JPH01144050A - Silver halide photographic sensitive material - Google Patents
Silver halide photographic sensitive materialInfo
- Publication number
- JPH01144050A JPH01144050A JP30389287A JP30389287A JPH01144050A JP H01144050 A JPH01144050 A JP H01144050A JP 30389287 A JP30389287 A JP 30389287A JP 30389287 A JP30389287 A JP 30389287A JP H01144050 A JPH01144050 A JP H01144050A
- Authority
- JP
- Japan
- Prior art keywords
- group
- silver halide
- layer
- light
- groups
- 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 79
- 239000004332 silver Substances 0.000 title claims abstract description 42
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 42
- 239000000463 material Substances 0.000 title claims abstract description 26
- 239000000839 emulsion Substances 0.000 claims abstract description 27
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 125000001424 substituent group Chemical group 0.000 claims abstract description 23
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 12
- 238000009835 boiling Methods 0.000 claims description 34
- 239000003960 organic solvent Substances 0.000 claims description 27
- 150000002989 phenols Chemical class 0.000 claims description 27
- 238000005562 fading Methods 0.000 abstract description 18
- 239000002904 solvent Substances 0.000 abstract description 12
- 238000004383 yellowing Methods 0.000 abstract description 12
- 229930185605 Bisphenol Natural products 0.000 abstract 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 abstract 2
- 239000003595 mist Substances 0.000 abstract 2
- 239000010410 layer Substances 0.000 description 54
- 125000000217 alkyl group Chemical group 0.000 description 32
- 108010010803 Gelatin Proteins 0.000 description 26
- 229920000159 gelatin Polymers 0.000 description 26
- 239000008273 gelatin Substances 0.000 description 26
- 235000019322 gelatine Nutrition 0.000 description 26
- 235000011852 gelatine desserts Nutrition 0.000 description 26
- 125000003118 aryl group Chemical group 0.000 description 17
- 239000011248 coating agent Substances 0.000 description 17
- 238000000576 coating method Methods 0.000 description 17
- 239000000975 dye Substances 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 239000003795 chemical substances by application Substances 0.000 description 14
- 125000003342 alkenyl group Chemical group 0.000 description 12
- 125000003545 alkoxy group Chemical group 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 10
- 239000006185 dispersion Substances 0.000 description 9
- 125000005843 halogen group Chemical group 0.000 description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 9
- 238000011282 treatment Methods 0.000 description 9
- 125000004104 aryloxy group Chemical group 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 125000004390 alkyl sulfonyl group Chemical group 0.000 description 7
- 238000011161 development Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 7
- 238000012545 processing Methods 0.000 description 7
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 7
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 125000004391 aryl sulfonyl group Chemical group 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 210000003127 knee Anatomy 0.000 description 6
- 206010070834 Sensitisation Diseases 0.000 description 5
- 229910021607 Silver chloride Inorganic materials 0.000 description 5
- SJOOOZPMQAWAOP-UHFFFAOYSA-N [Ag].BrCl Chemical compound [Ag].BrCl SJOOOZPMQAWAOP-UHFFFAOYSA-N 0.000 description 5
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 5
- 125000004429 atom Chemical group 0.000 description 5
- 125000000753 cycloalkyl group Chemical group 0.000 description 5
- 125000003438 dodecyl group Chemical group [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])* 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 description 5
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- 230000008313 sensitization Effects 0.000 description 5
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 125000002252 acyl group Chemical group 0.000 description 4
- 125000004422 alkyl sulphonamide group Chemical group 0.000 description 4
- 125000004421 aryl sulphonamide group Chemical group 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000000084 colloidal system Substances 0.000 description 4
- 125000001624 naphthyl group Chemical group 0.000 description 4
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- 239000007844 bleaching agent Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 125000004093 cyano group Chemical group *C#N 0.000 description 3
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 3
- 125000000623 heterocyclic group Chemical group 0.000 description 3
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 230000001235 sensitizing effect Effects 0.000 description 3
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 3
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 3
- NVBFHJWHLNUMCV-UHFFFAOYSA-N sulfamide Chemical group NS(N)(=O)=O NVBFHJWHLNUMCV-UHFFFAOYSA-N 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 2
- ZNBNBTIDJSKEAM-UHFFFAOYSA-N 4-[7-hydroxy-2-[5-[5-[6-hydroxy-6-(hydroxymethyl)-3,5-dimethyloxan-2-yl]-3-methyloxolan-2-yl]-5-methyloxolan-2-yl]-2,8-dimethyl-1,10-dioxaspiro[4.5]decan-9-yl]-2-methyl-3-propanoyloxypentanoic acid Chemical compound C1C(O)C(C)C(C(C)C(OC(=O)CC)C(C)C(O)=O)OC11OC(C)(C2OC(C)(CC2)C2C(CC(O2)C2C(CC(C)C(O)(CO)O2)C)C)CC1 ZNBNBTIDJSKEAM-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- 101150003532 CSH gene Proteins 0.000 description 2
- 101100342332 Mus musculus Klf16 gene Proteins 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 241000220317 Rosa Species 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000004442 acylamino group Chemical group 0.000 description 2
- 125000004423 acyloxy group Chemical group 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000005153 alkyl sulfamoyl group Chemical group 0.000 description 2
- 125000004414 alkyl thio group Chemical group 0.000 description 2
- 125000001118 alkylidene group Chemical group 0.000 description 2
- XYXNTHIYBIDHGM-UHFFFAOYSA-N ammonium thiosulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-UHFFFAOYSA-N 0.000 description 2
- 125000005110 aryl thio group Chemical group 0.000 description 2
- 235000019445 benzyl alcohol Nutrition 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 125000002704 decyl group Chemical group [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])* 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 125000006038 hexenyl group Chemical group 0.000 description 2
- 229910000378 hydroxylammonium sulfate Inorganic materials 0.000 description 2
- 125000005462 imide group Chemical group 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 125000005647 linker group Chemical group 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 125000001421 myristyl 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])[H] 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 125000001400 nonyl 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])[H] 0.000 description 2
- 125000005064 octadecenyl group Chemical group C(=CCCCCCCCCCCCCCCCC)* 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 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 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 2
- 229940001584 sodium metabisulfite Drugs 0.000 description 2
- 235000010262 sodium metabisulphite Nutrition 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 125000004079 stearyl 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])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000000565 sulfonamide group Chemical group 0.000 description 2
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- 125000005031 thiocyano group Chemical group S(C#N)* 0.000 description 2
