preservative agent Substances 0.000 description 2
- 230000002335 preservative effect Effects 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 230000001235 sensitizing effect Effects 0.000 description 2
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 150000003460 sulfonic acids Chemical class 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- FLFWJIBUZQARMD-UHFFFAOYSA-N 2-mercapto-1,3-benzoxazole Chemical compound C1=CC=C2OC(S)=NC2=C1 FLFWJIBUZQARMD-UHFFFAOYSA-N 0.000 description 1
- VXLKZBRLFFGAQT-UHFFFAOYSA-N 3h-benzimidazole-5-sulfonic acid Chemical compound OS(=O)(=O)C1=CC=C2N=CNC2=C1 VXLKZBRLFFGAQT-UHFFFAOYSA-N 0.000 description 1
- LRUDIIUSNGCQKF-UHFFFAOYSA-N 5-methyl-1H-benzotriazole Chemical compound C1=C(C)C=CC2=NNN=C21 LRUDIIUSNGCQKF-UHFFFAOYSA-N 0.000 description 1
- ILMHAGCURJPNRZ-UHFFFAOYSA-N 6-methoxy-1h-benzimidazole Chemical compound COC1=CC=C2N=CNC2=C1 ILMHAGCURJPNRZ-UHFFFAOYSA-N 0.000 description 1
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 208000019901 Anxiety disease Diseases 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-UHFFFAOYSA-N Hydrogen atom Chemical compound [H] YZCKVEUIGOORGS-UHFFFAOYSA-N 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 238000001016 Ostwald ripening Methods 0.000 description 1
- 102100040160 Rabankyrin-5 Human genes 0.000 description 1
- 101710086049 Rabankyrin-5 Proteins 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 125000004442 acylamino group Chemical group 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- 125000005035 acylthio group Chemical group 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical group 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical group 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 230000036506 anxiety Effects 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- TUZBYYLVVXPEMA-UHFFFAOYSA-N butyl prop-2-enoate;styrene Chemical compound C=CC1=CC=CC=C1.CCCCOC(=O)C=C TUZBYYLVVXPEMA-UHFFFAOYSA-N 0.000 description 1
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- UVSNFZAOYHOOJO-UHFFFAOYSA-N chembl1343456 Chemical compound OC1=CC=C2N=NNC2=C1 UVSNFZAOYHOOJO-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000000586 desensitisation Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229940043264 dodecyl sulfate Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 description 1
- 235000019252 potassium sulphite Nutrition 0.000 description 1
- 229930182490 saponin Natural products 0.000 description 1
- 235000017709 saponins Nutrition 0.000 description 1
- 150000007949 saponins Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000001953 sensory effect Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- ZDQYSKICYIVCPN-UHFFFAOYSA-L sodium succinate (anhydrous) Chemical compound [Na+].[Na+].[O-]C(=O)CCC([O-])=O ZDQYSKICYIVCPN-UHFFFAOYSA-L 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- JHJUUEHSAZXEEO-UHFFFAOYSA-M sodium;4-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=C(S([O-])(=O)=O)C=C1 JHJUUEHSAZXEEO-UHFFFAOYSA-M 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
- G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
- G03C1/067—Additives for high contrast images, other than hydrazine compounds
Landscapes
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Physics & Mathematics (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明はハロゲン化銀写真感光材料に関するものであり
、さらに詳しくは高コントラストであり、かつ現像時の
不均一な現像による画像濃度の不均一、いわゆる現像む
らの低減されたハロゲン化銀写真感光材料に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a silver halide photographic light-sensitive material, and more specifically, it has a high contrast and is free from non-uniform image density due to non-uniform development during development. This invention relates to a silver halide photographic material with reduced so-called development unevenness.
ハロゲン化銀写真感光材料を用いる写真用製版過程には
、連続階調の原稿を網点画像に交換する工程、すなわち
連続階調の濃度変化を該濃度に比例する面積を有する網
点の集合体に変換する工程及び該工程で得られた網点画
像をより鮮鋭度の良好な網点画像に変換する工程、すな
わち返し工程などが含まれている。The photoengraving process using silver halide photographic light-sensitive materials involves the process of replacing a continuous tone original with a halftone image, that is, the process of converting continuous tone density changes into a set of halftone dots having an area proportional to the density. and a step of converting the halftone dot image obtained in this step into a halftone dot image with better sharpness, that is, a turning step.
これらの工程に使用される感光材料は、良好な網点品質
を得る必要から高コントラストを有することが不可欠と
されている。It is essential that the photosensitive materials used in these processes have high contrast in order to obtain good halftone dot quality.
このような特性を得る方法として従来から比較的微粒子
で粒子径分布が狭く、かつ塩化銀含有率の高い塩臭化銀
乳剤よりなる感光材料を亜硫酸イオン濃度が非常に小さ
いアルカリハイドロキノン現像液で処理する方法、所謂
リス現像法が知られている。Conventionally, a method to obtain such characteristics is to process a photosensitive material made of a silver chlorobromide emulsion with relatively fine grains, a narrow particle size distribution, and a high silver chloride content using an alkaline hydroquinone developer with a very low sulfite ion concentration. A so-called lithographic development method is known.
しかし、この方法を用いると現像液中の亜硫酸イオン濃
度が小さい為保恒性が極めて悪く、かつハイドロキノン
単体主薬を用いる為に現像速度が遅く迅速処理ができな
いという問題点を有していた。However, when this method is used, the storage stability is extremely poor because the concentration of sulfite ions in the developer is low, and since hydroquinone is used as a single main agent, the development speed is slow and rapid processing is not possible.
従って保恒性が良好で迅速処理可能な超加成性現像主薬
を含有し、比較的高濃度の亜硫酸塩を含有する所謂PQ
型あるいはMQ型の現像液による処理によって高いコン
トラストが得られる新規な感光材料の開発が望まれてい
る。Therefore, so-called PQ contains a super-additive developing agent that has good storage stability and can be processed quickly, and contains a relatively high concentration of sulfite.
It is desired to develop a new photosensitive material that can obtain high contrast by processing with a type or MQ type developer.
