JPH0359652A - Silver halide photographic sensitive material subjected to antistatic treatment - Google Patents
Silver halide photographic sensitive material subjected to antistatic treatmentInfo
- Publication number
- JPH0359652A JPH0359652A JP19719489A JP19719489A JPH0359652A JP H0359652 A JPH0359652 A JP H0359652A JP 19719489 A JP19719489 A JP 19719489A JP 19719489 A JP19719489 A JP 19719489A JP H0359652 A JPH0359652 A JP H0359652A
- Authority
- JP
- Japan
- Prior art keywords
- group
- silver halide
- groups
- layer
- antistatic
- 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
- -1 Silver halide Chemical class 0.000 title claims abstract description 104
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 52
- 239000004332 silver Substances 0.000 title claims abstract description 52
- 239000000463 material Substances 0.000 title claims abstract description 25
- 238000011282 treatment Methods 0.000 title description 6
- 239000002245 particle Substances 0.000 claims abstract description 22
- 229920001940 conductive polymer Polymers 0.000 claims abstract description 12
- 229920001600 hydrophobic polymer Polymers 0.000 claims abstract description 11
- 239000002985 plastic film Substances 0.000 claims abstract description 8
- 229920006255 plastic film Polymers 0.000 claims abstract description 8
- 150000004696 coordination complex Chemical class 0.000 claims abstract description 6
- 239000011701 zinc Substances 0.000 claims abstract description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 5
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract 3
- 239000000839 emulsion Substances 0.000 claims description 30
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Substances NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 16
- 238000012545 processing Methods 0.000 abstract description 9
- 239000004848 polyfunctional curative Substances 0.000 abstract description 5
- 230000015556 catabolic process Effects 0.000 abstract 1
- 239000002872 contrast media Substances 0.000 abstract 1
- 238000006731 degradation reaction Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 55
- 150000001875 compounds Chemical class 0.000 description 19
- 108010010803 Gelatin Proteins 0.000 description 17
- 239000008273 gelatin Substances 0.000 description 17
- 229920000159 gelatin Polymers 0.000 description 17
- 235000019322 gelatine Nutrition 0.000 description 17
- 235000011852 gelatine desserts Nutrition 0.000 description 17
- 239000000203 mixture Substances 0.000 description 17
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 13
- 238000011161 development Methods 0.000 description 13
- 230000018109 developmental process Effects 0.000 description 13
- 229920000642 polymer Polymers 0.000 description 13
- 238000000034 method Methods 0.000 description 12
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 10
- 238000000576 coating method Methods 0.000 description 10
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 10
- 230000035945 sensitivity Effects 0.000 description 10
- 125000001424 substituent group Chemical group 0.000 description 9
- 239000000084 colloidal system Substances 0.000 description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 8
- 238000003860 storage Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- 239000004816 latex Substances 0.000 description 7
- 229920000126 latex Polymers 0.000 description 7
- 150000003283 rhodium Chemical class 0.000 description 7
- 229910052717 sulfur Inorganic materials 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- ZTHYODDOHIVTJV-UHFFFAOYSA-N Propyl gallate Chemical compound CCCOC(=O)C1=CC(O)=C(O)C(O)=C1 ZTHYODDOHIVTJV-UHFFFAOYSA-N 0.000 description 6
- 206010070834 Sensitisation Diseases 0.000 description 6
- 229910021607 Silver chloride Inorganic materials 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- 239000003513 alkali Substances 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 230000008313 sensitization Effects 0.000 description 6
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical group [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 6
- 239000011593 sulfur Substances 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 229920000139 polyethylene terephthalate Polymers 0.000 description 5
- 239000005020 polyethylene terephthalate Substances 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- KAMCBFNNGGVPPW-UHFFFAOYSA-N 1-(ethenylsulfonylmethoxymethylsulfonyl)ethene Chemical compound C=CS(=O)(=O)COCS(=O)(=O)C=C KAMCBFNNGGVPPW-UHFFFAOYSA-N 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- SJOOOZPMQAWAOP-UHFFFAOYSA-N [Ag].BrCl Chemical compound [Ag].BrCl SJOOOZPMQAWAOP-UHFFFAOYSA-N 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- 230000006866 deterioration Effects 0.000 description 4
- 125000000623 heterocyclic group Chemical group 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- LRUDIIUSNGCQKF-UHFFFAOYSA-N 5-methyl-1H-benzotriazole Chemical compound C1=C(C)C=CC2=NNN=C21 LRUDIIUSNGCQKF-UHFFFAOYSA-N 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- XCFIVNQHHFZRNR-UHFFFAOYSA-N [Ag].Cl[IH]Br Chemical compound [Ag].Cl[IH]Br XCFIVNQHHFZRNR-UHFFFAOYSA-N 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 3
- ZUIVNYGZFPOXFW-UHFFFAOYSA-N chembl1717603 Chemical compound N1=C(C)C=C(O)N2N=CN=C21 ZUIVNYGZFPOXFW-UHFFFAOYSA-N 0.000 description 3
- 125000004093 cyano group Chemical group *C#N 0.000 description 3
- 125000000753 cycloalkyl group Chemical group 0.000 description 3
- 238000007720 emulsion polymerization reaction Methods 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 150000002334 glycols Chemical class 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 3
- 239000006224 matting agent Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 235000010388 propyl gallate Nutrition 0.000 description 3
- 239000001397 quillaja saponaria molina bark Substances 0.000 description 3
- 229930182490 saponin Natural products 0.000 description 3
- 150000007949 saponins Chemical class 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea group Chemical group NC(=S)N UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- GGZHVNZHFYCSEV-UHFFFAOYSA-N 1-Phenyl-5-mercaptotetrazole Chemical compound SC1=NN=NN1C1=CC=CC=C1 GGZHVNZHFYCSEV-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- LPYUENQFPVNPHY-UHFFFAOYSA-N 3-methoxycatechol Chemical compound COC1=CC=CC(O)=C1O LPYUENQFPVNPHY-UHFFFAOYSA-N 0.000 description 2
- FJWJYHHBUMICTP-UHFFFAOYSA-N 4,4-dimethylpyrazolidin-3-one Chemical compound CC1(C)CNNC1=O FJWJYHHBUMICTP-UHFFFAOYSA-N 0.000 description 2
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 2
- INVVMIXYILXINW-UHFFFAOYSA-N 5-methyl-1h-[1,2,4]triazolo[1,5-a]pyrimidin-7-one Chemical compound CC1=CC(=O)N2NC=NC2=N1 INVVMIXYILXINW-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical class C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 125000003172 aldehyde group Chemical group 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000005250 alkyl acrylate group Chemical class 0.000 description 2
- 125000004414 alkyl thio group Chemical group 0.000 description 2
- 125000000304 alkynyl 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
- 125000003368 amide group Chemical group 0.000 description 2
- 125000004069 aziridinyl group Chemical group 0.000 description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 2
- 239000012964 benzotriazole Substances 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- IYCOKCJDXXJIIM-UHFFFAOYSA-N butyl prop-2-enoate;prop-2-enoic acid;styrene Chemical compound OC(=O)C=C.C=CC1=CC=CC=C1.CCCCOC(=O)C=C IYCOKCJDXXJIIM-UHFFFAOYSA-N 0.000 description 2
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 2
- 229920002301 cellulose acetate Polymers 0.000 description 2
- 229960004106 citric acid Drugs 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 2
- 229960000878 docusate sodium Drugs 0.000 description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 150000002503 iridium Chemical class 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 description 2
- 235000019252 potassium sulphite Nutrition 0.000 description 2
- 239000003755 preservative agent Substances 0.000 description 2
- 230000002335 preservative effect Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 235000010265 sodium sulphite Nutrition 0.000 description 2
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 2
- 235000019345 sodium thiosulphate Nutrition 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 150000003440 styrenes Chemical class 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 2
- 229920006027 ternary co-polymer Polymers 0.000 description 2
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-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
- NJVOHKFLBKQLIZ-UHFFFAOYSA-N (2-ethenylphenyl) prop-2-enoate Chemical compound C=CC(=O)OC1=CC=CC=C1C=C NJVOHKFLBKQLIZ-UHFFFAOYSA-N 0.000 description 1
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
- DTCCVIYSGXONHU-CJHDCQNGSA-N (z)-2-(2-phenylethenyl)but-2-enedioic acid Chemical compound OC(=O)\C=C(C(O)=O)\C=CC1=CC=CC=C1 DTCCVIYSGXONHU-CJHDCQNGSA-N 0.000 description 1
- QDNPCYCBQFHNJC-UHFFFAOYSA-N 1,1'-biphenyl-3,4-diol Chemical compound C1=C(O)C(O)=CC=C1C1=CC=CC=C1 QDNPCYCBQFHNJC-UHFFFAOYSA-N 0.000 description 1
- AIGNCQCMONAWOL-UHFFFAOYSA-N 1,3-benzoselenazole Chemical group C1=CC=C2[se]C=NC2=C1 AIGNCQCMONAWOL-UHFFFAOYSA-N 0.000 description 1
- 125000000355 1,3-benzoxazolyl group Chemical group O1C(=NC2=C1C=CC=C2)* 0.000 description 1
- ODIRBFFBCSTPTO-UHFFFAOYSA-N 1,3-selenazole Chemical group C1=C[se]C=N1 ODIRBFFBCSTPTO-UHFFFAOYSA-N 0.000 description 1
- OXLXSOPFNVKUMU-UHFFFAOYSA-N 1,4-dioctoxy-1,4-dioxobutane-2-sulfonic acid Chemical class CCCCCCCCOC(=O)CC(S(O)(=O)=O)C(=O)OCCCCCCCC OXLXSOPFNVKUMU-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- RVXJIYJPQXRIEM-UHFFFAOYSA-N 1-$l^{1}-selanyl-n,n-dimethylmethanimidamide Chemical compound CN(C)C([Se])=N RVXJIYJPQXRIEM-UHFFFAOYSA-N 0.000 description 1
- BHUXAQIVYLDUQV-UHFFFAOYSA-N 1-(diethylamino)propan-2-ol Chemical compound CCN(CC)CC(C)O BHUXAQIVYLDUQV-UHFFFAOYSA-N 0.000 description 1
- NXVHEHXRZVQDCR-UHFFFAOYSA-N 1-n,1-n-diethyl-2-methylbenzene-1,4-diamine Chemical compound CCN(CC)C1=CC=C(N)C=C1C NXVHEHXRZVQDCR-UHFFFAOYSA-N 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N 1-propanol Substances CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 229940044613 1-propanol Drugs 0.000 description 1
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- XIROXSOOOAZHLL-UHFFFAOYSA-N 2',3',4'-Trihydroxyacetophenone Chemical compound CC(=O)C1=CC=C(O)C(O)=C1O XIROXSOOOAZHLL-UHFFFAOYSA-N 0.000 description 1
- CTTJWXVQRJUJQW-UHFFFAOYSA-N 2,2-dioctyl-3-sulfobutanedioic acid Chemical compound CCCCCCCCC(C(O)=O)(C(C(O)=O)S(O)(=O)=O)CCCCCCCC CTTJWXVQRJUJQW-UHFFFAOYSA-N 0.000 description 1
- XIWRQEFBSZWJTH-UHFFFAOYSA-N 2,3-dibromobenzene-1,4-diol Chemical compound OC1=CC=C(O)C(Br)=C1Br XIWRQEFBSZWJTH-UHFFFAOYSA-N 0.000 description 1
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- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 description 1
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- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
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- AFOSIXZFDONLBT-UHFFFAOYSA-N divinyl sulfone Chemical group C=CS(=O)(=O)C=C AFOSIXZFDONLBT-UHFFFAOYSA-N 0.000 description 1
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- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
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- 150000004820 halides Chemical class 0.000 description 1
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- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
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- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Chemical class CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
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- 125000002971 oxazolyl group Chemical group 0.000 description 1
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- 125000004115 pentoxy group Chemical group [*]OC([H])([H])C([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- CMCWWLVWPDLCRM-UHFFFAOYSA-N phenidone Chemical compound N1C(=O)CCN1C1=CC=CC=C1 CMCWWLVWPDLCRM-UHFFFAOYSA-N 0.000 description 1
- 150000003057 platinum Chemical class 0.000 description 1
- 229920006289 polycarbonate film Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
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- 229940075579 propyl gallate Drugs 0.000 description 1
- NDGRWYRVNANFNB-UHFFFAOYSA-N pyrazolidin-3-one Chemical compound O=C1CCNN1 NDGRWYRVNANFNB-UHFFFAOYSA-N 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- 125000001422 pyrrolinyl group Chemical group 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 1
- 235000020185 raw untreated milk Nutrition 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 230000005070 ripening Effects 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 125000003748 selenium group Chemical group *[Se]* 0.000 description 1
- IYKVLICPFCEZOF-UHFFFAOYSA-N selenourea Chemical compound NC(N)=[Se] IYKVLICPFCEZOF-UHFFFAOYSA-N 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229940087562 sodium acetate trihydrate Drugs 0.000 description 1
- PPASLZSBLFJQEF-RKJRWTFHSA-M sodium ascorbate Substances [Na+].OC[C@@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RKJRWTFHSA-M 0.000 description 1
- 235000010378 sodium ascorbate Nutrition 0.000 description 1
- 229960005055 sodium ascorbate Drugs 0.000 description 1
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Inorganic materials [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
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- FZHLWVUAICIIPW-UHFFFAOYSA-M sodium gallate Chemical compound [Na+].OC1=CC(C([O-])=O)=CC(O)=C1O FZHLWVUAICIIPW-UHFFFAOYSA-M 0.000 description 1
- PPASLZSBLFJQEF-RXSVEWSESA-M sodium-L-ascorbate Chemical compound [Na+].OC[C@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RXSVEWSESA-M 0.000 description 1
- SDKPSXWGRWWLKR-UHFFFAOYSA-M sodium;9,10-dioxoanthracene-1-sulfonate Chemical compound [Na+].O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2S(=O)(=O)[O-] SDKPSXWGRWWLKR-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
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- 239000003381 stabilizer Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 125000000626 sulfinic acid group Chemical group 0.000 description 1
- 125000000565 sulfonamide group Chemical group 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 150000003866 tertiary ammonium salts Chemical class 0.000 description 1
- WAGFXJQAIZNSEQ-UHFFFAOYSA-M tetraphenylphosphonium chloride Chemical compound [Cl-].C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 WAGFXJQAIZNSEQ-UHFFFAOYSA-M 0.000 description 1
- 125000003831 tetrazolyl group Chemical group 0.000 description 1
- 150000003475 thallium Chemical class 0.000 description 1
- 125000002769 thiazolinyl group Chemical group 0.000 description 1
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylene diamine Substances C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 229920001567 vinyl ester resin Chemical class 0.000 description 1
- 239000012224 working solution Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、プラスチックフィルム支持体用の帯電防止層
に関し、特に帯電防止能の優れたハロゲン化銀写真感光
材料に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to an antistatic layer for a plastic film support, and more particularly to a silver halide photographic material with excellent antistatic ability.