- 125000002889 tridecyl 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])[H] 0.000 description 2
- IKQCSJBQLWJEPU-UHFFFAOYSA-N 2,5-dihydroxybenzenesulfonic acid Chemical compound OC1=CC=C(O)C(S(O)(=O)=O)=C1 IKQCSJBQLWJEPU-UHFFFAOYSA-N 0.000 description 1
- DSHDNZISTOXSKA-UHFFFAOYSA-J 2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate;iron(2+) Chemical compound [Fe+2].[Fe+2].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O DSHDNZISTOXSKA-UHFFFAOYSA-J 0.000 description 1
- MLRAJZNPKPVUDQ-UHFFFAOYSA-N 3-sulfanyl-1,2-dihydrotriazole Chemical compound SN1NNC=C1 MLRAJZNPKPVUDQ-UHFFFAOYSA-N 0.000 description 1
- 229940100484 5-chloro-2-methyl-4-isothiazolin-3-one Drugs 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 description 1
- 229920001174 Diethylhydroxylamine Polymers 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
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical group C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 241000131972 Sphingomonadaceae Species 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical group NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- HOLVRJRSWZOAJU-UHFFFAOYSA-N [Ag].ICl Chemical compound [Ag].ICl HOLVRJRSWZOAJU-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000005115 alkyl carbamoyl group Chemical group 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 229940101006 anhydrous sodium sulfite Drugs 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- 125000005161 aryl oxy carbonyl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- DKFFVMCMYIVCMK-UHFFFAOYSA-N azane 2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]acetic acid dihydrate Chemical compound O.[OH-].[NH4+].C(CN(CC(=O)O)CC(=O)O)N(CC(=O)O)CC(=O)O DKFFVMCMYIVCMK-UHFFFAOYSA-N 0.000 description 1
- 150000001558 benzoic acid derivatives Chemical class 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- DHNRXBZYEKSXIM-UHFFFAOYSA-N chloromethylisothiazolinone Chemical compound CN1SC(Cl)=CC1=O DHNRXBZYEKSXIM-UHFFFAOYSA-N 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical class OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 150000008050 dialkyl sulfates Chemical class 0.000 description 1
- 125000002720 diazolyl group Chemical group 0.000 description 1
- FVCOIAYSJZGECG-UHFFFAOYSA-N diethylhydroxylamine Chemical compound CCN(O)CC FVCOIAYSJZGECG-UHFFFAOYSA-N 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 125000004705 ethylthio group Chemical group C(C)S* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 125000002960 margaryl 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])C([H])([H])[H] 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 description 1
- 125000004170 methylsulfonyl group Chemical group [H]C([H])([H])S(*)(=O)=O 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 125000001196 nonadecyl 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])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000003356 phenylsulfanyl group Chemical group [*]SC1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 125000003170 phenylsulfonyl group Chemical group C1(=CC=CC=C1)S(=O)(=O)* 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 125000005498 phthalate group Chemical class 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical class OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 150000003022 phthalic acids Chemical class 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 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
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 229940001482 sodium sulfite Drugs 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- HLWRUJAIJJEZDL-UHFFFAOYSA-M sodium;2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]acetate Chemical compound [Na+].OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC([O-])=O HLWRUJAIJJEZDL-UHFFFAOYSA-M 0.000 description 1
- HFQQZARZPUDIFP-UHFFFAOYSA-M sodium;2-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HFQQZARZPUDIFP-UHFFFAOYSA-M 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 125000000475 sulfinyl group Chemical group [*:2]S([*:1])=O 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 125000003831 tetrazolyl group Chemical group 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 125000001425 triazolyl group Chemical group 0.000 description 1
- 150000003639 trimesic acids Chemical class 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
- G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
- G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
- G03C7/392—Additives
- G03C7/39208—Organic compounds
- G03C7/39212—Carbocyclic
- G03C7/39216—Carbocyclic with OH groups
-
- 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
- G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
- G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
- G03C7/3003—Materials characterised by the use of combinations of photographic compounds known as such, or by a particular location in the photographic element
- G03C7/3005—Combinations of couplers and photographic additives
- G03C7/3006—Combinations of phenolic or naphtholic couplers and photographic additives
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Silver Salt Photography Or Processing Solution Therefor (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し、詳しくはシ
アン色素画像の画像保存性が改良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 particularly to a silver halide photographic light-sensitive material in which the image storage stability of cyan dye images is improved.
[発明の背景〕
へロゲン化銀カラー写真感光材料を用いて色素画像を形
成するには1通常、芳香族第1級アミン系発色現像主薬
が、露光されたハロゲン化銀写真感光材料中のハロゲン
化銀粒子を還元する際に。[Background of the Invention] To form a dye image using a silver halide color photographic light-sensitive material, 1. Usually, an aromatic primary amine color developing agent is used to remove the halogen in the exposed silver halide photographic light-sensitive material. When reducing silver oxide particles.
自らが酸化され、この酸化体が、ハロゲン化銀写真感光
材料中に予め含有されたカプラーと反応して色素を形成
することによって行われる。そして、通常はカプラーと
しては、減色法による色再現を行うため、イエロー、マ
ゼンタ、シアンの3つの色素を形成する3種のカプラー
が用いられている。This is accomplished by oxidizing the silver halide itself and reacting the oxidized product with a coupler previously contained in the silver halide photographic light-sensitive material to form a dye. Generally, three types of couplers are used that form three dyes, yellow, magenta, and cyan, in order to perform color reproduction by the subtractive color method.
各カプラーは1通常、実質的に水不溶性の高沸点有機溶
媒あるいはこの溶媒に必要に応じて補助溶剤を併用して
溶解してハロゲン化銀乳剤中に添加される。Each coupler is usually added to the silver halide emulsion by being dissolved in a substantially water-insoluble high-boiling organic solvent or in this solvent, if necessary, in combination with an auxiliary solvent.
各カプラーに要求される基本的性質としては、先ず高沸
点有機溶媒に対する溶解性が大きいこと、ハロゲン化銀
乳剤中における分散性及び分散安定性が良好で容易に析
出しないこと1分光吸収特性に優れ1色調が良好、で広
範な色再現域における鮮明な色素画像が形成されること
、ならびに得られる色素画像が光、熱、湿気等に対して
堅牢性を有すること等が挙げられる。とりわけ、カラー
プリント材料に用いられるカプラーにおいては、写真画
像の記録保存という使命から、得られる色素画像の光堅
牢性及び暗所保存性(暗退色性)の両方をできるだけ高
めることが望まれている。とりわけシアンカプラーにつ
いては明所・暗所保存性がバランスよく改良されること
が望まれている。The basic properties required of each coupler are: firstly, high solubility in high-boiling organic solvents, good dispersibility and dispersion stability in silver halide emulsions, and no easy precipitation;1) excellent spectral absorption characteristics; Examples include that a clear dye image is formed in a wide color reproduction range with good one color tone, and that the obtained dye image has fastness to light, heat, moisture, and the like. In particular, for couplers used in color print materials, it is desirable to improve both the light fastness and dark storage stability (dark fading resistance) of the resulting dye image as much as possible due to the mission of preserving photographic images. . In particular, for cyan couplers, it is desired that the storage stability in light and dark places be improved in a well-balanced manner.