この新規な感光材料に関するものの1つとして、特公昭
59−17825号、同59−17sts号、同59−
17819号、同59−17820号、同59−178
21号、同59−17826号、同59−17822号
の各公報には、テトラゾリウム化合物を含有するハロゲ
ン化銀写真感光材料が開示されている。One of the things related to this new photosensitive material is Japanese Patent Publication No. 59-17825, Japanese Patent Publication No. 59-17sts, Japanese Patent Publication No. 59-17825,
No. 17819, No. 59-17820, No. 59-178
No. 21, No. 59-17826, and No. 59-17822 disclose silver halide photographic materials containing a tetrazolium compound.
これらのテトラゾリウム化合物を含有する感光材料を超
加成性現像液で処理し、高いコントラストを有する銀画
像を得る方法は、従来技術に対し極めて画期的技術とい
うことができる。The method of processing a photosensitive material containing these tetrazolium compounds with a superadditive developer to obtain a silver image with high contrast can be said to be an extremely innovative technology compared to conventional techniques.
しかし、ハロゲン化銀写真感光材料の階調を非常に高コ
ントラストにすると、現像のほんのわずかの不均一、例
えば現像主薬の拡散の不均一やBr−イオン等の現像抑
制物の拡散の不均一によって微妙に画像濃度が変化し、
使用上好ましくないという問題点があった。前記のリス
現像法におけるrBr−drug」という現象も、この
例である。However, when the gradation of a silver halide photographic light-sensitive material is made to have a very high contrast, slight nonuniformity in development, such as nonuniformity in the diffusion of a developing agent or nonuniformity in the diffusion of development inhibitors such as Br- ions, can cause The image density changes slightly,
There was a problem that it was not suitable for use. The phenomenon of "rBr-drug" in the above-mentioned Lith development method is also an example of this.
リス現像におけるrBr” drag」を改善する方法
としては、
■リス用感光材料のハロゲン化銀組成におけるBr含量
を減らす。Methods for improving rBr"drag" in lithographic development include: (1) reducing the Br content in the silver halide composition of the lithographic photosensitive material;
■アミン化合物を感材中に用いる、という方法が知られ
ているが、減感、Fog増を生じたり、その効果が不充
分であった。さらに前述のテトラゾリウムを含有した感
光材料も、リス現像の約3倍の現像スピードを持つ為、
高コントラストによる現像の不均一は処理条件によって
はより強くなって現われることがある。(2) A method of using an amine compound in a sensitive material is known, but this method causes desensitization and increase in fog, and its effects are insufficient. Furthermore, the photosensitive material containing tetrazolium mentioned above also has a development speed about three times that of lithium development.
Nonuniform development due to high contrast may become more pronounced depending on processing conditions.
本発明の目的は上記した従来技術を解決し、高コントラ
ストであり、かつ現像時の不均一現像による画像濃度の
不均一が低減されたハロゲン化銀写真感光材料を提供す
ることにある。An object of the present invention is to solve the above-mentioned prior art and to provide a silver halide photographic light-sensitive material which has high contrast and reduces unevenness in image density due to uneven development during development.
上記目的は支持体上に少なくとも一層のハロゲン化銀乳
剤層を有するハロゲン化銀写真感光材料の少なくとも一
層に下記一般式〔I〕で示される化合物の少なくとも一
種を含有し、かつ上記乳剤層に隣接する親水性コロイド
層に下記一般式(II)で示される化合物の少なくとも
一種を含有するハロゲン化銀写真感光材料によって達成
される。The above object is to provide a silver halide photographic material having at least one silver halide emulsion layer on a support, in which at least one layer contains at least one compound represented by the following general formula [I], and is adjacent to the emulsion layer. This is achieved by using a silver halide photographic material containing at least one compound represented by the following general formula (II) in the hydrophilic colloid layer.
一般式(1)
一般式〔■〕
〔式中、Yl及びY2は水素原子またはメルカプト基を
表し、R4は置換または未置換のアルキル基、アルケニ
ル基、アルキニル基、アリール基もしくはアルコキシ基
、または水素原子、)λロゲン原子、ニトロ基、アミノ
基、シアノ基、ヒドロキシカルボニル基、アルコキシカ
ルボニル基、アルキルカルボニル基、ヒドロキシ基、メ
ルカプト基またはスルホ基を表す。General formula (1) General formula [■] [In the formula, Yl and Y2 represent a hydrogen atom or a mercapto group, and R4 is a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, aryl group or alkoxy group, or hydrogen Atom, ) represents a λ rogen atom, a nitro group, an amino group, a cyano group, a hydroxycarbonyl group, an alkoxycarbonyl group, an alkylcarbonyl group, a hydroxy group, a mercapto group, or a sulfo group.
またAは窒素原子、炭素原子または酸素原子を表し、B
は窒素原子または炭素原子を表す。Aが炭素原子を表す
ときはn!は2であり、Aが窒素原子を表すときはR2
は1であり、Aが酸素原子を表すときはR2はOである
。Also, A represents a nitrogen atom, a carbon atom, or an oxygen atom, and B
represents a nitrogen atom or a carbon atom. When A represents a carbon atom, n! is 2, and when A represents a nitrogen atom, R2
is 1, and when A represents an oxygen atom, R2 is O.
またBが炭素原子を表すときはn、は1であり、Bが窒
素原子を表すときはnは0である。〕なお前記一般式(
1)において、R1−R2で表される置換基の好ましい
例としてアルキル基、アミノ基、アシルアミノ基、ヒド
ロキシル基、アルコキシ基、アシルオキシ基、ハロゲン
原子、カルバモイル基、アシルチオ基、アルコキシカル
ボニル基、カルボキシル基、アシル基、シアノ基、ニト
ロ基、メルカプト基、スルホオキシ基、アミノスルホキ
シ基のような基が挙げられる。Further, when B represents a carbon atom, n is 1, and when B represents a nitrogen atom, n is 0. ] Note that the above general formula (
In 1), preferred examples of the substituent represented by R1-R2 include an alkyl group, an amino group, an acylamino group, a hydroxyl group, an alkoxy group, an acyloxy group, a halogen atom, a carbamoyl group, an acylthio group, an alkoxycarbonyl group, and a carboxyl group. , an acyl group, a cyano group, a nitro group, a mercapto group, a sulfoxy group, and an aminosulfoxy group.