一般にプラスチイックフィルム支持体は、帯電性が強く
、これが使用上多くの制約を与えている例は多い。例え
ばハロゲン化銀写真感光材料においてはポリエチレンテ
レフタレートのような支持体が一般に使用されるが１、
特に冬季の如き低湿度において帯電し易い。最近のよう
に高感度写真乳剤を高速度で塗布したり、高感度の感光
材料を自動プリンターを通して露光処理をする場合、特
に帯電防止対策が重要である。Generally, plastic film supports have strong electrostatic properties, and this often imposes many restrictions on their use. For example, supports such as polyethylene terephthalate are generally used in silver halide photographic materials.
It is easy to be charged especially in low humidity such as winter. Antistatic measures are especially important when high-speed photographic emulsions are coated at high speeds or when high-sensitivity photosensitive materials are exposed to light using automatic printers, as has been the case recently.
感光材料が帯電すると、その放電によりスタチックマー
クがでたり、またはゴミ等の異物を付着し、これにより
ピンホールを発生させたりして著しく品質を劣化し、そ
の修正のため非常に作業性をおとしてしまう。このため
、一般に感光材料では帯電防止剤が使用され、最近では
、含フツ素界面活性剤、カチオン界面活性剤、両性界面
活性剤、ポリエチレンオキサイド基を含有する界面活性
剤ないし高分子化合物、スルホン酸又はリン酸基を分子
内に有するポリマー等が用いられている。When a photosensitive material is charged, static marks appear due to the discharge, or foreign matter such as dust adheres to it, which causes pinholes and significantly degrades the quality, making it extremely difficult to repair. I'll put it down. For this reason, antistatic agents are generally used in photosensitive materials, and recently, fluorine-containing surfactants, cationic surfactants, amphoteric surfactants, surfactants or polymer compounds containing polyethylene oxide groups, and sulfonic acid Alternatively, a polymer having a phosphoric acid group in the molecule is used.
特にフッ素系界面活性剤による帯電列調整、あるいは導
電性ポリマーによる導電性向上が多く使用されてきてお
り、例えば特開昭４９−９１１６５号および同４９−１
２１５２３号にはポリマー主鎖中に解離基を有するイオ
ン型ポリマーを適用する例が開示されている。In particular, adjusting the charge series using fluorine-based surfactants or improving conductivity using conductive polymers has been widely used, for example, in JP-A-49-91165 and JP-A-49-1.
No. 21523 discloses an example in which an ionic polymer having a dissociative group in the polymer main chain is applied.
しかしながら、これらの従来技術では、現像処理により
、帯電防止能が大幅に劣化してしまう。However, in these conventional techniques, the antistatic ability is significantly deteriorated by the development process.
これはアルカリを用いる現像工程、酸性の定着工程、水
洗等の工程を経ることにより帯電防止能が失われるもの
と思われる。したがって印刷感光材料等のように、処理
済みフィルムをさらに用いてプリントするような場合に
、ゴミの付着によるピンホール発生等の問題を生ずる。This is thought to be because the antistatic ability is lost through processes such as a developing process using an alkali, an acidic fixing process, and washing with water. Therefore, when a processed film is further used for printing, such as with printing photosensitive materials, problems such as pinholes occur due to adhesion of dust.
このため例えば特開昭５５−８４６５８号、同６１−１
７４５４２号ではカルボキシル基を有する水溶性導電性
ポリマー カルボキシル基を有する疎水性ポリマー及び
多官能アジリジンからなる帯電防止層が提案されている
。この方法によれば処理後にも帯電防止能を残すことが
できるが、この帯電防止層は、この層の上にハレーショ
ン防止層などの親水性コロイド層を設けた場合、経時保
存中にひび割れを生じ、商品価値を大きく損なうことが
分かった。さらに、この帯電防止層を有するプラスチッ
クフィルム支持体に、テトラゾリウム化合物またはヒド
ラジン化合物を使った超硬調化乳剤を適用した場合、経
時保存で減感する欠点を有することが分かった。For this reason, for example, JP-A Nos. 55-84658 and 61-1
No. 74542 proposes an antistatic layer comprising a water-soluble conductive polymer having a carboxyl group, a hydrophobic polymer having a carboxyl group, and a polyfunctional aziridine. Although this method allows antistatic properties to remain after treatment, this antistatic layer may crack during storage over time if a hydrophilic colloid layer such as an antihalation layer is provided on top of this layer. , it was found that the product value was significantly impaired. Furthermore, it has been found that when an ultra-high contrast emulsion using a tetrazolium compound or a hydrazine compound is applied to a plastic film support having this antistatic layer, it has the disadvantage of desensitization during storage over time.
上記のような問題に対し、本発明の目的は、現像処理等
の処理後も帯電防止能の劣化が起こらず、経時保存中に
ひび割れを生じないノ１０ゲン化銀写真感光材料を提供
することであり、別の目的としては、テトラゾリウム化
合物またはヒドラジン化合物を使った超硬調化乳剤を適
用した場合経時で減感せず安定性の高いノ１０ゲン化銀
写真感光材料を提供することである。In view of the above-mentioned problems, an object of the present invention is to provide a silver 10 genide photographic material that does not deteriorate in antistatic ability even after processing such as development and does not cause cracks during storage over time. Another object of the present invention is to provide a highly stable silver 10 genide photographic material that does not desensitize over time when an ultra-high contrast emulsion containing a tetrazolium compound or a hydrazine compound is applied.
本発明の上記目的は、■水溶性導電性ポリマー■疎水性
ポリマー粒子■硬化剤の反応生成物からなる帯電防止層
を有してなるプラスチックフィルム支持体において、該
硬化剤として亜鉛及びジルコニウム金属を含有する金属
錯体を用いることを特徴とする帯電防止層を有するハロ
ゲン化銀写真感光材料により達成された。The above-mentioned object of the present invention is to provide a plastic film support having an antistatic layer consisting of (1) a water-soluble conductive polymer, (2) hydrophobic polymer particles, and (3) a reaction product of a hardening agent, in which zinc and zirconium metals are used as the hardening agent. This was achieved by a silver halide photographic material having an antistatic layer characterized by using a metal complex containing the same.
尚、上記感光性乳剤層中には、ヒドラジン化合物または
テトラゾリウム化合物を含有することが望ましい。The photosensitive emulsion layer preferably contains a hydrazine compound or a tetrazolium compound.
以下、本発明の詳細について説明する。The details of the present invention will be explained below.
本発明の水溶性導電性ポリマーは、単独で使用すること
によっても透明な層を形成し得るが、少しの乾燥条件の
ブレによって層のひび割れを引き起こしてしまう。本発
明の構成ではそのひび割れを防ぐために疎水性ポリマー
粒子を含有しているが、その効果は大きい。Although the water-soluble conductive polymer of the present invention can form a transparent layer when used alone, a slight fluctuation in drying conditions may cause cracks in the layer. The structure of the present invention contains hydrophobic polymer particles to prevent cracking, and the effect is significant.
本発明の請求１１記載の水溶性導電性ポリマーについて
は、スルホン酸基、硫酸エステル基、４級アンモニウム
塩、３級アンモニウム塩、カルボキシル基、ポリエチレ
ンオキシド基から選ばれる少なくとも１つの導電性基を
有するポリマーが挙げられる。これらの基のうちスルホ
ン酸基、ｉｓエステル基、４級アンモニウム塩基が好ま
しい。The water-soluble conductive polymer according to claim 11 of the present invention has at least one conductive group selected from a sulfonic acid group, a sulfuric acid ester group, a quaternary ammonium salt, a tertiary ammonium salt, a carboxyl group, and a polyethylene oxide group. Examples include polymers. Among these groups, sulfonic acid groups, is ester groups, and quaternary ammonium bases are preferred.
導電性基はポリマー１分子当たり５重量％以上を必要と
する。水溶性の導電性ポリマー中に含まれるカルボキシ
基、ヒドロキシ基、アミノ基、エポキシ基、アジリジン
基、活性メチレン基、スルフィン酸基、アルデヒド基、
ビニルスルホン基のうち、カルボキシ基、ヒドロキシ基
、アミノ基、エポキシ基、アジリジン基、アルデヒド基
が好ましい。The amount of conductive groups required is 5% by weight or more per polymer molecule. Carboxy groups, hydroxy groups, amino groups, epoxy groups, aziridine groups, active methylene groups, sulfinic acid groups, aldehyde groups contained in water-soluble conductive polymers,
Among vinyl sulfone groups, carboxy groups, hydroxy groups, amino groups, epoxy groups, aziridine groups, and aldehyde groups are preferred.
これらの基はポリマー１分子当たり５重量％以上必要と
する。ポリマーの分子量は、３０００−１０００００で
あり、好ましくは３５００〜５ｏｏｏｏでアル。These groups are required in an amount of 5% by weight or more per polymer molecule. The molecular weight of the polymer is 3000-100000, preferably 3500-5oooo.
以下、本発明に用いられる水溶性導電性ポリマーの化合
物例を挙げるがこれに限定されるものでＡ−１
ホモポリマー
−２
ホモポリマー
−３
）す３Ｎａ
Ｓｏ 、 Ｎａ
−６
ＣＨｌ
Ｓｏ 、 Ｎａ
−７
−８
ＳＯ．Ｎａ
−９
−１０
− １１
− １２
ＣＨ。Examples of compounds of the water-soluble conductive polymer used in the present invention are listed below, but are not limited thereto. -8 SO. Na-9-10-11-12CH.