上記暗退色性を改良したシアンカプラーとして、フェノ
ールの2位及び5位がアシルアミノ基で置換された2、
5−ジアシルアミノフェノール系シアンカプラーが知ら
れており、例えば米国特許2.895,826号、特開
昭50−112038号、同53−109830号なら
びに同55−163537号各公報に記載されている。As the above-mentioned cyan coupler with improved dark fading property, 2, in which the 2- and 5-positions of the phenol are substituted with acylamino groups,
5-Diacylaminophenol cyan couplers are known, and are described, for example, in U.S. Pat. .
しかし、これらの2,5−ジアシルアミノフェノール系
シアンカプラーは確かに得られるシアン色素画像の暗退
色性は著しく改良されているものの、光堅牢性に3いて
著しく劣るものが多く、また光イエロースティン(光黄
色変)等の不都合が生じることがある。However, although these 2,5-diacylaminophenol-based cyan couplers do significantly improve the dark fading resistance of the cyan dye images obtained, many of them have significantly poor light fastness, and they also produce light yellow stains. (light yellowing) and other inconveniences may occur.
この2,5−ジアシルアミノフェノール系シアンカプラ
ーの画像保存性を改良する技術としては、特開昭59−
105645号、同59−124340号、q60−2
22853号及び同62−118344号各公報ならび
に特願昭61−291277号、同61−38893号
等に記載された方法が挙げられるが、いずれの方法も十
分ではなく、前記欠点を同時に改良する方法は見い出さ
れていない。As a technique for improving the image storage stability of this 2,5-diacylaminophenol cyan coupler,
No. 105645, No. 59-124340, q60-2
Examples include the methods described in Japanese Patent Application No. 22853 and No. 62-118344, as well as Japanese Patent Application No. 61-291277 and No. 61-38893, but none of these methods are sufficient, and there is a method for simultaneously improving the above-mentioned drawbacks. has not been found.
[発明の目的]
本発明の目的は、シアン色素画像の保存性特に暗退色性
、光堅牢性及び光黄色変が同時に改良されたハロゲン化
銀写真感光材料を提供することである。[Object of the Invention] An object of the present invention is to provide a silver halide photographic material in which the storage properties of cyan dye images, especially dark fading resistance, light fastness, and light yellowing are simultaneously improved.
[発明の構成]
上記目的は下記構成のハロゲン化銀写真感光材料によっ
て達成された。[Configuration of the Invention] The above object has been achieved by a silver halide photographic material having the following configuration.
支持体上に少なくとも一層のへロゲン化銀乳剤層を有す
るハロゲン化銀写真感光材料において。A silver halide photographic material having at least one silver halide emulsion layer on a support.
該乳剤層の少なくとも一層が2.5−ジアシルアミノフ
ェノール系シアンカプラー及び一方のフェノール性水酸
基が置換されており、かつ少なくとも一方のフェノール
環が置換基を有するビス型フェノール誘導体を同一高沸
点有機溶媒油滴中に含有することを特徴とするハロゲン
化銀写真感光材料。At least one of the emulsion layers contains a 2,5-diacylaminophenol-based cyan coupler and a bis-type phenol derivative in which one of the phenolic hydroxyl groups is substituted, and at least one of the phenol rings has a substituent in the same high-boiling point organic solvent. A silver halide photographic material characterized by containing oil in droplets.
以下、本発明を詳述する。The present invention will be explained in detail below.
前記2.5−ジアシルアミノフェノール系シアンカプラ
ーとして好ましいものは、下記一般式[工]で示される
。Preferable examples of the 2,5-diacylaminophenol cyan coupler are represented by the following general formula.
一般式[I]
Z+
式中、R1はアルキル11、アリール基、シクロアルキ
ル基款たは複素環基を表わす。R2はアルキル基または
アリール基を表わず。R3は水素原子、ハロゲン原子、
アルキル基またはアルコキシ基を表わず。Zlは水素原
子または芳雷族第1級アミン系発色現像主薬の酸化体と
の反応により#It説し得る基を表わず。General formula [I] Z+ In the formula, R1 represents alkyl 11, an aryl group, a cycloalkyl group, or a heterocyclic group. R2 does not represent an alkyl group or an aryl group. R3 is a hydrogen atom, a halogen atom,
Does not represent an alkyl or alkoxy group. Zl does not represent a hydrogen atom or a group that can be interpreted as #It by reaction with an oxidized product of an aromatic primary amine color developing agent.
前記一般式[I]のR1で表わされるアルキル1gは、
例えばメチル曇、エチル基、ブチル基、ヘキシル基、ト
リデシル基、ペシタデシル基、ヘプタデシル基等である
。、R1で表わされるアリール昌は、例えばフェニル基
、ナフチル基等であり、好ましくはフェニル基である。1g of alkyl represented by R1 in the general formula [I] is,
Examples include methyl cloud, ethyl group, butyl group, hexyl group, tridecyl group, pecitadecyl group, heptadecyl group, and the like. , R1 is, for example, a phenyl group, a naphthyl group, etc., and preferably a phenyl group.
R1で表わされる複素環基は、例えばピリジル1B、フ
ラン基笠であ以下余白
る。R1で表わされるシクロアルキル基は、例えばシク
ロプロピル基、シクロヘキシル基等である。The heterocyclic group represented by R1 is, for example, pyridyl 1B or a furan group. The cycloalkyl group represented by R1 is, for example, a cyclopropyl group or a cyclohexyl group.
これらのR1で表わされる多基は単一もしくは複数の置
換基を有するものも含み、例えばアリール基に導入され
る置換基としては代表的なものにハロゲン原子、アルキ
ル基、ヒドロキシル基、シアノ基、ニトロ基、カルボキ
シル基、アルコキシ基、アリールオキシ基、アルキルス
ルホニル基、アリールスルホニル基、アルキルスルホン
アミド基、アリールスルホンアミド基、アルキルスルフ
ァモイル基、アリールスルファモイル基、アルキルオキ
シカルボニル基、アリールオキシカルボニル基、アミノ
スルホンアミド基、アシルアミノ基、アシル基、アルキ
ルカルバモイル
モイル基などを挙げることができ、R1で表わされるア
ルキル基、シクロアルキル基および複素環基に導入され
る置換基についても上記と同様なものを挙げることがで
きる。These polygroups represented by R1 include those having single or multiple substituents; for example, typical substituents introduced into the aryl group include a halogen atom, an alkyl group, a hydroxyl group, a cyano group, Nitro group, carboxyl group, alkoxy group, aryloxy group, alkylsulfonyl group, arylsulfonyl group, alkylsulfonamide group, arylsulfonamide group, alkylsulfamoyl group, arylsulfamoyl group, alkyloxycarbonyl group, aryloxy Examples include carbonyl group, aminosulfonamide group, acylamino group, acyl group, alkylcarbamoyl group, etc. Substituents introduced into the alkyl group, cycloalkyl group, and heterocyclic group represented by R1 are also the same as above. I can list things.