前記Xeで示されるアニオンとしては、例えばハロゲン
イオン、無機酸の酸根、スルホン酸、カルボン酸等の有
機酸の酸根、アニオン系の活性剤、具体的には低級アル
キルベンゼンスルホン酸アニオン、高級アルキルベンゼ
ンスルホン酸アニオン、高級アルキル硫酸エステルアニ
オン、硼酸系アニオン、ジアルキルスルフオフサクシネ
ートアニオン、ポリエーテルアルコール硫酸エステルア
ニオン、高級脂肪酸アニオン、ポリアクリル酸アニオン
等のポリマーに酸根のついたもの等を挙げることができ
る。Examples of the anion represented by Xe include halogen ions, acid groups of inorganic acids, acid groups of organic acids such as sulfonic acids and carboxylic acids, anionic activators, specifically lower alkylbenzenesulfonic acid anions, higher alkylbenzenesulfonic acids Examples include polymers with acid groups attached, such as anions, higher alkyl sulfate anions, boric acid anions, dialkyl sulfofosuccinate anions, polyether alcohol sulfate anions, higher fatty acid anions, and polyacrylate anions.
以下、本発明に用いられる一般式(I)で表される化合
物の具体例を第1表に挙げるが、本発明筒 1 表
本発明に用いられるテトラゾリウム化合物は、例えばケ
ミカル・レビ、:L−(Chemical Revie
ws)第55巻、第335頁〜483頁に記載の方法に
従って容易に合成することができる。Specific examples of the compounds represented by the general formula (I) used in the present invention are listed in Table 1 below. (Chemical Revie
It can be easily synthesized according to the method described in Vol. 55, pp. 335-483.
本発明で用いる一般式(1)で表されるテトラゾリウム
化合物は、本発明のハロゲン化銀写真感光材料に含有さ
れるハロゲン化銀1モル当たり約1 mg以上約10g
まで、好ましくは約10■以上約2gの範囲で用いられ
るのが好ましい。The tetrazolium compound represented by the general formula (1) used in the present invention is about 1 mg or more and about 10 g per mole of silver halide contained in the silver halide photographic material of the present invention.
It is preferable to use the amount up to about 10 g to about 2 g.
次に一般式(II)の化合物の代表的具体例を挙げるが
、本発明はこれらに限定されるものではない。Next, typical examples of the compound of general formula (II) will be given, but the present invention is not limited thereto.
(例示化合物)
(II−1)ベンゾトリアゾール
(II−2)5−メチルベンゾトリアゾール(II−3
)5−クロルベンゾトリアゾール(II−4)5−ニト
ロベンゾトリアゾール(n−5)5−エチルベンゾトリ
アゾール(II−6)ヒドロキシカルボニルベンゾトリ
アゾール
(II−7)5−ヒドロキシベンゾトリアゾール(II
−8)5−アミノベンゾトリアゾール(If−9)5−
スルホンベンゾトリアゾール(n−10)5−シアノベ
ンゾトリアゾール(n−11) 5−メトキシベンゾ
トリアゾール(II−12) 5−エトキシベンゾト
リアゾール(U−13) 5−メルカプトベンゾトリ
アゾール(II−14)ベンズイミダゾール
(II−15) 5−スルホベンズイミダゾール(n
−16) 5−メトキシベンズイミダゾール(n−1
7) 5−クロロベンズイミダゾール(n−18)
5−ニトロインダゾール(n−19) 6−ニトロ
インダゾール(n−20)5−スルホインダゾール
(II−21)ベンズオキサゾール
(II−22) 2−メルカプト−5−スルホベンズイ
ミダゾール
(n−23)2−メルカプトベンズオキサゾール本発明
に用いられる前記一般式(II)の化合物の使用量は、
ハロゲン化銀使用量、前記一般式CI)の化合物量、等
によって左右され、−概には言えず、適時、適当量使用
するのが好ましいが、一般的には、ハロゲン化銀感光材
料1イ当たり0.1■〜1gが好ましく、1■〜100
■の範囲が特に好ましい。(Exemplary compounds) (II-1) Benzotriazole (II-2) 5-methylbenzotriazole (II-3
) 5-chlorobenzotriazole (II-4) 5-nitrobenzotriazole (n-5) 5-ethylbenzotriazole (II-6) hydroxycarbonylbenzotriazole (II-7) 5-hydroxybenzotriazole (II
-8) 5-Aminobenzotriazole (If-9) 5-
Sulfonebenzotriazole (n-10) 5-cyanobenzotriazole (n-11) 5-methoxybenzotriazole (II-12) 5-ethoxybenzotriazole (U-13) 5-mercaptobenzotriazole (II-14) Benzimidazole (II-15) 5-sulfobenzimidazole (n
-16) 5-methoxybenzimidazole (n-1
7) 5-chlorobenzimidazole (n-18)
5-Nitroindazole (n-19) 6-Nitroindazole (n-20) 5-Sulfoindazole (II-21) Benzoxazole (II-22) 2-Mercapto-5-sulfobenzimidazole (n-23) 2- Mercaptobenzoxazole The amount of the compound of general formula (II) used in the present invention is:
It depends on the amount of silver halide used, the amount of the compound of general formula CI), etc. - Although it cannot be generalized, it is preferable to use an appropriate amount at the right time, but in general, silver halide photosensitive material 1 0.1 - 1 g is preferable, and 1 - 100
The range (2) is particularly preferred.
本発明のハロゲン化銀写真感光材料は、支持体上に少な
くとも一層のハロゲン化銀乳剤層を包含する親水性コロ
イド層を塗設してなり、このハロゲン化銀乳剤層は支持
体上に直接塗設されるか、あるいはハロゲン化銀乳剤を
含まない親水性コロイド層を介して塗設され、該ハロゲ
ン化銀乳剤層の上にさらに保護層としての親水性コロイ
ド層を塗設してもよい。また、ハロゲン化銀乳剤層は異
なる感度、例えば高感度及び低感度のハロゲン化銀乳剤
層に分けてもよい。該ハロゲン化銀乳剤層は、この層の
間に、親水性コロイド層の中間層を設けてもよいし、ま
たハロゲン化銀乳剤層と保護層との間には中間層を設け
てもよい。The silver halide photographic light-sensitive material of the present invention is formed by coating a hydrophilic colloid layer containing at least one silver halide emulsion layer on a support, and this silver halide emulsion layer is coated directly onto the support. Alternatively, it may be coated via a hydrophilic colloid layer containing no silver halide emulsion, and a hydrophilic colloid layer as a protective layer may be further coated on the silver halide emulsion layer. The silver halide emulsion layer may also be divided into silver halide emulsion layers of different sensitivities, for example high and low sensitivity. An intermediate layer of a hydrophilic colloid layer may be provided between the silver halide emulsion layers, or an intermediate layer may be provided between the silver halide emulsion layer and the protective layer.