Ｑ −１３ − １４ − １５ Ｈ３ １７ ９ −２０ −２１ −２２ 八−２３ デキストランサルフエイト 置換度 ２．０ Ｍ −１０万 −２４ −２５ −２６ ７− Ｏ３Ｎａ −２９ −３０ −３１ −３２ Ａ −３３ Ａ−３４ 八−３５ −３６ −３７ −３８ −３９ −４０ ＣＨ。Q -13 -14 -15 H3 17 9 -20 -21 -22 8-23 dextran sulfate Degree of substitution 2.0 M - 100,000 -24 -25 -26 7- O3Na -29 -30 -31 -32 A-33 A-34 8-35 -36 -37 -38 -39 -40 CH.
−４１ Ｓｏ 、 Ｎａ −４２ −４３ ｘ：ｙ：ｚ−８０：１０：１０ Ｍｔ１万 Ｍ＃ｊカ −４４ −４５ −４６ ＣＨ。-41 So, Na -42 -43 x:y:z-80:10:10 Mt10,000 M #j Ka -44 -45 -46 CH.
ｘ：ｙ：ｚ：ｖ＝４０：３０：２０：１０Ｍ＃５万
Ａ−４７
Ａ−４８
−４９
）υ工Ｎａ
Ｍ均６万
−５０
尚、上記（１）〜（５ｏ）において、ｘ＊Ｙ＊Ｚはそれ
ぞれ単量体成分のモル％を、又Ｍは平均分子量（本明細
書中、平均分子量とは数平均分子量を示す。）を表す。x:y:z:v=40:30:20:10M#50,000A-47 A-48-49) υtechnical Na M60,000-50 In addition, in (1) to (5o) above, x* Y*Z each represents the mol% of the monomer component, and M represents the average molecular weight (in this specification, the average molecular weight refers to the number average molecular weight).
これらのポリマーは市販又は常法によって得られる七ツ
マ−を重合することにより合成することが出来る。これ
らの化合物の添加量は０．０１ｇ” １０ｇ／、２が好
ましく、特に好ましくは０．１ｇ〜５ｇ／ｌである。These polymers can be synthesized by polymerizing heptamers that are commercially available or obtained by conventional methods. The amount of these compounds added is preferably 0.01 g/10 g/l, particularly preferably 0.1 g/l to 5 g/l.
次に本発明の水溶性導電性ポリマー層中に含有させる疎
水性ポリマー粒子は、実質的に水に溶解しない所謂ラテ
ックス状で含有されている。この疎水性ポリマーは、ス
チレン、スチレン誘導体、アルキルアクリレート、アル
キルメタクリレート、オレフィン誘導体、ハロゲン化エ
チレン誘導体、アクリルアミド誘導体、メタクリルアミ
ド誘導体、ビニルエステル誘導体、アクリロニトリル等
の中から任意の組み合わせで選ばれた七ツマ−を重合し
て得られる。特にスチレン誘導体、アルキルアクリレー
ト、アルキルメタクリレートが少なくとも３０モル％含
有されているのが好ましい。特に５０モル％以上が好ま
しい。Next, the hydrophobic polymer particles contained in the water-soluble conductive polymer layer of the present invention are contained in a so-called latex form that is substantially insoluble in water. This hydrophobic polymer can be any combination of styrene, styrene derivatives, alkyl acrylates, alkyl methacrylates, olefin derivatives, halogenated ethylene derivatives, acrylamide derivatives, methacrylamide derivatives, vinyl ester derivatives, acrylonitrile, etc. - obtained by polymerizing. In particular, it is preferable that at least 30 mol% of styrene derivatives, alkyl acrylates, and alkyl methacrylates are contained. Particularly preferred is 50 mol% or more.
疎水性ポリマーをラテックス状にするには乳化重合をす
る、固体状のポリマーを低沸点溶媒に溶かして微分散後
、溶媒を留去するという２つの方法があるが粒径が細か
く、しかもそろったものができるという点で乳化重合す
ることが好ましい。There are two methods to make a hydrophobic polymer into a latex form: emulsion polymerization, or dissolving a solid polymer in a low boiling point solvent, finely dispersing it, and then distilling off the solvent. Emulsion polymerization is preferable because it can produce a product.
乳化重合の際に用いる界面活性剤としては、アニオン性
、ノニオン性を用いるのが好ましく、モノマーに対し１
０重量％以下が好ましい。多量の界面活性剤は導電性層
をくもらせる原因となる。As the surfactant used during emulsion polymerization, it is preferable to use an anionic or nonionic surfactant.
It is preferably 0% by weight or less. A large amount of surfactant causes clouding of the conductive layer.
疎水性ポリマーの分子量は３０００以上であれば良く、
分子量による透明性の差はほとんどない。The molecular weight of the hydrophobic polymer may be 3000 or more,
There is almost no difference in transparency depending on molecular weight.
本発明の疎水性ポリマーの具体例を挙げる。Specific examples of the hydrophobic polymer of the present invention will be given below.
７ ｌＯ １２ ＣＨ。7 lO 12 CH.
１３ ｃｏｏｃｎ ５ ＣＯＯＣ，Ｈ，０１（ ＣｏＯＨ −１４ ＣＨ。13 coocn 5 COOC,H,01( CoOH -14 CH.
１５
ＣＮ Ｃ００ＣａＨｓ ｎ Ｃｏ
ＯＨ次に、本発明に用いられる亜鉛及びジルコニウム金
属を含有する金属錯体の具体例を示すが、これに限定さ
れるものではない。15 CN C00CaHs n Co
OHNext, specific examples of metal complexes containing zinc and zirconium metals used in the present invention will be shown, but the invention is not limited thereto.
Ｃ−Ｉ Ｃ−２Ｚｎ（ＮＨ
３）ｉ（ＣＨｉＣＯＯ）ｚ Ｚｎ（ＮＨｓ
）ａｃｏｓ−３
（ＮＨａ）ＪｎＯＨ（ＣＯｓ）ｓ
上記金属錯体の使用量は導電性ポリマー１モルに対して
１０１〜１０’モルが好ましい。C-I C-2Zn(NH
3) i(CHiCOO)z Zn(NHs
) acos-3 (NHa)JnOH(COs)s The amount of the metal complex used is preferably 101 to 10' mol per 1 mol of the conductive polymer.
従来、有機架橋剤が主に使用されていたが、本発明の金
属錯体を使用することにより架橋が充分側われるように
なった。Conventionally, organic crosslinking agents have been mainly used, but by using the metal complex of the present invention, crosslinking can be sufficiently prevented.
本発明に用いられるヒドラジン化合物は、好ましくは下
記−数式（Ｈ）で表される化合物である。The hydrazine compound used in the present invention is preferably a compound represented by the following formula (H).
−数式（Ｈ） Ｒ，−Ｎ −Ｎ −Ｃ−Ｒ。-Formula (H) R, -N -N -C-R.
式中、Ｒ１は１価の有機残基を表し、Ｒ２は水素原子ま
たは１価の有機残基を表し、Ｑｌ及びＱ２は水素原子、
アルキルスルホニル基（置換基を有するものも含む）、
アリールスルホニル基（置換基を有するものも含む）を
表し、Ｘｌは酸素原子まｔ；はイオウ原子を表す。−数
式ＣＩ）で表される化合物のうち、ｘｌが酸素原子であ
り、かつＲ２が水素原子である化合物が更に好ましい。In the formula, R1 represents a monovalent organic residue, R2 represents a hydrogen atom or a monovalent organic residue, Ql and Q2 represent a hydrogen atom,
Alkylsulfonyl group (including those with substituents),
represents an arylsulfonyl group (including one having a substituent); Xl represents an oxygen atom; and Xl represents a sulfur atom. -Among the compounds represented by the formula CI), compounds in which xl is an oxygen atom and R2 is a hydrogen atom are more preferred.
上記Ｒ，及びＲ２の１価の有機残基としては、芳香族残
基、複素環残基及び脂肪族残基が包含される。The monovalent organic residues for R and R2 include aromatic residues, heterocyclic residues, and aliphatic residues.
芳香族残基としては、フェニル基、ナフチル基及びこれ
らに置換基（例えばアルキル基、アルコキシ基、アシル
ヒドラジノ基、ジアルキルアミノ基、アルコキシカルボ
ニル基、シアノ基、カルボキシ基、ニトロ基、アルキル
チオ基、ヒドロキシ基、スルホニル基、カルバモイル基
、ハロゲン原子、アシルアミノ基、スルホンアミド基、
ウレア基、チオウレア基など）のついたものを含む。置
換基のついたものの具体例として、例えば、４−メチル
フェニル基、４−エチルフェニル基、４−オキシエチル
フェニル基、４−ドデシルフェニル基、４−カルボキシ
フェニル基、４−ジエチルアミノフェニル基、４−オク
チルアミノフェニル基、４−ベンジルアミノフェニル基
、４−アセトアミド−２−メチルフェニル基、４−（３
−エチルチオウレイド）フェニル基、４−［２−（２，
４−ジーｔｅｒｔ−ブチルフェノキシ）ブチルアミド］
フェニル基、４−［２−（２，４−ジーｔａｒｔ−ブチ
ルフェノキシ）ブチルアミド］フェニル基などを挙げる
ことができる。Aromatic residues include phenyl groups, naphthyl groups, and substituents thereof (for example, alkyl groups, alkoxy groups, acylhydrazino groups, dialkylamino groups, alkoxycarbonyl groups, cyano groups, carboxy groups, nitro groups, alkylthio groups, and hydroxy groups). , sulfonyl group, carbamoyl group, halogen atom, acylamino group, sulfonamide group,
urea group, thiourea group, etc.). Specific examples of those with substituents include 4-methylphenyl group, 4-ethylphenyl group, 4-oxyethylphenyl group, 4-dodecylphenyl group, 4-carboxyphenyl group, 4-diethylaminophenyl group, -octylaminophenyl group, 4-benzylaminophenyl group, 4-acetamido-2-methylphenyl group, 4-(3
-ethylthioureido)phenyl group, 4-[2-(2,
4-di-tert-butylphenoxy)butyramide]
Examples include phenyl group, 4-[2-(2,4-di-tart-butylphenoxy)butyramido]phenyl group, and the like.
複素環残基としては、酸素、窒素、硫黄、またはセレン
原子のうち少なくとも一つを有する五員もしくは六員の
単環または縮合環で、これらに置換基がついてもよい。The heterocyclic residue is a five- or six-membered monocyclic ring or fused ring having at least one of oxygen, nitrogen, sulfur, or selenium atoms, and a substituent may be attached thereto.
具体的には例えば、ピロリン環、ピリジン環、キノリン
環、インドール環、オキサゾール環、ベンゾオキサゾー
ル環、ナフトオキサゾール環、イミダゾール環、ベンゾ
イミダゾール環、チアゾリン環、チアゾール環、ベンゾ
チアゾール環、ナフトチアゾール環、セレナゾール環、
ベンゾセレナゾール環、ナフトセレナゾール環などの残
基を挙げることが出来る。Specifically, for example, pyrroline ring, pyridine ring, quinoline ring, indole ring, oxazole ring, benzoxazole ring, naphthoxazole ring, imidazole ring, benzimidazole ring, thiazoline ring, thiazole ring, benzothiazole ring, naphthothiazole ring, selenazole ring,
Examples include residues such as a benzoselenazole ring and a naphthoselenazole ring.
これらの複素環は、メチル基、エチル基環炭素数１〜４
のアルキル基、メトキシ基、エトキシ基環炭素数ｌ〜４
のアルコキシ基、フェニル基等の炭素数６〜１８のアリ
ール基や、クロル、ブロム等のハロゲン原子、アルコキ
シカルボニル基、シアノ基、アミ７基等で置換されてい
てもよい。These heterocycles include a methyl group and an ethyl group having 1 to 4 carbon atoms.
Alkyl group, methoxy group, ethoxy group ring carbon number 1 to 4
may be substituted with an aryl group having 6 to 18 carbon atoms such as an alkoxy group or a phenyl group, a halogen atom such as chloro or bromine, an alkoxycarbonyl group, a cyano group, or an amide group.
脂肪族残基としては、直鎖及び分岐のアルキル基、シク
ロアルキル基及びこれらに置換基のついたもの、並びに
アルケニル基及びアルキニル基を含む。Aliphatic residues include linear and branched alkyl groups, cycloalkyl groups, and those with substituents, as well as alkenyl groups and alkynyl groups.
直鎖及び分岐のアルキル基としては、例えば炭素数１〜
１８、好ましくは１〜８のアルキル基であって、具体的
には例えばメチル基、エチル基、イソブチル基、ｌ−オ
クチル基等である。Straight-chain and branched alkyl groups include, for example, those having 1 to 1 carbon atoms.