R1で表わされる好ま゛しい基としては、フ刊ニル基ま
たはハロゲン原子、アルキルスルホンアミド基、アリー
ルスルホンアミド基、アルキルスルフ1モイル基、アリ
ールスルファモイル基、アルキルスルホニル基、アリー
ルスルホニル基、アシル基もしくはシアノ基を置換基と
して有するフェニル基である。Preferred groups represented by R1 include a fluorinyl group or a halogen atom, an alkylsulfonamide group, an arylsulfonamide group, an alkylsulfonyl moyl group, an arylsulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group, and an acyl group. Alternatively, it is a phenyl group having a cyano group as a substituent.
R2で表わされるアルキル基は、直鎖もしくは分岐のも
のであり例えば、メチル基、エチル基、プロピル基、ブ
チル基、オクチル基、トリデシル基等である。R2で表
わされるアリール基は、例えばフェニル基、ナフチル基
等である。これらのR2で表わされる多基は置換基を有
するものも含み、導入される置換基の例としては前記の
R1で表わされる基に尋人される置換基と同様なものが
挙げられる。The alkyl group represented by R2 is linear or branched, and includes, for example, a methyl group, ethyl group, propyl group, butyl group, octyl group, tridecyl group, and the like. The aryl group represented by R2 is, for example, a phenyl group or a naphthyl group. These multigroups represented by R2 include those having substituents, and examples of the substituents to be introduced include the same substituents as those for the group represented by R1 above.
R3で表わされるハロゲン原子は、例えばフッ素、塩素
、臭素等の各原子であり、アルキル基は、例えば、メチ
ル基、エチル基、プロピル基、ブチル基、ドデシル基等
であり、また、アルコキシ基は、例えばメトキシ基、エ
トキシ基、プロピルオキシ基、ブトキシ基等である.R
3の好ましくは水M原子またはハロゲン原子であり、特
に好ましくは水素原子である。The halogen atom represented by R3 is, for example, each atom such as fluorine, chlorine, or bromine, the alkyl group is, for example, a methyl group, ethyl group, propyl group, butyl group, dodecyl group, etc., and the alkoxy group is , for example, a methoxy group, an ethoxy group, a propyloxy group, a butoxy group, etc. R
3 is preferably a water M atom or a halogen atom, particularly preferably a hydrogen atom.
Zlで表わされる芳香族第1級アミン系発色現像主薬の
酸イヒ体との反応によりm1112t,得る基の代表的
なものとしては、例えばハロゲン原子、アルコキシ基、
アリールオキシ基、アリールアゾ基、チオエーテル、カ
ルバモイルオキシ基、アシルオキシ基、イミド基、スル
ホンアミド基、チオシアノ基、複策環基などが挙げられ
る。Zlで表わされる特に好適な例は、水素原子または
塩素原子である。Typical examples of the group obtained by reacting with the acid derivative of an aromatic primary amine color developing agent represented by Zl include a halogen atom, an alkoxy group,
Examples include an aryloxy group, an arylazo group, a thioether, a carbamoyloxy group, an acyloxy group, an imide group, a sulfonamide group, a thiocyano group, and a complex ring group. A particularly preferred example of Zl is a hydrogen atom or a chlorine atom.
本発明において一般式[I]で表わされるシアンカプラ
ーの好J二しくは、下記一般式【工′ ]で表わされる
化合物である。In the present invention, preferred cyan couplers represented by the general formula [I] are compounds represented by the following general formula [I].
一般式[I’ ]
一般式[工′ ]において、Rt+はアルキル長仕たは
アリール基を表わし、単一もしくは複数の置。General formula [I'] In the general formula [I'], Rt+ represents an alkyl group or an aryl group, and may be a single or multiple group.
1A基を有するものも含む。この置換基としては代表的
なものに、ハロゲン原子、ヒドロキシル基、カルボキシ
ル基、アルキル基、シアノ基、ニトロ基、アルコキシ基
、アリールオキシ基、アルキルスルホンアミド基、アリ
ールスルホンアミド基、アルキルスルファモイル基、ア
リールスルファモイル基、アルキルオキシカルボニル基
、アリールオキシカルボニル基、アミノスルホンアミド
基、アルキルスルホニル基、アリールスルボニル基、ア
シル基、アミノカルボニルアミド基、カルバモイル基、
スルフィニル基などを挙げることができる。Also includes those having a 1A group. Typical substituents include halogen atoms, hydroxyl groups, carboxyl groups, alkyl groups, cyano groups, nitro groups, alkoxy groups, aryloxy groups, alkylsulfonamide groups, arylsulfonamide groups, and alkylsulfamoyl groups. group, arylsulfamoyl group, alkyloxycarbonyl group, aryloxycarbonyl group, aminosulfonamide group, alkylsulfonyl group, arylsulfonyl group, acyl group, aminocarbonylamide group, carbamoyl group,
Examples include sulfinyl group.
R11で表わされる好ましい基としては、nj −0の
ときはアルキル基、n1=1以上のときはアリール基で
ある。R11で表わされるさらに好款しい基としては、
n1=0のときは置換基を除いた炭素数1〜22個のア
ルキル基であり、nl−1以上のときはフェニル基、ま
たはアルキル基、アルキルスルボンアミド基、アリール
スルホンアミド基、アミノスルホンアミド基、もしくは
アルキルオキシカルボニル基を置換基どして有するフェ
ニル基である。Preferred groups represented by R11 are an alkyl group when nj -0 and an aryl group when n1=1 or more. More preferable groups represented by R11 include:
When n1=0, it is an alkyl group having 1 to 22 carbon atoms excluding substituents, and when nl-1 or more, it is a phenyl group, or an alkyl group, an alkylsulfonamide group, an arylsulfonamide group, an aminosulfone It is a phenyl group having an amide group or an alkyloxycarbonyl group as a substituent.
R12はアルキレン基を表わし、好ましくは直鎖または
分岐の原素原子数1〜20個、更に好ましくは炭素原子
数1〜12個のアルキレン基である。R12 represents an alkylene group, preferably a linear or branched alkylene group having 1 to 20 atoms, more preferably 1 to 12 carbon atoms.
nl はOまたは正の整数であり、好ましくは0または
1である。nl is O or a positive integer, preferably 0 or 1.
Xは2価基を表わし、この2価基としては例えば−〇−
1−CO−1−COO−1−OCO−1−8O2NR’
−1−NR’ 302 NR″−1−S−1−SO−1
−3O2−等が挙げられる。X represents a divalent group, and examples of this divalent group include -〇-
1-CO-1-COO-1-OCO-1-8O2NR'
-1-NR' 302 NR''-1-S-1-SO-1
-3O2- and the like.