具体的には、感光層であるハロゲン化銀乳剤層が支持体
の片面に一層設けられているもの、支持体の両面に各一
層設けられているもの、支持体の片面に一層、他の片面
に非感光層に属する中間層を介して二層以上設けられて
いるもの、並びに支持体の両面に非感光層を介して二層
以上設けられているもの等が挙げられる。なお支持体表
面には非感光層に属する下地層が、一番表面には保護層
が設けられていてもよく、性能を落とさない限り種々の
ものが設けられていてもよい。Specifically, the silver halide emulsion layer, which is a photosensitive layer, is provided on one side of the support, one layer is provided on both sides of the support, and one layer is provided on one side of the support, and one layer is provided on the other side. Examples include those in which two or more layers are provided via an intermediate layer belonging to a non-photosensitive layer, and those in which two or more layers are provided on both sides of the support with non-photosensitive layers interposed therebetween. Note that the surface of the support may be provided with a base layer belonging to a non-photosensitive layer, the outermost layer may be provided with a protective layer, and various other materials may be provided as long as performance is not degraded.
親水性コロイド層は、主に感光層と非感光層とに大別す
ることができる。感光層はハロゲン化銀乳剤層が代表的
であり、非感光層は下地層、中間層、保護層等が挙げら
れる。The hydrophilic colloid layer can be roughly divided into a photosensitive layer and a non-photosensitive layer. The photosensitive layer is typically a silver halide emulsion layer, and the non-photosensitive layers include an underlayer, an intermediate layer, a protective layer, and the like.
本発明で用いる一般式(I)で表されるテトラゾリウム
化合物が含有せしめられる層はハロゲン化銀乳剤層であ
り、一般式(H)で表される化合物が含有せしめられる
層は、該ハロゲン化銀乳剤層に隣接する親水性コロイド
層である。The layer containing the tetrazolium compound represented by the general formula (I) used in the present invention is a silver halide emulsion layer, and the layer containing the compound represented by the general formula (H) is the silver halide emulsion layer. A hydrophilic colloid layer adjacent to the emulsion layer.
本発明で用いる一般式(I)で表されるテトラゾリウム
化合物及び一般式〔■〕で表される化合物を親水性コロ
イド層に含有せしめるには、適宜の水及び/または有機
溶媒に両者を溶解して添加する方法、あるいは有機溶媒
に溶かした液をゼラチンあるいはゼラチン誘導体等の親
水性コロイドマトリックス中に分散してから添加する方
法またはラテックス中に分散して添加する方法等が挙げ
られる。本発明はこれらの方法のいづれを用いてもよい
。In order to incorporate the tetrazolium compound represented by the general formula (I) and the compound represented by the general formula [■] used in the present invention into the hydrophilic colloid layer, both are dissolved in appropriate water and/or an organic solvent. Examples include a method in which a solution dissolved in an organic solvent is added after being dispersed in a hydrophilic colloid matrix such as gelatin or a gelatin derivative, or a method in which a solution is added after being dispersed in latex. The present invention may use any of these methods.
本発明において用いられる一般式(1)で表されるテト
ラゾリウム化合物は、1種を用いてもまた2種以上を適
宜の比率で組み合わせて用いてもよい。さらに本発明の
テトラゾリウム化合物と本発明外のテトラゾリウム化合
物を適宜の割合で組み合わせて用いてもよい。 。The tetrazolium compound represented by the general formula (1) used in the present invention may be used alone or in combination of two or more in an appropriate ratio. Furthermore, the tetrazolium compound of the present invention and the tetrazolium compound outside the present invention may be used in combination in an appropriate ratio. .
本発明において、本発明で用いるテトラゾリウム化合物
と結合し、本発明のテトラゾリウム化合物の親水性を下
げるアニオンを併用すると、特に好ましい結果が得られ
る。このようなアニオンとしては例えば過塩素酸等の無
機酸の酸根、スルホン酸、カルボン酸等の有機酸の酸根
、アニオン系の活性剤、具体的にはp−1ルエンスルホ
ン酸アニオン等の低級アルキルベンゼンスルホン酸アニ
オン、p−ドデシルベンゼンスルホン酸アニオン類、ア
ルキルナフタレンスルホン酸アニオン類、ラウリルスル
フェートアニオン類、テトラフェニールボロン類、ジー
2−エチルへキシルスルホサクシネートアニオン類等の
ジアルキルスルフオサクシネートアニオン、セチルポリ
エテノキシサルフェートアニオン等のポリエーテルアル
コール硫酸エステルアニオン、ステアリン酸アニオン類
等、ポリアクリル酸アニオン類等を挙げることができる
。In the present invention, particularly favorable results can be obtained when an anion that binds to the tetrazolium compound used in the present invention and lowers the hydrophilicity of the tetrazolium compound of the present invention is used in combination. Examples of such anions include acid groups of inorganic acids such as perchloric acid, acid groups of organic acids such as sulfonic acids and carboxylic acids, anionic activators, and specifically lower alkylbenzenes such as p-1 luenesulfonic acid anions. Dialkyl sulfosuccinate anions such as sulfonate anions, p-dodecylbenzenesulfonate anions, alkylnaphthalenesulfonate anions, lauryl sulfate anions, tetraphenylborons, di-2-ethylhexylsulfosuccinate anions, etc. , polyether alcohol sulfate anions such as cetyl polyethenoxysulfate anions, stearate anions, and polyacrylate anions.
このようなアニオンは、本発明のテトラゾリウム化合物
と予め混合した後、親水性コロイド層へ添加してもよい
し、また単独で本発明のテトラゾリウムを含有もしくは
含有しないハロゲン化銀乳剤層または親水性コロイド層
に添加することかできる。Such anions may be added to the hydrophilic colloid layer after being premixed with the tetrazolium compound of the present invention, or may be added alone to the silver halide emulsion layer or hydrophilic colloid containing or not containing the tetrazolium of the present invention. Can be added to the layer.