18, preferably an alkyl group of 1 to 8, and specific examples include a methyl group, ethyl group, isobutyl group, l-octyl group, and the like.
シクロアルキル基としては、例えば炭素数３〜ｌＯのも
ので、具体的には例えばシクロプロピル基、シクロヘキ
シル基、アダマンチル基等である。アルキル基やシクロ
アルキル基に対する置換基としてはアルコキシ基（例え
ばメトキシ基、エトキシ１基、プロポキシ基、ブトキシ
基等）、アルコキシカルボニル基、カルバモイル基、ヒ
ドロキシ基、アルキルチオ基、アミド基、アシロキシ基
、シアノ基、スルホニル基、ハロゲン原子（例えば塩素
、臭素、弗素、沃素など）、アリール基（例えば）工二
ル基、ハロゲン置換フェニル基、アルキル置換フェニル
基）等であり、置換されたものの具体例としては例えば
３−メトキシゾロビル基、エトキシカルボニルメチル基
、４−クロロシクロヘキシル基、ヘンシル基、ｐ−メチ
ルベンジル基、ｐ−クロロベンジル基などを挙げること
ができる。また、アルケニル基としては例えばアリル（
ａｌｌｙｌ）基、アルキニル基としては例えばプロバル
ギル基を挙げることができる。Examples of the cycloalkyl group include those having 3 to 10 carbon atoms, such as cyclopropyl, cyclohexyl, adamantyl, and the like. Substituents for alkyl groups and cycloalkyl groups include alkoxy groups (e.g. methoxy, ethoxy, propoxy, butoxy, etc.), alkoxycarbonyl groups, carbamoyl groups, hydroxy groups, alkylthio groups, amide groups, acyloxy groups, cyano groups, etc. groups, sulfonyl groups, halogen atoms (e.g., chlorine, bromine, fluorine, iodine, etc.), aryl groups (e.g., diyl groups, halogen-substituted phenyl groups, alkyl-substituted phenyl groups), etc., and specific examples of substituted ones include Examples of the group include 3-methoxyzorobyl group, ethoxycarbonylmethyl group, 4-chlorocyclohexyl group, Hensyl group, p-methylbenzyl group, and p-chlorobenzyl group. In addition, examples of alkenyl groups include allyl (
Examples of the allyl) group and the alkynyl group include a probargyl group.
本発明のヒドラジン化合物の好ましい具体例を以下に示
すが、
本発明は何等これによって限定さ
れるものではない。Preferred specific examples of the hydrazine compound of the present invention are shown below, but the present invention is not limited thereto in any way.
− − − −６ Ｃ，Ｈ。− − − -6 C,H.
−７ Ｈ−８ −９ −１０ −１１ ２ −１４ −１６ −１７ −１８ −１９ ０ １ ３ ＣＨ。-7 H-8 -9 -10 -11 2 -14 -16 -17 -18 -19 0 1 3 CH.
し１１３ −２４ −２５ −２８ ＣＨ１ Ｈ−２９ Ｈ−３３ −３４ −３５ −３８ −３９ Ｌｕｌ′Ｉ。113 -24 -25 -28 CH1 H-29 H-33 -34 -35 -38 -39 Lul'I.
−４１
−４２
−４３
ＣＨ３
−４４
−４５
−４６
一般式（Ｈ）で表わされるヒドラジン化合物の添加位置
はハロゲン化銀乳剤層及び／または支持体上のハロゲン
化銀乳剤層側にある非感光層であるが、好ましくは、ハ
ロゲン化銀乳剤層及び／またはその下層である。添加量
は、１０”’〜１０−１モル／銀１モルが好ましく、更
に好ましくは１０−′〜１Ｏ−２モル／銀１モルである
。-41 -42 -43 CH3 -44 -45 -46 The hydrazine compound represented by general formula (H) is added to the silver halide emulsion layer and/or the non-photosensitive layer on the silver halide emulsion layer side of the support. However, preferred is the silver halide emulsion layer and/or its lower layer. The amount added is preferably 10'' to 10-1 mol/mol of silver, and more preferably 10'' to 10-2 mol/mol of silver.
次に本発明に用いられるテトラゾリウム化合物について
説明する。Next, the tetrazolium compound used in the present invention will be explained.
テトラゾリウム化合物は下記−数式で示すことができる
。The tetrazolium compound can be represented by the following formula.
一般式
（Ｔ）
本発明において、上記一般式（Ｔ）で示されるトリノエ
ニルテトラゾリウム化合物のフェニル基の置換基ＲＩ、
Ｒ！、Ｒ３は水素原子もしくは電子吸引仕度を示すハメ
ットのシグマ値（σＰ）が負又は正のものが好ましい。General formula (T) In the present invention, a substituent RI of the phenyl group of the trinoenyltetrazolium compound represented by the above general formula (T),
R! , R3 preferably have a hydrogen atom or a Hammett's sigma value (σP) indicating the ability to attract electrons is negative or positive.
特に負のものが好ましい。In particular, negative ones are preferred.
フェニル置換におけるハメットのシグマ値は多くの文献
、例えばジャーナル・オブ・メディカルケ ミ ス ト
リ − （Ｊｏｕｒｎａｌ ｏｆ Ｍｅｄｉｃａ
ｌ Ｃｈｅｍｉｓｔｒｙ）第２０巻、３０４頁、１９
７７午、記載のＣ，ハンクス（Ｃ。The Hammett sigma value for phenyl substitution has been reported in many publications, such as the Journal of Medical Chemistry.
l Chemistry) Volume 20, Page 304, 19
77 pm, C. Hanks (C.
Ｈａｎｓｃｂ）等の轍叉等に見ることが出来、とくに好
ましい負のシグマ値を有する基としては、例えばメチル
基（σＰ−−０．１７以下いずれもσＰ値）エチル基（
−０，１５）、シクロプロピル基（−０，２１）、ｎ−
プロピル基（−０，１３）、ｉｓｏプロピル基（−０，
１５）、シクロブチル基（−０，１５）、ｎ−ブチル基
（−０，１６）、１ｓＯ−ブチル基（−０，２０）、ｎ
−ペンチル基（−０，１５）、シクロヘキシル基（−０
，２２）、アミノ基（−０，６６）、アセチルアミノ基
（−０，１５）、 ヒドロキシル基（−０，３７）、
メトキシ基（−０，２７）、エトキシ基（−０，２４）
、プロポキシ基（−０，２５）、ブトキシ基（−０，３
２）、ペントキシ基（−０，３４）等が挙げられ、これ
らはいずれも本発明の一般式〔Ｔ〕の化合物の置換基と
して有用である。Particularly preferable groups having a negative sigma value include, for example, a methyl group (σP value of 0.17 or less), an ethyl group (
-0,15), cyclopropyl group (-0,21), n-
Propyl group (-0,13), isopropyl group (-0,
15), cyclobutyl group (-0,15), n-butyl group (-0,16), 1sO-butyl group (-0,20), n
-pentyl group (-0,15), cyclohexyl group (-0
,22), amino group (-0,66), acetylamino group (-0,15), hydroxyl group (-0,37),
Methoxy group (-0,27), ethoxy group (-0,24)
, propoxy group (-0,25), butoxy group (-0,3
2), pentoxy group (-0,34), etc., and these are all useful as substituents for the compound of general formula [T] of the present invention.
以下本発明に用いられる一般式（Ｔ）の化合物の具体例
を挙げるが、本発明の化合物はこれに限＼、・１．ｒ／
＼□□□□□□□□□□□□□−一、／（例示化合物）
−１
−４
−５
−６−
７−
Ｔ−９
Ｔ −１０
−１１
−１２
−１３
−１４
−１５
−１６
−１７
−１８
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・レビュー（Ｃｈｅｍｉｃａｌ Ｒｅｖｉｅｗｓ
）第５５巻、第３３５頁〜４８３頁に記載の方法に従っ
て容易に合皮することができる。Specific examples of the compound of general formula (T) used in the present invention are listed below, but the compounds of the present invention are limited to these\, 1. r/ \□□□□□□□□□□□□□-1, / (exemplary compound) -1 -4 -5 -6- 7- T-9 T -10 -11 -12 -13 -14 - 15 -16 -17 -18 The tetrazolium compound used in the present invention is described, for example, in Chemical Reviews.
) Vol. 55, pp. 335-483, it can be easily made into synthetic leather.
本発明のテトラゾリウム化合物は、本発明のハロゲン化
銀写真感光材料中に含有されるハロゲン化銀１モル当り
約１ｍｇ以上１０ｇまで、好ましくは約１０ａ＋ｇ以上
約２ｇまでの範囲で用いられるのが好ましい。The tetrazolium compound of the present invention is preferably used in an amount of about 1 mg to 10 g, preferably about 10 a+g to about 2 g, per mole of silver halide contained in the silver halide photographic material of the present invention.
本発明に使用するテトラゾリウム化合物は、単独でもち
いることにより好ましい特性を得ることができるが、複
数をいかなる比率で組み合わせても好ましい特性を劣化
させることはない。The tetrazolium compounds used in the present invention can provide preferable properties when used alone, but the preferable properties will not deteriorate even when a plurality of them are combined in any ratio.
本発明の好ましい一つの実施態様として、本発明に係わ
るテトラゾリウム化合物をハロゲン化銀乳剤層中に添加
することが挙げられる。又本発明の別の好ましい実施態
様においては、ハロゲン化銀乳剤層に直接隣接する親水
性コロイド層、又は中間層を介して隣接する親水性コロ
イド層に添加される。One preferred embodiment of the present invention is to add the tetrazolium compound according to the present invention to a silver halide emulsion layer. In another preferred embodiment of the invention, it is added to a hydrophilic colloid layer directly adjacent to the silver halide emulsion layer, or to a hydrophilic colloid layer adjacent via an intermediate layer.
又別の態様としては、本発明に係わるテトラゾリウム化
合物を適当な有機溶媒、例えばメタノール、エタノール
等のアルコール類やエーテル類、エステル類等に溶解し
てオーバーコート法等によりハロゲン化銀写真感光材料
のハロゲン化銀乳剤層側の最外層になる部分に直接塗布
してハロゲン化銀写真感光材料に含有せしめてもよい。In another embodiment, the tetrazolium compound according to the present invention is dissolved in a suitable organic solvent, for example, alcohols such as methanol and ethanol, ethers, esters, etc., and then applied to a silver halide photographic light-sensitive material by an overcoating method or the like. It may be incorporated into the silver halide photographic material by directly coating the outermost layer on the side of the silver halide emulsion layer.
本発明に係るハロゲン化銀写真感光材料に用いるハロゲ
ン化銀は、任意の組成の塩化銀、塩臭化銀、塩沃臭化銀
等で少なくとも５０モル％の塩化銀を含有することが好
ましい。ハロゲン化銀粒子の平均粒径は０．０２５〜０
．５μｍの範囲のものが好ましく用いられるが０．０５
〜０．３０μｍがより好ましい。The silver halide used in the silver halide photographic material according to the present invention preferably has an arbitrary composition of silver chloride, silver chlorobromide, silver chloroiodobromide, etc., and preferably contains at least 50 mol % of silver chloride. The average grain size of silver halide grains is 0.025 to 0.
．． Those in the range of 5 μm are preferably used, but 0.05
-0.30 micrometer is more preferable.
本発明に係るハロゲン化銀粒子の単分散度は、下記式（
１）で定義され、その値は５〜６０が好ましく、より好
ましくは８〜３０となるよう調製する。The monodispersity of the silver halide grains according to the present invention is expressed by the following formula (
1), and its value is preferably adjusted to 5-60, more preferably 8-30.
本発明に係るハロゲン化銀粒子の粒径は、便宜的に立方
晶粒子の校長で表し、単分散度は粒径の標準偏差を平均
粒径で割った値を１００倍した数値で表す。The grain size of the silver halide grains according to the present invention is conveniently expressed as the principal dimension of cubic grains, and the monodispersity is expressed as the value obtained by dividing the standard deviation of the grain size by the average grain size times 100.