ここで、Rl 、RLJはアルキル基を表わし、R′、
Rrrはそれぞれ買換基を有するものも含む。Xの好ま
しくは一〇−1−S−1−SO−1−3O2−である。Here, Rl and RLJ represent an alkyl group, R',
Rrr includes those each having an exchange group. X is preferably 10-1-S-1-SO-1-3O2-.
R+ ’ 、R3’ およびZ+ ’ はそれぞれ前記
−般式[I’]におけるR+ 、R3およびZlと同義
である。R+', R3' and Z+' have the same meanings as R+, R3 and Zl in the above-mentioned formula [I'], respectively.
以下余白
以下にZ、”+−5Fアシルアミ/7エ/−ル系シアン
カプラーの代表的具体例を示すが、これらに限定される
ものではない。Typical specific examples of Z, ``+-5F acylami/7-el cyan couplers are shown below in the margins, but the invention is not limited to these.
GすC,2H2,So2Nl−I
C411,(nl
C4Ll、(ul
し1□112.tlll
C,2II、、、+Il+
し°e
1−−i 9
また2、5−ジアシルアミノフェノール系シアンカブ2
−は単独でmいても適宜他のシアンカプラーと併用して
もよく、併用に好ましいものは下記−股式〔「ゴで示さ
れるシアンカプラーである。GsuC,2H2,So2Nl-I C411, (nl C4Ll, (ul し1□112.tllll C,2II,,, +Il+ shi°e 1--i 9 Also 2,5-diacylaminophenol cyankabu 2
- may be used alone or in combination with other cyan couplers as appropriate, and preferred for use in combination are the following cyan couplers:
−服代[1[]
(式中、R4はアルキル基を表わし、R5はアルキル基
、テリール基、アルコキシ基、アワールオキシ基、アル
キルチオ基、アリールチオ基、アルキルスルホニル基ま
たはアリールスルホニル基たは芳香族第一級アミン系発
色現像主薬の酸化体との反応により離脱し得る基を表わ
す、)以下余白
本発明において、前記−服代[11]で表わされるシア
ンカプラーは、J:り好ましくは下記−服代[■′ ]
で表わされるものである。-Fukudai[1[] (In the formula, R4 represents an alkyl group, R5 is an alkyl group, a teryl group, an alkoxy group, an awaroxy group, an alkylthio group, an arylthio group, an alkylsulfonyl group, an arylsulfonyl group, or an aromatic group. Represents a group that can be separated by reaction with an oxidized product of a primary amine color developing agent. generation [■′]
It is expressed as
−服代[■′〕
式中、R++およびR+2は、同一でありまたは異なり
、水素原子、アルキル基(例えばメチル基、エチル基、
プロピル基、ブチル基、アミル基、オクチル基、ドデシ
ル基等)、アルコキシI(IrAえばメ1−キシ4B、
エトキシ基等)を表わす。-Fukudai [■'] In the formula, R++ and R+2 are the same or different and represent a hydrogen atom, an alkyl group (for example, a methyl group, an ethyl group,
propyl group, butyl group, amyl group, octyl group, dodecyl group, etc.), alkoxy I (for example, IrA, me-1-xy 4B,
ethoxy group, etc.).
但しPUTとRI2の炭素原子数の総和は8〜16個で
ある。より好ましくは、R++およびR+2が、それぞ
れブチル基またはアミル基である。However, the total number of carbon atoms in PUT and RI2 is 8 to 16. More preferably, R++ and R+2 are each a butyl group or an amyl group.
R13は水素原子またはアルキル基(例えばメチル基、
エチル基、プロピル基、ブチル基、オクチル基等)であ
る。R13 is a hydrogen atom or an alkyl group (for example, a methyl group,
(ethyl group, propyl group, butyl group, octyl group, etc.).
好ましくは水素原子、ニブル基、ブチル基であ以下余白 る。Preferably a hydrogen atom, a nibble group, or a butyl group, with a blank space below. Ru.
R’5は前記−服代[II]のR5と同義である。R'5 has the same meaning as R5 in the above-mentioned clothing charge [II].
即ちアルキルM(例えばメチル基、エチル基、プロピル
基、ブチル基、ドデシル基等)、アリール基(例えばフ
ェニル基等)、アルコキシ基(例えばメトキシ基、エト
キシ基等)、アリールオキシ基(例えばフェニルオキシ
基等)、アルキルチオ基(例えばメチルチオ基、エチル
チオ基等)、アリールチオ基(例えばフェニルチオ基等
)、アルキルスルボニル基(例えばメタンスルホニル基
、エタンスルホニル基等)またはアリールスルホニル基
(例えばベンゼンスルホニル基等)であり、R′5の好
ましくはアルキル基であり、さらに好ましくはメチル基
、エチル基である。That is, alkyl M (e.g., methyl group, ethyl group, propyl group, butyl group, dodecyl group, etc.), aryl group (e.g., phenyl group, etc.), alkoxy group (e.g., methoxy group, ethoxy group, etc.), aryloxy group (e.g., phenyloxy group, etc.). ), alkylthio groups (e.g. methylthio group, ethylthio group etc.), arylthio group (e.g. phenylthio group etc.), alkylsulfonyl group (e.g. methanesulfonyl group, ethanesulfonyl group etc.) or arylsulfonyl group (e.g. benzenesulfonyl group etc.) ), and R'5 is preferably an alkyl group, more preferably a methyl group or an ethyl group.
mは0〜2の整数を表わす、Z4は水素原子、または芳
昏族第1級アミン系発色現像主薬の酸化体との反応によ
り離脱し得る基を表わす。m represents an integer of 0 to 2; Z4 represents a hydrogen atom or a group capable of being separated by reaction with an oxidized product of an aromatic primary amine color developing agent;
式[【1、[1]、[1′1および[■′]において、
Z9、Z3、Z1′および Z、で表わされる芳香族第
1級アミン系発色現像主薬の酸化体との反応によりf’
lJI l1liし得る基は、当業者の周知のものであ
り、カプラーの反応性を改質し、またはカプラーからI
IJI Jul シて、ハロゲン化銀カラー写真感光材
わ1中のカプラーを含む塗布層もしくはその他の層にお
いて、現象抑制、漂白抑制、色補正などのは能をはだす
ことにより有利に作用するものである1代表的なものと
しては、例えば7%ロデン原子、アルコキシ基、アリー
ルオキシ基、アリールアゾ基、千オニーチル、カルバモ
イルオキシ基、アシルオキシ基、イミド基、スルホンア
ミド基、チオシアノ基または複索環基(例えば、オキサ
シリル、ジアゾリル、トリアゾリル、テトラゾリル等)
などが挙げられろ、Z″C表わされる特に好適な例は、
水素原子または塩素原子である。In the formula [[1, [1], [1'1 and [■'],
f' by reaction with oxidized products of aromatic primary amine color developing agents represented by Z9, Z3, Z1' and Z.