本発明のハロゲン化銀写真感光材料に用いるハ
−ロゲン化銀については、特に限定はないが、塩化銀も
しくは塩臭化銀が好ましい。塩臭化銀の組成は八gcf
fi/AgBr= 100/ O〜2 /98のいずれ
でもよいが、好ましくはAg C1/ AgBr =
80/ 20〜30/ 70のモル比である。ハロゲン
化銀粒子の平均粒径は0.10μm〜0.40μmが好
ましく、(粒径の標準偏差)/(平均粒径)xlOOで
表される変動係数が15%以下の粒径分布の狭いものが
より好ましい。Silver halide used in the silver halide photographic light-sensitive material of the present invention
- Silver halide is not particularly limited, but silver chloride or silver chlorobromide is preferred. The composition of silver chlorobromide is 8 gcf
fi/AgBr=100/O~2/98, preferably AgC1/AgBr=
The molar ratio is 80/20 to 30/70. The average grain size of the silver halide grains is preferably 0.10 μm to 0.40 μm, and has a narrow grain size distribution with a coefficient of variation expressed by (standard deviation of grain size)/(average grain size) x lOO of 15% or less. is more preferable.
本発明において用いられるハロゲン化銀は、種々な増感
剤、増感色素、安定剤等を用いることができる。For the silver halide used in the present invention, various sensitizers, sensitizing dyes, stabilizers, etc. can be used.
本発明による前記ハロゲン化銀及びテトラゾリウム化合
物及び一般式(I[)で表される化合物は、親水性コロ
イド層中に添加せしめられるが、本発明に特に有利に用
いられる親水性コロイドはゼラチンである。またゼラチ
ン以外の親水性コロイドも用いることができる。The silver halide and tetrazolium compounds according to the present invention and the compound represented by the general formula (I[) are added to the hydrophilic colloid layer, and the hydrophilic colloid particularly advantageously used in the present invention is gelatin. . Hydrophilic colloids other than gelatin can also be used.
これらの親水性コロイドはハロゲン化銀を含有しない層
、例えばハレーション防止層、保st層、中間層等にも
適用できる。These hydrophilic colloids can also be applied to layers that do not contain silver halide, such as antihalation layers, storage layers, intermediate layers, etc.
本発明に用いる支持体としては、例えばポリエステルフ
ィルム等感光材料業界で用いている各種支持体を用いる
ことができる。As the support used in the present invention, various supports used in the photosensitive material industry, such as polyester films, can be used.
本発明の感光材料は適度の膜厚を有する保護層、即ち好
ましくは0.1〜10μm、特に好ましくは0.8〜2
μmのゼラチン保護層が塗設されているのが望ましい。The photosensitive material of the present invention has a protective layer having an appropriate thickness, that is, preferably 0.1 to 10 μm, particularly preferably 0.8 to 2 μm.
Preferably, a gelatin protective layer of .mu.m is coated.
本発明に用いられる前記親水性コロイド層には必要に応
じて各種写真用添加剤、例えばゼラチン可塑剤、硬膜剤
、界面活性剤、画像安定剤、紫外線吸収剤、アスチステ
イン剤、pHtA整剤、酸化防止剤、帯電防止剤、増粘
剤、粒状性向上剤、染料、モルダント、増白剤、現像速
度調整剤、マット剤等を本発明の効果が損なわれない範
囲内で使用することができる。The hydrophilic colloid layer used in the present invention may optionally contain various photographic additives, such as gelatin plasticizers, hardeners, surfactants, image stabilizers, ultraviolet absorbers, astistein agents, pHtA adjusters, Antioxidants, antistatic agents, thickeners, graininess improvers, dyes, mordants, brighteners, development speed regulators, matting agents, etc. can be used within the range that does not impair the effects of the present invention. .
本発明のテトラゾリウム化合物及び一般式〔■〕で表さ
れる化合物を含有するハロゲン化銀写真感光材料′は、
下記一般式(III)で表される化合物を含有する現像
液で現像されることが好ましい。The silver halide photographic material' containing the tetrazolium compound of the present invention and the compound represented by the general formula [■] is
It is preferable to develop with a developer containing a compound represented by the following general formula (III).
一般式(I[[)
表す。Mは水素原子、アルカリ金属原子、アルカリ土類
金属原子またはアンモニウムイオンなどのカチオンを表
す、)
−a式(III)で表す具体的化合物として、5−ニト
ロインダゾール、6−ニトロインダゾールなどが挙げら
れるが、本発明は何等これに限定されるものではない。Represented by the general formula (I[[). M represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, or a cation such as an ammonium ion;) -a Specific compounds represented by formula (III) include 5-nitroindazole, 6-nitroindazole, etc. However, the present invention is not limited to this in any way.
一般式(I[[)で表す化合物は、ジエチレングリコー
ル、トリエチレングリコール、エタノール、ジェタノー
ルアミン及びトリエタノールアミン等の有機溶剤、水酸
化ナトリウムなどのアルカリ及び酢酸等の酸等に溶解し
て現像液に添加してもよいし、そのまま添加してもよい
。The compound represented by the general formula (I It may be added to, or may be added as is.
一般式(I[[)で表される化合物は現像液11当たり
約1■から1 、000■が好ましく、より好ましくは
約50mgから300■の濃度範囲で含まれる。The compound represented by the general formula (I[[) is contained in a concentration range of preferably about 1 to 1,000, more preferably about 50 to 300, per developer.