又、本発明で用い得るハロゲン化銀としては、少なくと
も２層の多層積層構造を有するタイプのものを好ましく
用いることができる。たとえばコア部に塩化銀、シェル
部に臭化銀、逆にコア部を臭化銀、シェル部を塩化銀で
ある塩臭化銀粒子であってもよい。このときヨードは任
意の層に５％モル以内で含有させることができる。Further, as the silver halide that can be used in the present invention, a type having a multilayer laminated structure of at least two layers can be preferably used. For example, silver chlorobromide particles may have silver chloride in the core and silver bromide in the shell, or conversely, silver bromide in the core and silver chloride in the shell. At this time, iodine can be contained in any layer within 5% by mole.
又、少なくとも２種類の粒子を混合して用いることもで
きる。例えば生乳粒子は１０モル％以下の塩化銀及び５
モル％以下のヨードを含有する立方晶、八面体又は平板
状の塩沃臭化銀粒子であり、副粒子はヨード５モル％以
下で塩化銀５０モル％以上含有する立方晶、八面体又は
平板状塩沃臭化銀粒子からなる混合粒子とすることがで
きる。このように粒子を混合して用いる場合は、主・副
粒子の化学増感は任意であるが、副粒子は主粒子より化
学増感（イオウ増感や金増感）を控えることにより感度
を低くしてもよいし、粒子径や内部にドープするロジウ
ムなどの貴金属の量を調節して感度を低下させてもよい
。また副粒子の内部を金でカブらせてもよいし、コア／
シェル法でコアとシェルの組成を変化させてカブらせて
もよい。主粒子と副粒子は小粒子程よいが、例えば０．
０２５μｍ〜１．０μｍの任意の値をとることができる
。Furthermore, a mixture of at least two types of particles can also be used. For example, raw milk grains contain up to 10 mol% silver chloride and 5
Cubic, octahedral, or tabular silver chloroiodobromide grains containing iodine of mol% or less; subgrains are cubic, octahedral, or tabular grains containing iodine of 5 mol% or less and silver chloride of 50 mol% or more. The mixed grains may be made of silver chloroiodobromide grains. When using a mixture of particles in this way, chemical sensitization of the main and sub particles is optional, but the sensitivity of the sub particles can be increased by refraining from chemical sensitization (sulfur sensitization or gold sensitization) compared to the main particles. The sensitivity may be lowered, or the sensitivity may be lowered by adjusting the particle size or the amount of noble metal such as rhodium doped inside. Furthermore, the inside of the sub-particle may be covered with gold, or the core/particle may be covered with gold.
Foaming may also be achieved by changing the composition of the core and shell using the shell method. The smaller the main particles and sub-particles, the better, for example 0.
It can take any value from 0.025 μm to 1.0 μm.
本発明に用いるハロゲン化銀乳剤調製時には、ロジウム
塩を添加して感度または階調をコントロールする事がで
きる。ロジウム塩の添加は一般には粒子形成時が好まし
いが、化学熟成時、乳剤塗布液１製時でも良い。When preparing the silver halide emulsion used in the present invention, a rhodium salt can be added to control the sensitivity or gradation. It is generally preferable to add the rhodium salt at the time of grain formation, but it may also be added at the time of chemical ripening or at the time of preparing the emulsion coating solution 1.
本発明に用いるハロゲン化銀乳剤に添加されるロジウム
塩は、単純な塩の他に複塩でも良い。代表的には、ロジ
ウムクロライド、ロジウムトリクロライド、ロジウムア
ンモニウムクロライドなどが用いられる。The rhodium salt added to the silver halide emulsion used in the present invention may be a simple salt or a double salt. Typically, rhodium chloride, rhodium trichloride, rhodium ammonium chloride, etc. are used.
ロジウム塩の添加量は、必要とする感度、階調により自
由に変えられるが銀１モルに対して１０−’モルから１
０１モルの範囲が特に有用である。The amount of rhodium salt added can be freely changed depending on the required sensitivity and gradation, but it ranges from 10-' mol to 1 mol per mol of silver.
A range of 0.01 mole is particularly useful.
またロジウム塩を使用するときに、他の無機化合物例え
ばイリジウム塩、白金塩、タリウム塩、コバルト塩、金
塩などを併用しても良い。イリジウム塩はしばしば高照
度特性の改良の目的で、銀１モル当りｉｏ−’モルから
ｌｏ−６モルの範囲まで好ましく用いることができる。Furthermore, when using a rhodium salt, other inorganic compounds such as an iridium salt, a platinum salt, a thallium salt, a cobalt salt, a gold salt, etc. may be used in combination. Iridium salts can be used preferably in the range of io-' to lo-6 moles per mole of silver, often for the purpose of improving high-intensity properties.
本発明において用いられるハロゲン化銀は種々の化学増
感剤によって増感することができる。増感剤としては、
例えば活性ゼラチン、硫黄増感剤（チオ硫酸ソーダ、ア
リルチオカルバミド、チオ尿素、アリルイソチオシアネ
ート等）、セレン増感剤（Ｎ、Ｎ−ジメチルセレノ尿素
、セレノ尿素等）、還元増感剤（トリエチレンテトラミ
ン、塩化第１スズ等）、例えばカリウムクロロオーライ
ト、カリウムオーリチオシアネート、カリウムクロロオ
ーレート、２−オーロスルホベンゾチアゾールメチルク
ロライド、アンモニウムクロロバラデート、カリウムク
ロロプラチ不−ト、ナトリウムクロロバラダイト等で代
表される各種貴金属増感剤等をそれぞれ単独で、あるい
は２種以上併用して用いることができる。なお金増感剤
を使用する場合は助剤的にロダンアンモンを使用するこ
ともできる。The silver halide used in the present invention can be sensitized with various chemical sensitizers. As a sensitizer,
For example, activated gelatin, sulfur sensitizers (sodium thiosulfate, allylthiocarbamide, thiourea, allyl isothiocyanate, etc.), selenium sensitizers (N,N-dimethylselenourea, selenourea, etc.), reduction sensitizers (triple ethylenetetramine, stannous chloride, etc.), such as potassium chloroaurite, potassium aurithiocyanate, potassium chloroaurate, 2-olosulfobenzothiazole methyl chloride, ammonium chlorovaladate, potassium chloroplatinate, sodium chlorovaladite Various noble metal sensitizers represented by the following can be used alone or in combination of two or more. When using a metal sensitizer, rhodanammonium can also be used as an auxiliary agent.
まｔ；本発明に用いられるハロゲン化銀乳剤は、例えば
米国特許第３．５６７．４５６号、同３，６１５，６３
９、同３．５７９，３４５、同３，６１５，６０８、同
３，５９８，５９６、同３，５９８゜９５５、同３，５
９２，６５３、同３，５８２，３４３号、特公昭４０−
２６７５１１同４０−２７３３２、同４３−１３１６７
、同４５−８８３３、同４７−８７４６号等の明細書に
記載されている減感色素及び／又は紫外線吸収剤を用い
ることができる。The silver halide emulsion used in the present invention is disclosed in, for example, U.S. Pat.
9, 3.579,345, 3,615,608, 3,598,596, 3,598°955, 3.5
92,653, No. 3,582,343, Special Publication No. 1977-
267511 40-27332, 43-13167
, 45-8833, 47-8746, and the like can be used.
さらに本発明に用いられるハロゲン化銀乳剤は、例えば
米国特許第２，４４４，６０７号、同第２．７１６，０
６２号、同第３，５１２．９８２号、西独国出願公告第
１．１８９．３８０号、同第２，０５８，６２６号、同
第２．１１８．４１１号、特公昭４３−４１３３号、米
国特許第３，３４２，５９６号、特公昭４７−４４１７
号、西独国出願公告第２．１４９，７８９号、特公昭３
９−２８２５号、特公昭４９−１３５６６号等に記載さ
れている化合物、好ましくは、例えば５．６− トリメ
チレン−７ヒドロキシンーＳ−トリアゾロ（１，５−ａ
）ピリミジン、５．６−テトラメチレンー７−ヒドロキ
シーＳ−トリアゾロ（１，５−ａ）ピリミジン、５−メ
チル−７−ヒドロキシ−Ｓ−トリアゾロ（１，５−ａ）
ピリミジン、５−メチル−７−ヒドロキシ−Ｓ−トリア
ゾロ（１，５−ａ）ピリミジン、７−ヒドロキシン−８
−トリアシロン（１，５−ａ）ピ・リミジン、５−メチ
ル−６−プロモーフ−ヒドロキシ−Ｓ−トリアゾロ（１
゜５−ａ）ピリミジン、没食子酸エステル（例えば没食
子酸イソアミル、没食子酸ドデシル、没食子酸プロピル
、没食子酸ナトリウム）、メルカプタン類（１−フェニ
ル−５−メルカプトテトラゾール、２−メルカプトベン
ツチアゾール）、ベンゾトリアゾールｆｆ（５−ブロム
ベンツトリアゾール、５−メチルベンツトリアゾール）
、ベンツイミダゾール類（６−ニドロベンツイミダゾー
ル）等を用いて安定化することができる。Furthermore, the silver halide emulsion used in the present invention is disclosed in, for example, U.S. Pat.
No. 62, No. 3,512.982, West German Application Publication No. 1.189.380, No. 2,058,626, No. 2.118.411, Japanese Patent Publication No. 43-4133, U.S. Patent No. 3,342,596, Special Publication No. 47-4417
No., West German Application Publication No. 2.149,789, Special Publication No. 3
Compounds described in Japanese Patent Publication No. 9-2825, Japanese Patent Publication No. 49-13566, etc., preferably, for example, 5,6-trimethylene-7hydroxyne-S-triazolo(1,5-a
) Pyrimidine, 5,6-tetramethylene-7-hydroxy-S-triazolo(1,5-a) Pyrimidine, 5-methyl-7-hydroxy-S-triazolo(1,5-a)
Pyrimidine, 5-methyl-7-hydroxy-S-triazolo(1,5-a)pyrimidine, 7-hydroxyne-8
-triacylon(1,5-a)pi-rimidine,5-methyl-6-promorph-hydroxy-S-triazolo(1
゜5-a) Pyrimidine, gallic acid ester (e.g. isoamyl gallate, dodecyl gallate, propyl gallate, sodium gallate), mercaptans (1-phenyl-5-mercaptotetrazole, 2-mercaptobenzthiazole), benzotriazole ff (5-bromobenztriazole, 5-methylbenztriazole)
, benzimidazole (6-nidrobenzimidazole), etc. can be used for stabilization.
本発明に係るハロゲン化銀写真感光材料及び／又は現像
液中には、アミノ化合物を含有することが好ましい。The silver halide photographic material and/or developer according to the present invention preferably contains an amino compound.
本発明に好ましく用いられるアミノ化合物は、第１級〜
第４級アミンすべてを包含する。好ましいアミノ化合物
の例としてアルカノールアミン類が挙げられる。以下、
好ましい具体例を列挙するが、これらに限定されるもの
でない。The amino compounds preferably used in the present invention are primary to
Includes all quaternary amines. Examples of preferred amino compounds include alkanolamines. below,
Preferred specific examples will be listed, but the invention is not limited thereto.
ジエチルアミノエタノール
ジエチルアミノブタノール
ジエチルアミノプロパン−１，２−ジオールジメチルア
ミノプロパン−１，２−ジオールジェタノールアミン
ジエチルアミノ−１−プロパノール
トリエタノールアミン
ジグロビルアミノプロバン−１，２−ジオールジオクチ
ルアミノ−１−エタノール
ジオクチルアミノプロパン−１，２−ジオールドデシル
アミノプロパン−１，２−ジオールドデシルアミノ−１
−プロパツール
ドデシルアミノ−ｌ−エタノール
アミノプロパン−１，２−ジオール
ジエチルアミノ−２−プロパノール
ジブロバノールアミン
グリシン
トリエチルアミン
トリエチレンジアミン
アミノ化合物はハロゲン化銀写真感光材料の感光層側の
塗設層（例えばハロゲン化銀乳剤層、保護層、下引層の
親水性コロイド層）の少なくとも１７１及び／又は現像
液中に含有させればよく、好ましい実施態様は現像液中
に含有する態様である。diethylaminoethanoldiethylaminobutanoldiethylaminopropane-1,2-dioldimethylaminopropane-1,2-diolgetanolaminediethylamino-1-propanoltriethanolaminediglobylaminoprobane-1,2-dioldioctylamino-1-ethanoldioctylamino Propane-1,2-diolddecylaminopropane-1,2-diolddecylamino-1
-propanol dodecylamino-l-ethanolaminopropane-1,2-diol diethylamino-2-propanol dibrobanolamine glycine triethylamine triethylene diamine It may be contained in at least 171 of the hydrophilic colloid layer (silveride emulsion layer, protective layer, subbing layer) and/or the developer, and a preferred embodiment is a mode in which it is contained in the developer.