Groups that can be used to modify the reactivity of the coupler or remove I from the coupler are well known to those skilled in the art.
IJI Jul In fact, in the coating layer or other layers containing a coupler in the silver halide color photographic light-sensitive material 1, it works advantageously by exerting functions such as phenomenon suppression, bleaching suppression, and color correction. One representative example is, for example, a 7% lodene atom, an alkoxy group, an aryloxy group, an arylazo group, a 1,000-onythyl group, a carbamoyloxy group, an acyloxy group, an imide group, a sulfonamide group, a thiocyano group, or a polycyclic group ( For example, oxacylyl, diazolyl, triazolyl, tetrazolyl, etc.)
A particularly preferred example represented by Z″C is
It is a hydrogen atom or a chlorine atom.
以下に式[111で表わされるシアンカプラーの代表的
具体IP11を示すが、これらに限定されるものではな
い。Typical examples of the cyan coupler IP11 represented by the formula [111] are shown below, but the invention is not limited thereto.
以下余白
t
CL
前記本発明においてシアンカプラーの添加量はシアンカ
プラー総量としてハロゲン化銀1モル当たり2X10−
’モル−1モルが好ましく、より好ましくは1×10−
2モル−8X10−’モルの範囲である。Below is a margin t CL In the present invention, the amount of cyan coupler added is 2X10- per mole of silver halide as the total amount of cyan coupler.
'mol - 1 mol is preferred, more preferably 1 x 10 -
The range is 2 moles - 8X10 moles.
また、本発明に係る2、5−ジアシルアミノフェノール
系シアンカプラーと一般式[111で表わされるシアン
カプラーを併用する場合、その割合は前者のシアンカプ
ラーに対して一般式[■1のシアンカプラーカ弓O〜9
0モル%が好ましく、より好ましくは20〜90モル%
である。In addition, when the 2,5-diacylaminophenol cyan coupler according to the present invention and the cyan coupler represented by the general formula [111] are used together, the ratio of the cyan coupler of the general formula [■1] to the former cyan coupler is Bow O~9
Preferably 0 mol%, more preferably 20 to 90 mol%
It is.
次に、一方のフェノール性水酸基が置換されており、か
つ少なくとも一方のフェノール環が置換基を有するビス
型フェノール誘導体(以下、ビス型フェノール誘導体と
称す。)について説明する。Next, a bis-type phenol derivative (hereinafter referred to as a bis-type phenol derivative) in which one phenolic hydroxyl group is substituted and at least one phenol ring has a substituent will be described.
一方のフェノール性水酸基の置換基としては、例えば脂
肪族炭化水素(例えばアルキル基、アルケニル基)、脂
環式炭化水素(例えばシクロアルキル基)、芳香族炭化
水素基、スルホニル基(例えばアリールスルホニル基、
アルキルスルホニル基)、アシル基が挙げられ、該置換
基は更に置換基を有するものを含む。Substituents for one phenolic hydroxyl group include, for example, aliphatic hydrocarbons (e.g. alkyl groups, alkenyl groups), alicyclic hydrocarbons (e.g. cycloalkyl groups), aromatic hydrocarbon groups, sulfonyl groups (e.g. arylsulfonyl groups). ,
(alkylsulfonyl group) and acyl group, and the substituents include those having further substituents.
ビス型フェノール誘導体における2つのフェノール環は
直接結合していても、結合基を介して結合していてもよ
い。該結合基としては、例えばアルキリデン基、アルキ
レン基、スルホニル基、ペテロ原子(例えば酸素、硫黄
)が挙げられ、好ましくはアルキリデン基、硫黄原子が
挙げられる。The two phenol rings in the bis-type phenol derivative may be bonded directly or may be bonded via a bonding group. Examples of the bonding group include an alkylidene group, an alkylene group, a sulfonyl group, and a petero atom (eg, oxygen, sulfur), and preferably an alkylidene group and a sulfur atom.
又2つのフェノール環は結合位置は、フェノール性水酸
基及び置換されたフェノール性水酸基に対してオルト位
同士であることが好ましい。Further, the bonding positions of the two phenol rings are preferably ortho positions relative to the phenolic hydroxyl group and the substituted phenolic hydroxyl group.
ビス型フェノール誘導体におけるフェノール環には、フ
ェノール性のベンゼン環に他の環が縮合した縮合環も包
含される。The phenol ring in the bis-type phenol derivative also includes a fused ring in which another ring is fused to a phenolic benzene ring.
ビス型フェノール誘導体における少なくとの一方のフェ
ノール環が有する置換基としては1例えばアルキル基、
シクロアルキル基、アルケニル基、アリール基が挙げら
れる。Examples of substituents on at least one phenol ring in the bis-type phenol derivative include 1, for example, an alkyl group,
Examples include a cycloalkyl group, an alkenyl group, and an aryl group.
これら置換基の置換位置としては、フェノール性水酸基
及び置換されたフェノール性水酸基のオルト位及び/又
はバラ位が好ましく、両基のオルト位の置換基同士及び
バラ位の置換基同士が、それぞれ同一であることが好ま
しい。The substitution positions of these substituents are preferably the ortho position and/or the rose position of the phenolic hydroxyl group and the substituted phenolic hydroxyl group, and the substituents at the ortho position and the rose position of both groups are the same, respectively. It is preferable that
次にビス型フェノール誘導体の具体的代表例を示すが本
発明は、これらに限定されるものではない。Next, specific representative examples of bis-type phenol derivatives will be shown, but the present invention is not limited thereto.
CH31−Ha
1;tls CHt−C*H*(t)本発明のビス型
フェノール誘導体はフェノール性水酸基が置換されてい
ないビス型フェノール化合物に、例えばハロゲン化アル
キル、カルボン酸ハロゲン化物、スルホン酸ハロゲン化
物、ジアルキル硫酸等を反応させることにより得ること
ができる。CH31-Ha 1; tls CHt-C*H*(t) The bis-type phenol derivative of the present invention is a bis-type phenol compound in which the phenolic hydroxyl group is not substituted, for example, an alkyl halide, a carboxylic acid halide, a sulfonic acid halide. It can be obtained by reacting compounds, dialkyl sulfates, etc.
ビス型フェノール誘導体の添加場所としてはカプラーを
含有するハロゲン化銀乳剤層又はその隣接層が好ましく
、特に高沸点有機溶媒中にカプラーと共存していること
が好ましい。The bis-type phenol derivative is preferably added to a silver halide emulsion layer containing a coupler or a layer adjacent thereto, and it is particularly preferred that the bis-type phenol derivative coexists with the coupler in a high-boiling organic solvent.
ビス型フェノール誘導体の添加量としてはカプラー1モ
ル当り 0.1〜2.0モルが好ましく、特に0.2〜
1.0モルが好ましい。The amount of bis-type phenol derivative added is preferably 0.1 to 2.0 mol, particularly 0.2 to 2.0 mol per mol of coupler.