本発明のハロゲン化銀写真感光材料の現像に用いられる
現像主薬としては、T、H。ジェームス著ザ・セオリイ
・オブ・ザ・フォトグラフインク・プロセス第4版(T
he Theory of thePhotograp
hic Process、Fourth Editio
n)第291〜334頁及びジャーナル・オブ・ザ・ア
メリカン・ケミカル・ソサイティ(Journal
ofthe American Chemical 5
ociety)第73巻、第3,100頁(1951)
に記載されているごとき現像剤が本発明に有効に使用し
得るものである。これらの現像剤は単独で使用しても2
種以上を組合わせてもよいが、2種以上組合せて用いる
方が好ましい。また本発明の感光材料の現像に使用する
現像液には保恒剤として、例えば亜硫酸ナトリウム、亜
硫酸カリウム等の亜硫酸塩を用いても、本発明の効果が
損なわれることなく、本発明の1つの特徴として挙げる
ことができる。また保恒剤とじてヒドロキシルアミン、
ヒドラジド化合物を用いてもよい。その他一般白黒現像
液で用いられるような苛性アルカリ、炭酸アルカリまた
はアミン等によるpHの調整とバッファー機能を持たせ
ること、及びブロムカリなど無機現像抑制剤及びベンゾ
トリアゾール等の有機現像抑制剤、エチレンジアミン四
酢酸等の金属イオン捕捉剤、メタノール、エタノール、
ベンジルアルコール、ポリアルキレンオキシド等の現像
促進剤、アルキルアリールスルホン酸ナトリウム、天然
のサポニン、糖類または前記化合物のアルキルエステル
物等の界面活性剤、グルタルアルデヒド、ホルマリン、
グリオキザール等の硬膜剤、硫酸ナトリウム等のイオン
強度調整剤等の添加を行うことは任意である。The developing agent used for developing the silver halide photographic light-sensitive material of the present invention includes T and H. The Theory of the Photographic Process by James, 4th Edition (T
the theory of the photograp
hic Process, Fourth Edition
n) pp. 291-334 and Journal of the American Chemical Society (Journal
of the American Chemical 5
73, page 3,100 (1951)
Developers such as those described in the following can be effectively used in the present invention. Even if these developers are used alone, 2
Although more than one type may be used in combination, it is preferable to use two or more types in combination. Further, even if a sulfite salt such as sodium sulfite or potassium sulfite is used as a preservative in the developer used for developing the photosensitive material of the invention, the effects of the invention will not be impaired, and one of the effects of the invention will be improved. This can be mentioned as a characteristic. Also, hydroxylamine as a preservative,
A hydrazide compound may also be used. In addition, adjusting the pH with caustic alkali, alkali carbonate, or amines used in general black and white developers and providing a buffer function, inorganic development inhibitors such as brompotali, organic development inhibitors such as benzotriazole, and ethylenediaminetetraacetic acid. Metal ion scavengers such as methanol, ethanol, etc.
Development accelerators such as benzyl alcohol and polyalkylene oxide, sodium alkylarylsulfonate, natural saponins, surfactants such as sugars or alkyl esters of the above compounds, glutaraldehyde, formalin,
It is optional to add a hardening agent such as glyoxal, an ionic strength regulator such as sodium sulfate, etc.
本発明の感光材料の現像に使用される現像液には、有機
溶剤としてアルカノールアミン類やグリコール類を含有
させてもよい。上記のアルカノールアミンとしては、例
えばモノエタノールアミン、ジェタノールアミン、トリ
エタノールアミン等があるが、トリエタノールアミンが
好ましく用いられる・これらアルカノールアミンの好ま
しい使用量は現像液12当たり5〜500gで、より好
ましくは20〜200gである。The developer used for developing the photosensitive material of the present invention may contain alkanolamines or glycols as an organic solvent. Examples of the alkanolamines mentioned above include monoethanolamine, jetanolamine, triethanolamine, etc., but triethanolamine is preferably used. The preferable amount of these alkanolamines used is 5 to 500 g per 12 of the developer, and more Preferably it is 20-200g.
また上記のグリコール類としては、エチレングリコール
、ジエチレングリコール、プロピレングリコール、トリ
エチレングリコール、1.4−ブタンジオール、1,5
−ベンタンジオール等があるが、ジエチレングリコール
が好ましく用いられる。そしてこれらグリコール類の使
用量は現像液12当たり5〜500 gがよく、より好
ましくは2゜〜200gである。これらの有機溶媒は、
単独でも併用しても用いることができる。In addition, the above glycols include ethylene glycol, diethylene glycol, propylene glycol, triethylene glycol, 1,4-butanediol, 1,5
-bentanediol and the like, but diethylene glycol is preferably used. The amount of these glycols used is preferably 5 to 500 g, more preferably 2 to 200 g per 12 of the developer. These organic solvents are
They can be used alone or in combination.
本発明のハロゲン化銀写真感光材料は、上記の現像液を
用いて現像処理することにより極めて保存安定性に優れ
た感光材料を得ることができる。The silver halide photographic light-sensitive material of the present invention can be developed with the above developer to obtain a light-sensitive material with extremely excellent storage stability.
上記の組成になる現像液のPHは9〜12がよいが、保
恒性及び写真特性上からpH値は10〜11の範囲が好
ましい。The pH value of the developer having the above composition is preferably 9 to 12, but from the viewpoint of stability and photographic properties, the pH value is preferably in the range of 10 to 11.
本発明のハロゲン化銀写真感光材料は、種々の条件で処
理することができる。処理条件は、例えば現像温度は5
0″C以下が好ましく、特に30°C前後が好ましく、
また現像時間は3分以内に終了することが一般的である
が、特に好ましくは1分以内が好結果をもたらすことが
多い、また現像以外の処理工程、例えば水洗、停止、安
定、定着、さらに必要に応じて前硬膜、中和等の工程を
採用することは任意であり、これらは適宜省略すること
もできる。さらにまた、これらの処理は皿現像、枠現像
等いわゆる手現像処理でも、ローラー現像、ハンガー現
像など機械現像であってもよい。The silver halide photographic material of the present invention can be processed under various conditions. The processing conditions are, for example, the development temperature is 5
The temperature is preferably 0″C or less, particularly preferably around 30°C,
In addition, it is common for the development time to be completed within 3 minutes, but it is particularly preferable that the development time is within 1 minute, which often brings good results. It is optional to employ steps such as preduralization and neutralization as needed, and these steps can be omitted as appropriate. Furthermore, these treatments may be so-called manual development such as plate development or frame development, or mechanical development such as roller development or hanger development.
以下、具体的に実施例を示す。 Examples will be specifically shown below.
(乳剤(A)の調整方法)
次に示すA液、B液、C液の溶液を用いて塩臭化銀乳剤
を調整した。(Method for Preparing Emulsion (A)) A silver chlorobromide emulsion was prepared using the following solutions of liquid A, liquid B, and liquid C.
〈ン容液A〉
〈溶液B〉
〈溶液C〉
溶液Aを40℃に保温した後EAg値が160mvにな
るように塩化ナトリウムを添加した。<Solution A><SolutionB><SolutionC> After keeping solution A at 40° C., sodium chloride was added so that the EAg value was 160 mv.