アミノ化合物の含有量は含有させる対象、アミノ化合物
の種類等によって異なるが、コントラスト促進量が必要
である。The content of the amino compound varies depending on the object to be included, the type of the amino compound, etc., but a contrast promoting amount is required.
又現像性を高めるために、フェニドンやハイドロキノン
のような現像主薬、ベンゾトリアゾールのような抑制剤
を乳剤側に含有せしめることができる。あるいは処理液
の処理能力を上げるために、バッキング層に現像主薬や
抑制剤を含有せしめることができる。Further, in order to improve the developability, a developing agent such as phenidone or hydroquinone or an inhibitor such as benzotriazole may be contained in the emulsion. Alternatively, in order to increase the processing ability of the processing solution, the backing layer can contain a developing agent or an inhibitor.
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
ンであるが、ゼラチン以外の親水性コロイドとしては、
例えばコロイド状アルブミン、寒天、アラビアゴム、ア
ルギン酸、加水分解されたセルロースアセテート、アク
リルアミド、イミド化ポリアミド、ポリビニルアルコー
ル、加水分解されたポリビニルアセテート、ゼラチン誘
導体、例えば米国特許第２，６１４．９２８号、同第２
．５２５．７５３号に記載されている如きフェニルカル
バミルゼラチン、アシル化ゼラチン、フタル化ゼラチン
、あるいは米国特許第２．５４８．５２０号、同第２．
８３１．７６７号に記載されている如きアクリル酸スチ
レン、アクリル酸エステル、メタクリル酸、メタクリル
酸エステル等のエチレン基を持つ重合可能な単量体をゼ
ラチンにグラフト重合したもの等を挙げることができ、
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、保護層、中間層等にも適
用できる。The hydrophilic colloid particularly advantageously used in the present invention is gelatin, but hydrophilic colloids other than gelatin include:
For example, colloidal albumin, agar, gum arabic, alginic acid, hydrolyzed cellulose acetate, acrylamide, imidized polyamide, polyvinyl alcohol, hydrolyzed polyvinyl acetate, gelatin derivatives, such as U.S. Pat. Second
．． Phenylcarbamyl gelatin, acylated gelatin, phthalated gelatin as described in U.S. Pat. No. 525.753, or U.S. Pat.
Examples include gelatin graft polymerized with polymerizable monomers having an ethylene group such as styrene acrylate, acrylic ester, methacrylic acid, and methacrylic ester as described in No. 831.767.
These hydrophilic colloids can also be applied to layers that do not contain silver halide, such as antihalation layers, protective layers, intermediate layers, etc.
本発明に用いる支持体としては、例えばバライタ紙、ポ
リエチレン被覆紙、ポリプロピレン合成紙、ガラス板、
セルロースアセテート、セルロースナイトレート、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、ポリアミドフィルム、ポリプロピレンフィルム、ポ
リヵーホネートフイルム、ポリスチレンフィルム等が代
表的なものとして包含される。これらの支持体は、それ
ぞれハロゲン化銀写真感光材料の使用目的に応じて適宜
選択される。Examples of the support used in the present invention include baryta paper, polyethylene-coated paper, polypropylene synthetic paper, glass plate,
Typical examples include cellulose acetate, cellulose nitrate, polyester films such as polyethylene terephthalate, polyamide films, polypropylene films, polycarbonate films, and polystyrene films. These supports are appropriately selected depending on the intended use of the silver halide photographic material.
本発明に係る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次のものが挙げられる。ＨＯ−（
ＣＨ−ＣＨ）、 −ＯＨ型現像主薬の代表的なものとし
ては、ハイドロキノンがあり、その他にカテコール、ピ
ロガロール及びその誘導体ならびにアスコルビン酸、ク
ロロハイドロキノン、フロモハイドロキノン、メチルハ
イドロキノン、２．３−ジブロモハイドロキノン、２，
５−ジエチルハイドロキノン、カテコール、４−クロロ
カテコール、４−フェニル−カテコール、３−メトキシ
−カテコール、４−アセチル−ピロガロール、アスコル
ビン酸ソーダ等がある。Examples of developing agents used in developing the silver halide photographic material according to the present invention include the following. HO-(
Typical examples of the -OH type developing agent include hydroquinone, as well as catechol, pyrogallol and its derivatives, ascorbic acid, chlorohydroquinone, furomohydroquinone, methylhydroquinone, and 2,3-dibromohydroquinone. ,2,
Examples include 5-diethylhydroquinone, catechol, 4-chlorocatechol, 4-phenyl-catechol, 3-methoxy-catechol, 4-acetyl-pyrogallol, and sodium ascorbate.
また、ＨＯ（ＣＨ＝ ＣＨ） 、 ＮＨ２型現像剤と
しては、オルト及びパラのアミノフェノールが代表的な
もので、４−アミノフェノール、２−アミノ−６−フェ
ニルフェノール、２−アミノ−４−クロロ−６−フェニ
ルフェノール、Ｎ−メチル−ｐ−アミノフェニール等が
ある。In addition, as HO (CH= CH), NH2 type developers, ortho and para aminophenols are typical, and 4-aminophenol, 2-amino-6-phenylphenol, 2-amino-4-chloro -6-phenylphenol, N-methyl-p-aminophenyl, etc.
更に、Ｈ２Ｎ（ＣＨ−ＣＨ）−ＮＨｉ型現像剤としては
例えば４−アミノ−２−メチル−Ｎ、Ｎ−ジエチルアニ
リン、２．４−ジアミノ−Ｎ、Ｎ−ジエチルアニリン、
Ｎ−（４−アミノ−３−メチルフェニル）−七ルホリン
、ｐ−フェニレンジアミン等がある。Furthermore, examples of H2N(CH-CH)-NHi type developers include 4-amino-2-methyl-N,N-diethylaniline, 2.4-diamino-N,N-diethylaniline,
Examples include N-(4-amino-3-methylphenyl)-7ulfoline and p-phenylenediamine.
ヘテロ環型現像剤としては、ｌ−フェニル−３−ピラゾ
リドン、ｌ−７エニルー４．４−ジメチル−３−ピラゾ
リドン、１−フェニル−４−メチル−４−ヒドロキシメ
チル−３−ピラゾリドンのような３−ピラゾリドン類、
ｌ−フェニル−４−アミノ−５−ピラゾロン、５−アミ
ノラウシル等を挙げることができる。Examples of the heterocyclic developer include 3-pyrazolidone such as l-phenyl-3-pyrazolidone, l-7enyl-4,4-dimethyl-3-pyrazolidone, and 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone. -pyrazolidones,
Examples include l-phenyl-4-amino-5-pyrazolone and 5-aminolaucil.
その他、Ｔ、Ｈ，ジェームス著ザ・セオリイオプ・ザ・
ホトグラフィック・プロセス第４版（Ｔｈｅ Ｔｈｅｏ
ｒｙ ｏｆ Ｐｈｏｔｏｇｒａｐｈｉｃ Ｐｒｏｃｅｓ
ｓ ＦｏｕｒｔｈＥｄｉｔｉｏｎ）第２９１〜３３４頁
及びジャーナル・オプ・ジ・アメリカン・ケミカル・ソ
サエティ（ｊｏｕｒｎａｌ ｏｆｔｈｅ Ａｍｅｒｉｃ
ａｎ Ｃｈｅｍｉｃａｌ ５ｏｃｉｅｔｙ）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種以上組み合わせてもよい
が、２種以上を組み合わせて用いる方が好ましい。また
本発明にかかる感光材料の現像に使用する現像液には保
恒剤として、例えば亜硫酸ソーダ、亜硫酸カリ、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はな
い。又１保恒剤としてヒドロキシルアミン、ヒドラジド
化合物を用いることができ、この場合その使用量は現像
液ｌａ当たり５〜５００ｇが好ましく、より好ましくは
２０〜２００ｇである。Others: The Theory Op, by T. H. James
The Photographic Process 4th Edition (The Theo
ry of Photographic Processes
s Fourth Edition) pages 291-334 and the Journal of the American Chemical Society (Journal of the American Chemical Society).
an Chemical 5ociety) Volume 73,
Developers such as those described on page 3, 100 (1951) can be effectively used in the present invention. These developers may be used alone or in combination of two or more types, but 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 according to the invention, the effects of the invention will not be impaired. Further, hydroxylamine or a hydrazide compound can be used as a preservative, and in this case, the amount used is preferably 5 to 500 g, more preferably 20 to 200 g, per developer la.
また現像液には有機溶媒としてグリコール類を含有させ
てもよく、そのようなグリコール類としプロピレングリ
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
コール類の好ましい使用量は現像液ＩＱ当たり５〜５０
０ｇで、より好ましくは２０〜２００ｇ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。The developer may also contain glycols as an organic solvent. Examples of such glycols include propylene glycol, triethylene glycol, 1.4-butanediol, 1.5-bentanediol, and diethylene glycol. Preferably used. The preferred amount of these glycols used is 5 to 50 per developer IQ.
0g, more preferably 20-200g. These organic solvents can be used alone or in combination.
本発明に係るハロゲン化銀写真感光材料は、上記の如き
現像抑制剤を含んだ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。By developing the silver halide photographic material according to the present invention using a developer containing the above-mentioned development inhibitor, a photographic material having extremely excellent storage stability can be obtained.
上記の組成になる現像液のｐＨ値は好ましくは９〜１３
であるが、保恒性及び写真特性上からｐＨ値は１０〜１
２の範囲が更に好ましい。現像液中の陽イオンについて
は、ナトリウムよりカリウムイオンの比率が高い程現像
液の活性度を高めることができるので好ましい。The pH value of the developer having the above composition is preferably 9 to 13.
However, the pH value is 10 to 1 from the viewpoint of storage stability and photographic properties.
A range of 2 is more preferred. Regarding cations in the developer, it is preferable that the ratio of potassium ions is higher than that of sodium because the activity of the developer can be increased.
本発明に係る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。処理温度は、〜４０°Ｃ前後
が好ましく、又現像時間は２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１０秒〜５０秒が好効果
をもたらすことが多い。又現像以外の処理工程、例えば
水洗、停止、安定、定着、更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。更にまた、これらの処理は正現
像、枠現像など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 according to the present invention can be processed under various conditions. The processing temperature is preferably around 40 DEG C., and the development time is generally completed within 2 minutes, particularly preferably 10 seconds to 50 seconds, which often brings about good effects. Furthermore, it is optional to employ processing steps other than development, such as washing with water, stopping, stabilizing, fixing, and if necessary, prehardening and neutralization, and these steps can be omitted as appropriate. Furthermore, these treatments may be so-called manual development such as regular development or frame development, or mechanical development such as roller development or hanger development.
以下実施例によって本発明を具体的に説明する。 EXAMPLES The present invention will be specifically explained below with reference to Examples.
尚、当然のことではあるが、本発明は以下述べる実施例
に限定されるものではない。It should be noted that, as a matter of course, the present invention is not limited to the embodiments described below.
実施例１
下引き処理したポリエチレンテレフタレートに８ Ｗ／
ｍ”−ｗｉｎのエネルギーでコロナ放電した後下記構成
の帯電防止液を、下記の付量になる様に３０ｍ／ｗｉｎ
の速さでロールフィツトコーティングパン及びエアーナ
イフを使用して塗布した。Example 1 Subbing treated polyethylene terephthalate with 8 W/
After corona discharge with energy of m"-win, apply antistatic liquid of the following composition at 30 m/win in the amount shown below.
The coating was applied using a roll-fit coating pan and an air knife at a speed of .
（帯電防止層）
水溶性導電性ポリマー表−■に示す ０．６ｇ／ｍ２疎
水性ポリマー粒子 表−１に示す ０．４ｇ／ｍ２硬嗅
剤（Ｃ） Ｏ，１ｇ／ｍ’９０
°Ｃ１２分間乾燥し１４０°Ｃ１９０秒間熱処理した。(Antistatic layer) Water-soluble conductive polymer Shown in Table-■ 0.6g/m2 Hydrophobic polymer particles Shown in Table-1 0.4g/m2 Hard olfactory agent (C) O, 1g/m'90
It was dried at 140°C for 12 minutes and heat treated at 140°C for 190 seconds.