1.0 mol is preferred.
本発明においてビス型フェノール誘導体は、高沸点有機
溶媒の同一油滴中に2,5−ジアシルアミノフェノール
系シアンカプラーと共存した状態てハロゲン化銀乳剤層
中に含有せしめられるが、該高沸点有機溶媒としては沸
点が150°C以上の水と非混和性のものが好ましく、
例えば現像主薬の酸化体と反応しないフェノール誘導体
、フタル酸エステル、リン酸エステル、クエン酸エステ
ル、安息香酸エステル、アルキルアミド、脂肪酸エステ
ル、脂肪酸アミド、トリメシン酸エステル等が挙げられ
る。In the present invention, the bis-type phenol derivative is contained in the silver halide emulsion layer in the same oil droplet of a high-boiling point organic solvent, in coexistence with a 2,5-diacylaminophenol cyan coupler. The solvent is preferably one that is immiscible with water and has a boiling point of 150°C or higher;
Examples include phenol derivatives, phthalate esters, phosphate esters, citric acid esters, benzoate esters, alkylamides, fatty acid esters, fatty acid amides, trimesic acid esters, and the like, which do not react with the oxidized product of the developing agent.
高沸点有機溶媒の中でも、誘電率が6.0以下のものが
好ましい。Among high boiling point organic solvents, those with a dielectric constant of 6.0 or less are preferred.
誘電率が6.0以下の高沸点有機溶媒は、例えば誘電率
6.0以下のフタル酸エステル、燐酸エステル等のエス
テル類、有機酸アミド類、ケトン類、炭化水素化合物等
である。好ましくは誘電率6.0以下1.9以上で10
0℃における蒸気圧が0.5mmHg以下の高沸点有機
溶媒である。またより好ましくは、該高沸点有機溶媒中
のフタル酸エステル類或いは燐酸エステル類である。更
に、該高沸点有機溶媒は2種以上の混合物であってもよ
い。Examples of high-boiling organic solvents having a dielectric constant of 6.0 or less include esters such as phthalates and phosphoric esters, organic acid amides, ketones, and hydrocarbon compounds having a dielectric constant of 6.0 or less. Preferably, the dielectric constant is 6.0 or less and 1.9 or more and 10
It is a high boiling point organic solvent with a vapor pressure of 0.5 mmHg or less at 0°C. Even more preferred are phthalic esters or phosphoric esters in the high-boiling organic solvent. Furthermore, the high boiling point organic solvent may be a mixture of two or more.
なお、本発明での誘電率とは、30℃における誘電率を
示している。Note that the dielectric constant in the present invention refers to the dielectric constant at 30°C.
本発明において有利に用いられるフタル酸エステルとし
ては、下記−服代[m]て示されるものが挙げられる。Examples of phthalic acid esters advantageously used in the present invention include those shown below.
一般式[II[コ
式中、 R,及びR2はそれぞれアルキル基、アルケニ
ル基又はアリール基を表す。但し、 R1及びR2で表
される基の炭素数の総和は12ないし32である。また
より好ましくは炭素数の総和が16ないし24である。In the general formula [II], R and R2 each represent an alkyl group, an alkenyl group, or an aryl group. However, the total number of carbon atoms in the groups represented by R1 and R2 is 12 to 32. More preferably, the total number of carbon atoms is 16 to 24.
本発明において、前記−服代[m]のR1及びR2で表
されるアルキル基は、直鎖でも分岐のものでもよく、例
えばブチル基、ペンチル基、ヘキシル基、2−エチルヘ
キシル基、 3,5.5−トリメチルヘキシル基、オク
チル基、ノニル基、デシル基、ドデシル基、テトラデシ
ル基、ヘキサデシル基、オクタデシル基等である。R8
及びR2て表されるアリール基は、例えばフェニル基、
ナフチル基等であり、アルケニル基は、例えばヘキセニ
ル基、ヘプテニル基、オクタデセニル基等である。In the present invention, the alkyl group represented by R1 and R2 in the above-mentioned -clothing cost [m] may be linear or branched, such as a butyl group, a pentyl group, a hexyl group, a 2-ethylhexyl group, 3,5 .5-trimethylhexyl group, octyl group, nonyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, etc. R8
The aryl group represented by and R2 is, for example, a phenyl group,
Examples of the alkenyl group include a naphthyl group, and examples of the alkenyl group include a hexenyl group, a heptenyl group, and an octadecenyl group.
これらのアルキル基、アルケニル基及びアリール基は、
単一もしくは複数の置換基を有するものも含み、アルキ
ル基及びアルケニル基の置換基としては、例えばハロゲ
ン原子、アルコキシ基、アリール基、アリールオキシ基
、アルケニル基、アルコキシカルボニル基等が挙げられ
、アリール基の置換基としては、例えばハロゲン原子、
アルキル基、アルコキシ基、アリール基、アリールオキ
シ基、アルケニル基、アルコキシカルボニル基等を挙げ
ることができる。These alkyl groups, alkenyl groups and aryl groups are
Substituents for alkyl and alkenyl groups include, for example, halogen atoms, alkoxy groups, aryl groups, aryloxy groups, alkenyl groups, alkoxycarbonyl groups, etc. Examples of substituents of the group include halogen atoms,
Examples include an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an alkenyl group, and an alkoxycarbonyl group.
上記において、R8及びR2は好ましくはアルキル基で
あり1例えば2−エチルヘキシル基、3,5゜5−トリ
メチルヘキシル基、n−オクチル基、n−ノニル基等で
ある。In the above, R8 and R2 are preferably alkyl groups, such as 2-ethylhexyl group, 3,5°5-trimethylhexyl group, n-octyl group, n-nonyl group, etc.
本発明において有利に用いられる燐酸エステルとしては
、下記−服代[■]で示されるものが挙げられる。Phosphoric esters that are advantageously used in the present invention include those shown below.
一般式[IV]
式中、 R3,R4及びR5はそれぞれアルキル基、ア
ルケニル基又はアリール基を表す、但し、R3、R4及
びR,で表される基の炭素数の総和は24ないし54で
ある。General formula [IV] In the formula, R3, R4 and R5 each represent an alkyl group, an alkenyl group or an aryl group, provided that the total number of carbon atoms in the groups represented by R3, R4 and R is 24 to 54. .
一般式[17]のR3、R4及びR,て表されるアルキ
ル基は、例えばブチル基、ペンチル基、ヘキシル基、2
−エチルヘキシル基、ヘプチル基、ノニル基、デシル基
、ドデシル基、テトラデシル・基、ヘキサデシル基、オ
クタデシル基、ノナデシル基等であり、アリール基とし
ては、例えばフェニル基、ナフチル基等であり、またア
ルケニル基としては、例えばヘキセニル基、ヘプテニル
基、オクタデセニル基等である。The alkyl groups represented by R3, R4 and R in general formula [17] are, for example, butyl group, pentyl group, hexyl group, 2
- Ethylhexyl group, heptyl group, nonyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, nonadecyl group, etc.; examples of the aryl group include phenyl group, naphthyl group, etc., and alkenyl group Examples include hexenyl group, heptenyl group, octadecenyl group, and the like.