次に特開昭57−92523号と同57−92524号
記載の混合攪拌機を用いて、ダブルジェット法にて溶液
B及び溶液Cを添加した。Next, solutions B and C were added by a double jet method using the mixer described in JP-A-57-92523 and JP-A-57-92524.
添加流量は第2表に示した様に全添加時間80分の間に
わたって、徐々に添加流量を増加させEAgを一定に保
ちながら添加を行った。As shown in Table 2, the addition flow rate was gradually increased over a total addition time of 80 minutes, and addition was carried out while keeping EAg constant.
EAg値は160mvより添加開始5分後に3戚/lの
塩化ナトリウム水溶液を用いてEAg値120mνに変
化させ、以後混合の完了までこの値を維持した。The EAg value was changed from 160 mv to 120 mv using an aqueous solution of sodium chloride of 3 mol/l 5 minutes after the start of addition, and this value was maintained thereafter until the completion of mixing.
EAg値を一定に保つ為、3モル/Ilの塩化ナトリウ
ム水溶液を用いてEAg値を制御した。In order to keep the EAg value constant, the EAg value was controlled using a 3 mol/Il aqueous sodium chloride solution.
EAg値の測定には、金属銀電極と、ダブルジャンクシ
ョン型飽和Ag/AgC1比較電極を用いた(電極の構
成は、特開昭57−197534号に開示されるダブル
ジャンフシボンを使用した。)。To measure the EAg value, a metal silver electrode and a double junction type saturated Ag/AgC1 comparison electrode were used (the electrode configuration used was a double junction fusibon disclosed in JP-A-57-197534). .
また、溶液B液、C液の添加には、流量可変型のローラ
ーチューブ定量ポンプを用いた。Further, a variable flow rate roller tube metering pump was used to add solutions B and C.
また添加中、乳剤のサンプリングにより、系内に新たな
粒子の発生が認められないことを電子顕微鏡により観察
し、確認している。Furthermore, during the addition, the emulsion was sampled and observed using an electron microscope to confirm that no new particles were generated within the system.
また添加中、系のpH値を3.0に一定に保つ様に3%
硝酸水溶液で制御した。Also, during addition, 3% was added to keep the pH value of the system constant at 3.0.
It was controlled with a nitric acid aqueous solution.
B液、C液を添加終了後、乳剤は10分間オストワルド
熟成したのち、常法により脱塩、水洗を行い、その後オ
セインゼラチンの水溶液600m(オセインゼラチン3
0g含有)を加えて、55°C30分間攪拌により分散
した後、750ccに調製した。After addition of solutions B and C, the emulsion was subjected to Ostwald ripening for 10 minutes, then desalted and washed with water in a conventional manner.
After dispersion by stirring at 55° C. for 30 minutes, the volume was adjusted to 750 cc.
実施例1
乳剤(A)に対して金硫黄増惑を施し、安定剤として6
−メチル−4−ヒドロキシ−1,3,3a、7−チトラ
ザインデンを加え、増感色素として1−(β−ヒドロキ
シエチル)−3−フェニル−5−[(3−α−スルホプ
ロピル−α−ペンゾオキサゾリデン)−エチリデンコチ
オヒダントインを乳剤中に含まれるハロゲン化銀1モル
当たり150mg添加した。Example 1 Emulsion (A) was enriched with gold and sulfur, and 6 was added as a stabilizer.
-Methyl-4-hydroxy-1,3,3a,7-titrazaindene was added and 1-(β-hydroxyethyl)-3-phenyl-5-[(3-α-sulfopropyl-α-pene) was added as a sensitizing dye. 150 mg of zooxazolidene)-ethylidene cothiohydantoin was added per mole of silver halide contained in the emulsion.
次いでハロゲン化銀1モル当たり第3表に示す如く一般
式(1)の化合物を加え、更にp−ドデシルベンゼンス
ルホン酸ソーダ300mg、スチレン−マレイン酸共重
合体Iポリマー2g、スチレン−ブチルアクリレート−
アクリル酸共重合体ラテックス(平均粒径約0.25μ
m)15gを加えて、Agf!3.5g/rd、ゼラチ
ン量2.0g/rrrになるように特開昭59−199
41号公報実施例(1)に記載の下引を施したポリエチ
レンテレフタレートフィルムベース上に塗布した。その
際ゼラチン!1.0g/ボになるように延展剤として、
1−デシル−2−(3−イソペンチル)サクシネート−
2−スルホン酸ソーダを30■/rrf、ハロゲン化銀
1モル当たり第2表に示す如く一般式(II)の化合物
を加え、更に硬膜剤としてホルマリン25■/rrrを
含む保護層を同時重層塗布した。上述のようにして得ら
れた試料を、第2表に示した。Next, the compound of general formula (1) was added as shown in Table 3 per mole of silver halide, and 300 mg of sodium p-dodecylbenzenesulfonate, 2 g of styrene-maleic acid copolymer I polymer, and styrene-butyl acrylate were added.
Acrylic acid copolymer latex (average particle size approximately 0.25μ
m) Add 15g and Agf! 3.5 g/rd, gelatin amount 2.0 g/rrr
It was coated on a subbed polyethylene terephthalate film base as described in Example (1) of Publication No. 41. Gelatin then! As a spreading agent so that the amount is 1.0g/bo,
1-decyl-2-(3-isopentyl)succinate-
Sodium 2-sulfonate was added at 30 μ/rrf, and the compound of general formula (II) as shown in Table 2 was added per mole of silver halide, and a protective layer containing 25 μ/rr of formalin as a hardening agent was simultaneously layered. Coated. The samples obtained as described above are shown in Table 2.
得られた試料をそれぞれ二分し、−半はウェッジを用い
タングステン光源によって露光を行った。Each of the obtained samples was divided into two parts, and the other half was exposed to light using a tungsten light source using a wedge.
他の一半は、濃度が1.0になるように露光した。The other half was exposed to light at a density of 1.0.
上記テストサンプルを下記の処方による現像液及び定着
液とを用いて自動現像機にて処理した。The above test sample was processed in an automatic processor using a developer and a fixer having the following formulation.