この帯電防止層の上にゼラチンを２．０ｇ／ｍ２になる
様に塗布しヒビワレ試験を行った。ゼラチンの硬膜剤と
しては、ホルマリン、２，４−ジクロロ−６−ヒドロキ
シ−Ｓ−トリアジンナトリウムを用いた。結果を表−ｌ
に示す。Gelatin was coated on this antistatic layer at a concentration of 2.0 g/m 2 and a cracking test was conducted. Formalin and sodium 2,4-dichloro-6-hydroxy-S-triazine were used as hardeners for gelatin. Table of results
Shown below.
くヒビワレ試験〉
試験片を乾燥したシリカゲルで相対湿度がほぼ０％にな
った容器に入れ密封し、４０℃で３日保存する。保存後
試験片を容器から取り出し、ヒビワレの程度を目視でラ
ンク付けした。Crack Test> A test piece is sealed with dry silica gel in a container with a relative humidity of approximately 0%, and stored at 40°C for 3 days. After storage, the test pieces were taken out of the container and visually ranked for the degree of cracking.
○：ヒヒワレナシ
△、ヒヒワレは若干上じるが実用上回
ａ：特開昭５５−８４６５８号記載
表−１の結果より本発明の試料はヒビワレに対して優れ
た効果を有することが明らかである。○: No fissure cracks △, slight increase in fissure cracks, but above practical level a: From the results in Table 1 described in JP-A No. 55-84658, it is clear that the sample of the present invention has an excellent effect on fissure cracks. .
実施例２
（乳剤の調製）
ｐＨ３，０の酸性雰囲気下でコンドロールドダブルジェ
ット法によりロジウム塩を、銀１モル当たり１０−’モ
ル含有する平均粒径０．１１μｍ、ハロゲン化銀組成単
分散度１５、臭化銀を５モル％含む塩臭化銀粒子を作成
した。粒子の成長は、ベンジルアデニンを１％のゼラチ
ン水溶液Ｈ当たり３０ｍｇ含有する系で行った。銀とハ
ライドの混合後、６−メチル−４−ヒドロキシ−１，３
，３ａ、７テトラザインデンをハロゲン化銀１モル当た
り６００ｍｇ加え、その後水洗、脱塩した。Example 2 (Preparation of emulsion) An emulsion containing 10-' mol of rhodium salt per mol of silver, an average grain size of 0.11 μm, and a monodispersed silver halide composition was prepared by the Chondrold double jet method in an acidic atmosphere at pH 3.0. Silver chlorobromide grains containing 5 mol % of silver bromide were prepared. Particle growth was performed in a system containing 30 mg of benzyladenine per 1% gelatin aqueous solution H. After mixing silver and halide, 6-methyl-4-hydroxy-1,3
, 3a, 7 Tetrazaindene was added in an amount of 600 mg per mole of silver halide, followed by washing with water and desalting.
次いで、ハロゲン化銀１モル当たり６０＋ｎｇの６−メ
チル−４−ヒドロキシ−１，３，３ａ、７−テトラザイ
ンデンを加えた後、ハロゲン化銀１モル当たり１５＋ｎ
ｇのチオ硫酸ナトリウムを加え、６０℃でイオウ増感を
した。イオウ増感後安定剤として６−メチル−４−ヒド
ロキシ−１，３，３ａ、７−テトラザインデンをハロゲ
ン化銀１モル当たり６００ｍｇ加えた。Then 60+ng of 6-methyl-4-hydroxy-1,3,3a,7-tetrazaindene per mole of silver halide was added followed by 15+n per mole of silver halide.
g of sodium thiosulfate was added, and sulfur sensitization was carried out at 60°C. After sulfur sensitization, 600 mg of 6-methyl-4-hydroxy-1,3,3a,7-tetrazaindene was added per mole of silver halide as a stabilizer.
得られた乳剤に添加剤を下記の付量になるように調製添
加し、特開昭５９−１９９４１号の実施例−１によりラ
テックス下引処理した厚さ１００μｍのポリエチレンテ
レフタレート支持体上に塗布した。Additives were added to the obtained emulsion in the amounts shown below, and the mixture was coated on a 100 μm thick polyethylene terephthalate support that had been subjected to latex subbing treatment according to Example 1 of JP-A-59-19941. .
ラテックスポリマー：スチレン−ブチルアクリレート−
アクリル酸３元共重合
ポリマー １．０ ｇ／ｍ’テトラフ
ェニルホスホニウムクロライド３０ ｍｇ／ｍ”
サポニン ２００ ｍｇ／ｍ２
ポリエチレングリコール １００ ｍｇ／ｍ”
ハイドロキノン ２００ ｍｇ／ｍ”
スチレン−マレイン酸共重合体 ２０ ｍｇ／ｍ’ヒ
ドラジン化合物（表−２に示す） ５０ ｍｇ／ｍ２
５−メチルベンゾトリアゾール ３０ ｍｇ／ｍ
”減感色素（Ｍ） ２０ ｍｇ
／ｍ”アルカリ処理ゼラチン（等電点４．９）１．５
ｇ／ｍ”ビス（ビニルスルホニルメチル）エーテル１５
ｍｇ／ａ＋”
銀量 ２．８ ｇ／ｍ”減感
色素Ｍ
（乳剤層保護膜）
乳剤層保護膜として、下記の付量になる製し、乳剤とと
もに同時重層塗布した。Latex polymer: styrene-butyl acrylate
Acrylic acid ternary copolymer 1.0 g/m'Tetraphenylphosphonium chloride 30 mg/m"Saponin 200 mg/m2
Polyethylene glycol 100 mg/m”
Hydroquinone 200 mg/m”
Styrene-maleic acid copolymer 20 mg/m' Hydrazine compound (shown in Table 2) 50 mg/m2
5-methylbenzotriazole 30 mg/m
"Desensitizing dye (M) 20 mg
/m” Alkali-treated gelatin (isoelectric point 4.9) 1.5
g/m” bis(vinylsulfonylmethyl)ether 15
mg/a+'' Silver amount: 2.8 g/m'' Desensitizing Dye M (Emulsion layer protective film) An emulsion layer protective film was prepared in the amount shown below and coated simultaneously with the emulsion in a multilayer manner.
よう調
弗素化ジオクチルスルホコハク酸エステル２００ｍｇ／
ｍ”
ドデシルベンゼンスルホン酸ナトリウム１００ｍｇ／ｍ
”
マット剤：ポリメタクリル酸メチル（平均粒径３．５μ
” １００ Ｂ／ｍ”硝酸リチ
ウム塩 ３０ ｍｇ／ｍ”没食子酸
プロピルエステル ３００ ｍｇ／ｍ’２−メル
カプトベンツイミダゾール−
酸ナトリウム ３０ ｍｇ／ｍ”
アルカリ処理ゼラチン（等電点４．９） １．３ ｇ／
ｍ”コロイダルシリカ ３０ ｍｇ／
ｍ’スチレン−マレイン酸共重合体 １００ ｍｇ／
ｍ”ビス（ビニルスルホニルメチル）エーテル１５
ｍｇ／ｍ２
つぎに、乳剤層と反対側の支持体上に、あらかじめ３０
Ｗ／ｍ”ｍｉｎのパワーでコロナ放電した後、ポリ（ス
チレン−ブチルアクリレート−グリシジルメタクリレー
ト）ラテックスポリマーをヘキサメチレンアジリジン硬
膜剤の存在下で塗布し、さらに帯電防止層を実施例１と
同様に塗布し、ついで下記組成のバッキング層を添加剤
が下記付量になるように調製し、塗布した。Prepared fluorinated dioctyl sulfosuccinate 200mg/
m” Sodium dodecylbenzenesulfonate 100mg/m
” Matting agent: Polymethyl methacrylate (average particle size 3.5μ
"100 B/m"Lithium nitrate 30 mg/m"Gallic acid propyl ester 300 mg/m'2-Mercaptobenzimidazole-acid sodium 30 mg/m"
Alkali-treated gelatin (isoelectric point 4.9) 1.3 g/
m” Colloidal Silica 30 mg/
m' styrene-maleic acid copolymer 100 mg/
m”bis(vinylsulfonylmethyl)ether 15
mg/m2 Next, apply 30 mg/m2 in advance on the support opposite to the emulsion layer.
After corona discharge with a power of W/m”min, poly(styrene-butyl acrylate-glycidyl methacrylate) latex polymer was applied in the presence of hexamethylene aziridine hardener and an additional antistatic layer was applied as in Example 1. Then, a backing layer having the following composition was prepared and applied so that the amount of additives was as shown below.
（バッキング層）
ラテックスポリマー：ブチルアクリレート−スチレン共
重合体 ０．５ ｇ／ｍ”スチレン−マレイ
ン酸共ＩＫ合体１００ ｍｇ／ｍ”クエン酸（塗布後
ｐＨ５．４に調製） ４０ ｍｇ／ｍ２サポニン
２００ ｍｇ／ｍ２硝酸リチウム
塩 ３０ ｍｇ／ｍ２バッキング染料
（ａ）
（ｂ）
（ｃ）
Ｏ３Ｎａ
アルカリ処理ゼラチン
２、０ｇ／＋ａ”
ビス（ビニルスルホニルメチル）エーテル１５ ｍｇ
／＋ｎ２
（バッキング層保護膜）
添加剤を下記付量になるよう調製し、
グ層上部に同時Ｉｉ層層重布た。(Backing layer) Latex polymer: Butyl acrylate-styrene copolymer 0.5 g/m" Styrene-maleic acid co-IK combination 100 mg/m" Citric acid (adjusted to pH 5.4 after coating) 40 mg/m2 Saponin
200 mg/m2 Lithium nitrate salt 30 mg/m2 Backing dye (a) (b) (c) O3Na Alkali-processed gelatin 2,0 g/+a” Bis(vinylsulfonylmethyl) ether 15 mg
/+n2 (backing layer protective film) Additives were prepared in the amounts shown below, and layer Ii was simultaneously applied on top of the layer.
ジオクチルスルホコハク酸エステル
パツキン
００
ｆｆ１ｇ／ｍ”
マット剤：ポリメタクリル酸メチル
（平均粒径４．０μｍ）
アルカリ処理ゼラチン（等電点４．９）０
ｍｇ／ｍ”
１、０ｇ／ａ”
弗素化ドデシルベンゼンスルホン酸
ナトリウム
０
ＩＩ１ｇ／ｍ２
ビス（ビニルスルホニルメチル）
エーテル ２０ ｍｇ／ｍ２
なお、上記塗布液のｐＨはあらかじめ５．４に調製して
から塗布した。Dioctylsulfosuccinate ester packing 00 ff1g/m" Matting agent: Polymethyl methacrylate (average particle size 4.0 μm) Alkali-treated gelatin (isoelectric point 4.9) 0 mg/m" 1.0 g/a" Fluorinated dodecyl Sodium benzenesulfonate 0 II 1g/m2 Bis(vinylsulfonylmethyl) ether 20 mg/m2
Note that the pH of the coating solution was adjusted to 5.4 in advance before coating.
以上のようにして得られた試料をそれぞれ２つに分け、
一方は２３℃相対湿度５５％で３日間保存した。残りの
一方は２３℃相対湿度５５％で３時間調湿し後、重ねた
状態で防湿袋に封入し、５５°Ｃで３日間保存して強制
劣化させ経時代用試料を作成した。Divide each sample obtained as above into two,
One was stored for 3 days at 23° C. and 55% relative humidity. The remaining one was conditioned for 3 hours at 23° C. with relative humidity of 55%, sealed in a moisture-proof bag in a stacked state, and stored at 55° C. for 3 days to undergo forced deterioration to create an aging sample.
両方の試料を、ステップウェッジを通して露光後、下記
に示す現像液、定着液を使用して現像処理した後、感度
及び表面比抵抗を求めた。なお感度は光学濃度で１．０
になる露光量とし、相対感度で表した。結果を表２に示
した。After both samples were exposed through a step wedge and developed using the developer and fixer shown below, sensitivity and surface resistivity were determined. The sensitivity is 1.0 in terms of optical density.
The exposure amount is expressed as relative sensitivity. The results are shown in Table 2.