第 3 表
〈現像処理条件〉
(工 程) (温 度) (時 間)現像 28
°C30秒
定 着 28 °C約20秒
水洗 常温 約20秒
乾燥 50 ’C15秒
(組成A)
(組成り)
現像液の使用時に水500d中に上記組成A、組成りの
順に溶かし、12に仕上げて用いた。Table 3 <Development processing conditions> (Process) (Temperature) (Time) Development 28
Fixation at 30 °C for 30 seconds Washing at 28 °C for about 20 seconds Dry at room temperature for about 20 seconds 50'C for 15 seconds (composition A) (Composition) When using a developer, dissolve the above composition A in the order of 12 in 500 d of water. I finished it and used it.
〈定着液処方〉
(組成A)
(組成り)
定着液の使用時に水500戚中に上記組成A、組成りの
順に溶かし、1j2に仕上げて用いた。この定着液のp
Hは、約4.3であった。<Fixer Prescription> (Composition A) (Composition) When using a fixer, the above composition A was dissolved in 500% water in that order, and the composition was finished to 1j2. This fixer p
H was approximately 4.3.
現像処理した試料について写真特性曲線を書き、コント
ラストは光学濃度0.2及び1.5を与える露光量に対
するガンマ値で示した。更に現像の不均一による画像濃
度の不安の尺度として、濃度1.0の試料におけるムラ
を官能評価した。そしてランク3は、業界で認められる
下限を示し、ランク5は全く問題のないレベルを示す。Photographic characteristic curves were drawn for the developed samples, and the contrast was expressed as a gamma value with respect to the exposure amount giving optical densities of 0.2 and 1.5. Further, as a measure of anxiety in image density due to non-uniform development, unevenness in a sample with a density of 1.0 was sensory evaluated. Rank 3 indicates the lower limit accepted in the industry, and rank 5 indicates a level at which there is no problem at all.
それらの結果を、第4表にまとめて示した。The results are summarized in Table 4.
尚、比較して次の化合物(A)を、添加した。For comparison, the following compound (A) was added.
比較化合物(A)
O
ε・ヅ、・
第 4 表
第4表から明らかなように本発明に属する試料N013
〜Nα22は、コントラストが25〜27と良好であり
、現像ムラもランクが4もしくは5と実用に耐えるレベ
ルであることがわかる。これに対して比較例に属する第
4表の試料kl、2.23はコントラストが7と悪いか
、あるいは現像ムラがランク2と悪くて実用に耐えなか
った。Comparative Compound (A) O ε・ㅅ,・Table 4 As is clear from Table 4, sample No. 013 belongs to the present invention.
It can be seen that ~Nα22 has a good contrast of 25 to 27, and development unevenness has a rank of 4 or 5, which is at a level suitable for practical use. On the other hand, sample kl, 2.23 in Table 4, which belongs to Comparative Examples, had a poor contrast of 7 or a poor development unevenness of rank 2, and was not suitable for practical use.
以上述べたように本発明によれば、高コントラストであ
り、現像時の不均一現像による画像濃度の不均一が低減
されたハロゲン化銀写真感光材料が得られる。As described above, according to the present invention, it is possible to obtain a silver halide photographic light-sensitive material which has high contrast and reduces unevenness in image density due to uneven development during development.
Claims (1)
有するハロゲン化銀写真感光材料において、該乳剤層の
少なくとも一層に下記一般式〔 I 〕で示される化合物
の少なくとも一種を含有し、かつ上記乳剤層に隣接する
親水性コロイド層に下記一般式〔II〕で示される化合物
の少なくとも一種を含有することを特徴とするハロゲン
化銀写真感光材料。 一般式〔 I 〕 ▲数式、化学式、表等があります▼ 一般式〔II〕 ▲数式、化学式、表等があります▼ 〔式中、Y_1及びY_2は水素原子またはメルカプト
基を表し、R^4は置換または未置換のアルキル基、ア
ルケニル基、アルキニル基、アリール基もしくはアルコ
キシ基、または水素原子、ハロゲン原子、ニトロ基、ア
ミノ基、シアノ基、ヒドロキシカルボニル基、アルコキ
シカルボニル基、アルキルカルボニル基、ヒドロキシ基
、メルカプト基またはスルホ基を表す。 またAは窒素原子、炭素原子または酸素原子を表し、B
は窒素原子または炭素原子を表す。Aが炭素原子を表す
ときはn_2は2であり、Aが窒素原子を表すときはn
_2は1であり、Aが酸素原子を表すときはn_2は0
である。 またBが炭素原子を表すときはn_1は1であり、Bが
窒素原子を表すときはnは0である。〕[Scope of Claims] 1. In a silver halide photographic material having at least one silver halide emulsion layer on a support, at least one of the emulsion layers contains at least one compound represented by the following general formula [I]. 1. A silver halide photographic light-sensitive material, which contains at least one compound represented by the following general formula [II] in a hydrophilic colloid layer adjacent to the emulsion layer. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ General formula [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, Y_1 and Y_2 represent a hydrogen atom or a mercapto group, and R^4 Substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, aryl group or alkoxy group, or hydrogen atom, halogen atom, nitro group, amino group, cyano group, hydroxycarbonyl group, alkoxycarbonyl group, alkylcarbonyl group, hydroxy group , represents a mercapto group or a sulfo group. Also, A represents a nitrogen atom, a carbon atom or an oxygen atom, and B
represents a nitrogen atom or a carbon atom. When A represents a carbon atom, n_2 is 2, and when A represents a nitrogen atom, n_2 is 2.
_2 is 1, and when A represents an oxygen atom, n_2 is 0
It is. Further, when B represents a carbon atom, n_1 is 1, and when B represents a nitrogen atom, n is 0. ]
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP8351787A JPS63249142A (en) | 1987-04-04 | 1987-04-04 | Silver halide photographic sensitive material with reduced uneven development |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP8351787A JPS63249142A (en) | 1987-04-04 | 1987-04-04 | Silver halide photographic sensitive material with reduced uneven development |
Publications (1)
Publication Number | Publication Date |
---|---|
JPS63249142A true JPS63249142A (en) | 1988-10-17 |
Family
ID=13804675
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP8351787A Pending JPS63249142A (en) | 1987-04-04 | 1987-04-04 | Silver halide photographic sensitive material with reduced uneven development |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS63249142A (en) |
-
1987
- 1987-04-04 JP JP8351787A patent/JPS63249142A/en active Pending
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