現像処理条件 工程 温度 時間 現像 ３４℃ １５秒 定着 ３２°０ １０秒 水洗 常温 １０秒 現像液処方 ハイドロキノン ｌ−フェニル−４，４ジメチル−３− ピラゾリドン 臭化ナトリウム ５−メチルベンゾトリアゾール ５−ニトロインダゾール ジエチルアミノプロパン ０．４ ｇ ｇ Ｏ１３ｇ ０．０５ｇ １．２−ジオール ０ ｇ ０ ｇ ５ ｇ ５ 亜硫酸カリウム ５−スルホサリチル酸ナトリウム エチレンジアミン四酢酸ナトリウム 水でＩＱに仕上げた。Development processing conditions Process Temperature Time Development 34℃ 15 seconds Fixation 32°0 10 seconds Wash with water, room temperature, 10 seconds developer prescription hydroquinone l-phenyl-4,4dimethyl-3- Pyrazolidone sodium bromide 5-methylbenzotriazole 5-nitroindazole diethylaminopropane 0.4 g g O13g 0.05g 1.2-diol 0g 0g 5 g 5 potassium sulfite Sodium 5-sulfosalicylate Sodium ethylenediaminetetraacetate I made it into IQ with water.
ｐＨは、苛性ソーダで１１．５とした。The pH was adjusted to 11.5 with caustic soda.
定着液処方
（組成Ａ）
チオ硫酸アンモニウム（７２，５ｗ％水溶液）２４０
１ＩＩＱ
亜硫酸ナトリウム １７ ｇ酢酸ナ
トリウム・３水塩 ６．５ｇ硼酸
６ｇクエン酸ナトリウム・２水
塩 ２ｇ酢酸（９０Ｗ％水溶液）
１３．６ｍｆｆ（組成Ｂ）
純水（イオン交換水） １７ ｔｎ（
を硫酸（５０Ｗ％ の水溶液） ４．７ｇ
硫酸アルミニウム （ＡＩ２２０３換算含量が８．１ｗ
％の水溶液） ２６．５ｇ定着液の使
用時に水５００ｍｆｆ中に上記組成Ａ１組成Ｂの順に溶
かし、ｌＱに仕上げて用いた。この表２の結果から本発
明の試料は、経時保存による感度低下が少なく、また処
理後の帯電防止能の劣化も少ないことが分かる。Fixer formulation (composition A) Ammonium thiosulfate (72.5w% aqueous solution) 240
1IIQ Sodium sulfite 17 g Sodium acetate trihydrate 6.5 g Boric acid
6g sodium citrate dihydrate 2g acetic acid (90W% aqueous solution)
13.6 mff (composition B) Pure water (ion exchange water) 17 tn (
4.7g of sulfuric acid (50W% aqueous solution)
Aluminum sulfate (AI2203 equivalent content is 8.1w
% aqueous solution) When using 26.5 g of the fixer, the above compositions A and B were dissolved in the order of 500 mff of water and finished to 1Q before use. From the results in Table 2, it can be seen that the samples of the present invention show less deterioration in sensitivity due to storage over time, and less deterioration in antistatic ability after processing.
実施例３
実施例２と同様にして、ロジウム塩を銀１モル当たり１
０−’モルを含有し、平均粒径０．２０μｍ１単分散度
２０の臭化銀を２モル％含む塩臭化銀粒子を作成した。Example 3 In the same manner as in Example 2, rhodium salt was added at 1 mole of silver per mole of silver.
Silver chlorobromide particles containing 2 mol % of silver bromide with an average particle diameter of 0.20 μm and a monodispersity of 20 were prepared.
これを実施例２と同様に処理、水洗、脱塩後イオウ増感
を施した。This was treated in the same manner as in Example 2, washed with water, desalted, and then sulfur sensitized.
得られた乳剤に添加剤を下記の付量になるように調製添
加し、実施例１で用いた下引加工済ポリエチレンテレフ
タレート支持体上に塗布した。Additives were added to the obtained emulsion in the amounts shown below, and the mixture was coated on the undercoated polyethylene terephthalate support used in Example 1.
ラテックスポリマー：
スチレン−ブチルアクリレートアクリル酸３元共重合ポ
リマー １．０ｇ／＋ｍ”フェノール
ｌ ｒｓｇ／ｍ”サポニン
２００＋ａｇ／ｍ’ドデシル
ベンゼン
スルホン酸ナトリウム ５０ｍｇ／ｍ”テ
トラゾリウム化合物（表−３に示す） ５０＋ａｇ／ｍ
”化合物（Ｎ）
化合物（０）
スチレン−マレイン酸共重合体
アルカリ処理ゼラチン（等電点４．９）銀量
ホルマリン
化合物（Ｎ）
’ Ｏｅａ ｇ ／ ｔｓ ｘ
５０ｍｇ／ｍ”
２０ωｇ７ｍ２
２−Ｏｇ／ｍ”
３−５ｇ／ｍ”
１０ｍｇ／ｍ’
化合物（０）
尚、塗布液はあらかじめ水酸化ナトリウムｐＨ６，５に
調整したのち塗布した。乳剤保護膜として、添加剤を下
記の付量になるように調製し、乳剤塗布液とともに同時
重層塗布した。Latex polymer: Styrene-butyl acrylate acrylic acid ternary copolymer 1.0g/+m”phenol
l rsg/m”saponin
200+ag/m' Sodium dodecylbenzenesulfonate 50mg/m'' Tetrazolium compound (shown in Table-3) 50+ag/m
"Compound (N) Compound (0) Styrene-maleic acid copolymer Alkali-treated gelatin (isoelectric point 4.9) Silver amount Formalin compound (N) ' Oea g / ts x 50 mg/m" 20ωg7m2 2-Og/m "3-5 g/m" 10 mg/m' Compound (0) The coating solution was coated after adjusting the pH to 6.5 with sodium hydroxide in advance. As an emulsion protective film, additives were prepared in the amounts shown below and were coated simultaneously with the emulsion coating solution.
弗素化ジオクチル
スルホコハク酸エステル １００ｍｇ／ｍ”ジ
オクチルスルホコハク酸ニス７− ／Ｌ＝ １００ｍ
ｇ／＋”マット剤：不定型シリカ ５０ｍ
ｇ／ｍ”化合物（０） ３０
ｎ＋ｇ／ｍ”５−メチルベンゾトリアゾール
２０ｍｇ／ｌ化合物（Ｐ ）
５００ａ＋ｇ／ｍ”没食子酸プロピルエステル
３００Ｂ／ｍ”スチレン−マレインｒｌｌ 共重合
体１００ｍｇ／ｍ”アルカリ処理ゼラチン（等電点４．
９） １．Ｏｇ／＋＋＋”ホルマリン
１０ｍｇ／ｍ”尚、あらかじめクエン酸
でｐＨ５，４に調整したのち塗布した。Fluorinated dioctyl sulfosuccinate ester 100mg/m"Dioctylsulfosuccinic acid varnish 7-/L= 100m
g/+” Matting agent: Amorphous silica 50m
g/m” Compound (0) 30
n+g/m”5-methylbenzotriazole
20mg/l compound (P)
500a+g/m” gallic acid propyl ester
300B/m" styrene-malein rll copolymer 100mg/m" alkali-treated gelatin (isoelectric point 4.
9) 1. Og/+++” formalin
10 mg/m'' The pH was adjusted to 5.4 with citric acid before coating.
化合物（Ｐ）
次に乳剤層とは、反対側の支持体上に、実施例２と全く
同様にして帯電防止層、バッキング層を設けた。Ｉ；だ
しこの時のバッキング層の硬膜剤はホルマリンを使用し
た。Compound (P) Next, an antistatic layer and a backing layer were provided on the support opposite to the emulsion layer in exactly the same manner as in Example 2. I: Formalin was used as the hardening agent for the backing layer.
実施例２と同様に処理し、評価した。It was treated and evaluated in the same manner as in Example 2.
ただし、現像液は下記のものを用いた。得られた結果を
表−３に示す。However, the following developer was used. The results obtained are shown in Table 3.
（組成Ａ）
純水（イオン交換水） １５０ｍｆｆ
エチレンジアミン四酢酸二ナトリウム塩 ２ｇジエチレ
ングリコール ５０ｇ亜硫酸カリウム
（５５％ｖ／ｙ水溶液） １００ｍ＋２炭酸カリ
ウム ５０ｇハイドロキノン
１５ｇ１−フェニル−５−メ
ルカプトテトラゾール ３０ｍｇ水酸化カリウム 使
用液のｐＨを１ｏ、４にする量臭化カリウム
４．５ｇ（組成Ｂ）
純水（イオン交換水）３ｍｇ
ジエチレングリコール ５０ｇエチレ
ンジアミン四酢酸二
ナトリウム塩 ２５ｍｇ酢酸
（９０％水溶液） ０．３ｙｒＱ１
−７エニルー３−ピラゾリドン
５００ｍｇ
現像液の使用時に水５００ｍＱ中に上記組成Ａ１組成
表３の結果からも実施例２のヒドラジン化合物の場合と
同様に本発明の試料は経時保存による感度低下が少なく
、処理後の帯電防止能の劣化も少ない。(Composition A) Pure water (ion exchange water) 150mff
Ethylenediaminetetraacetic acid disodium salt 2g diethylene glycol 50g potassium sulfite (55% v/y aqueous solution) 100m+2 potassium carbonate 50g hydroquinone 15g 1-phenyl-5-mercaptotetrazole 30mg potassium hydroxide Amount to bring the pH of the working solution to 1o, 4 Potassium bromide
4.5g (Composition B) Pure water (ion-exchanged water) 3mg Diethylene glycol 50g Ethylenediaminetetraacetic acid disodium salt 25mg Acetic acid (90% aqueous solution) 0.3yrQ1
-7 enyl-3-pyrazolidone 500 mg in 500 mQ of water when using a developer The above composition A1 From the results in Table 3, the sample of the present invention shows little sensitivity loss due to storage over time, similar to the case of the hydrazine compound of Example 2. There is also little deterioration in antistatic ability after treatment.
本発明により、処理後も帯電防止能の劣化がおこらず、
しかも親水性コロイド層を上層に設けた場合のひびわれ
を生じないプラスティックフィルム支持体用の帯電防止
層及びこの帯電防止層を超硬調乳剤に適用した場合、経
時で減感しない安定性の高いハロゲン化銀写真感光材料
を提供することができた。According to the present invention, the antistatic ability does not deteriorate even after treatment,
Moreover, when a hydrophilic colloid layer is provided as an upper layer, an antistatic layer for a plastic film support that does not cause cracking, and when this antistatic layer is applied to an ultra-high contrast emulsion, a highly stable halogenated layer that does not desensitize over time. We were able to provide a silver photographic material.
Claims (2)
ー粒子［３］硬化剤の反応生成物からなる帯電防止層を
有してなるプラスチックフィルム支持体において、該硬
化剤として亜鉛及びジルコニウム金属を含有する金属錯
体を用いることを特徴とする帯電防止層を有するハロゲ
ン化銀写真感光材料。(1) In a plastic film support comprising an antistatic layer made of a reaction product of [1] a water-soluble conductive polymer [2] hydrophobic polymer particles [3] a hardening agent, zinc and zirconium are used as the hardening agent. A silver halide photographic light-sensitive material having an antistatic layer characterized by using a metal complex containing a metal.
ゾリウム化合物を含有することを特徴とする請求項１記
載のハロゲン化銀写真感光材料。(2) The silver halide photographic material according to claim 1, wherein the photosensitive emulsion layer contains a hydrazine compound or a tetrazolium compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19719489A JPH0359652A (en) | 1989-07-28 | 1989-07-28 | Silver halide photographic sensitive material subjected to antistatic treatment |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19719489A JPH0359652A (en) | 1989-07-28 | 1989-07-28 | Silver halide photographic sensitive material subjected to antistatic treatment |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0359652A true JPH0359652A (en) | 1991-03-14 |
Family
ID=16370374
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19719489A Pending JPH0359652A (en) | 1989-07-28 | 1989-07-28 | Silver halide photographic sensitive material subjected to antistatic treatment |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0359652A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005082853A1 (en) * | 2004-02-26 | 2005-09-09 | Merck Patent Gmbh | Semicarbazide derivatives as kinase inhibitors |
-
1989
- 1989-07-28 JP JP19719489A patent/JPH0359652A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005082853A1 (en) * | 2004-02-26 | 2005-09-09 | Merck Patent Gmbh | Semicarbazide derivatives as kinase inhibitors |
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