これらのアルキル基、アルケニル基及びアリール基は、
単一もしくは複数の置換基を有するものも含む、好まし
くはR3、R4及びR5はアルキル基であり1例えば2
−エチルヘキシル基、n−オクチル基、3,5.5−ト
リメチルヘキシル基、n−ノニル基、n−デシル基、5
ec−デシル基、 5ee−ドデシル基、t−オクチル
基等が挙げられる。These alkyl groups, alkenyl groups and aryl groups are
Preferably R3, R4 and R5 are alkyl groups, including those having single or multiple substituents, such as 1, for example 2
-ethylhexyl group, n-octyl group, 3,5.5-trimethylhexyl group, n-nonyl group, n-decyl group, 5
Examples include ec-decyl group, 5ee-dodecyl group, t-octyl group, and the like.
以下に、本発明に用いられる高沸点有機溶媒の代表的具
体例を示すが、本発明はこれらに限定されるものではな
い。Typical specific examples of high boiling point organic solvents used in the present invention are shown below, but the present invention is not limited thereto.
例示有機溶媒 C!2H5 2H5 S−9 S−10 02H。Exemplary organic solvent C! 2H5 2H5 S-9 S-10 02H.
0−0H20H(OH2) 30H3
0H20H(OH2)3(3H3
2H5
0−Og HIg(i)
0=P−0−0,H,、(i)
0−09H19(i)
0−C3H+5(II)
0=P−00sH1g(n)
0−CsHxs(n)
001oHzl(i)
富
o =p o c 10H21(’)■
0 01oH21(i)
o−C1oH2□(n)
O−C工OH2□(rl)
0−C1□H23(i)
0=P 0−011H23(1)
0− CoHz3(i)
0−C1zHzs(i)
o=p−o−cm2H25(z)
0−C1□H25(i)
高沸点有機溶媒の使用量としては、カプラー1gに対し
、 0.1〜10Il1文が好ましく、特に0.5〜2
mfLが好ましい。0-0H20H(OH2) 30H3 0H20H(OH2)3(3H3 2H5 0-Og HIg(i) 0=P-0-0,H,, (i) 0-09H19(i) 0-C3H+5(II) 0= P-00sH1g(n) 0-CsHxs(n) 001oHzl(i) Wealth o = p oc 10H21(')■ 0 01oH21(i) o-C1oH2□(n) O-COH2□(rl) 0- C1□H23(i) 0=P 0-011H23(1) 0- CoHz3(i) 0-C1zHzs(i) o=po-o-cm2H25(z) 0-C1□H25(i) High boiling point organic solvent The amount used is preferably 0.1 to 10 Il1, particularly 0.5 to 2
mfL is preferred.
カプラー及びビス型フェノール誘導体の添加方法として
は氷中油滴型乳化分散法が好ましい。The preferred method for adding the coupler and bis-type phenol derivative is an oil-in-ice emulsion dispersion method.
氷中油滴型乳化分散法は、カプラー等の疎水性添加物を
高沸点有機溶媒に、必要に応じて低沸点および/または
水溶性有機溶媒を併用して溶解し、ゼラチン水溶液等の
親水性バインダー中に界面活性剤を用いて攪拌器、ホモ
ジナイザー、コロイドミル、フロージットミキサー、超
音波装設等の分散手段を用いて、乳化分散した後、目的
とする親水性コロイド層中に添加すればよい。分散液又
は分散と同時に低沸点有機溶媒を除去する工程を入れて
もよい。In the oil-in-ice emulsion dispersion method, hydrophobic additives such as couplers are dissolved in a high-boiling organic solvent, if necessary in combination with a low-boiling point and/or water-soluble organic solvent, and a hydrophilic binder such as an aqueous gelatin solution is dissolved. After emulsifying and dispersing the mixture using a dispersion means such as a stirrer, homogenizer, colloid mill, flow jet mixer, or ultrasonic device using a surfactant, it can be added to the desired hydrophilic colloid layer. . A step of removing the low boiling point organic solvent may be included simultaneously with the dispersion or dispersion.
本発明のへロゲン化銀写真感光材料は、例えばカラーネ
ガ及びポジフィルム、ならびにカラー印画紙等であるこ
とかでき、単色用のものでも多色用のものてもよい。The silver halide photographic light-sensitive material of the present invention can be, for example, color negative and positive films, color photographic paper, etc., and may be one for monochrome use or one for multicolor use.
多色用ハロゲン化銀写真感光材料の場合には、通常、マ
ゼンタ、イエロー及びシアンの各カプラーを含有するハ
ロゲン化銀乳剤層ならびに非感光性層が、支持体上に適
宜の暦数及び層順で積層した構造を有しているが、該層
数及び層順は重点性能、使用目的によって適宜変更して
もよい。In the case of multicolor silver halide photographic light-sensitive materials, silver halide emulsion layers containing magenta, yellow, and cyan couplers and non-light-sensitive layers are usually formed on a support in an appropriate number and layer order. Although it has a laminated structure, the number and order of layers may be changed as appropriate depending on the important performance and purpose of use.
本発明のハロゲン化銀写真感光材料に用いられるハロゲ
ン化銀乳剤としては臭化銀、沃臭化銀、沃塩化銀、塩臭
化銀及び塩化銀等の通常ハロゲン化銀乳剤に使用される
任意のものを用いることができる。Silver halide emulsions used in the silver halide photographic light-sensitive material of the present invention include silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, silver chloride, and any other commonly used silver halide emulsions. can be used.
本発明に用いられるハロゲン化銀乳剤は、硫黄増感法、
セレン増感法、還元増感法、貴金属増感法等により化学
増感される。The silver halide emulsion used in the present invention can be prepared by sulfur sensitization method,
Chemically sensitized by selenium sensitization, reduction sensitization, noble metal sensitization, etc.
本発明に用いられるハロゲン化銀乳剤は、写真業界にお
いて、増感色素として知られている色素を用いて、所望
の波長域に光学的に増感できる。The silver halide emulsion used in the present invention can be optically sensitized to a desired wavelength range using a dye known as a sensitizing dye in the photographic industry.
本発明のハロゲン化銀写真感光材料に用いられるバイン
ダー(又は保護コロイド)としては、ゼラチンを用いる
のが有利であるが、それ以外にゼラチン誘導体、ゼラチ
ンと他の高分子のグラフトポリマー、蛋白質、糖誘導体
、セルロース誘導体、単一あるいは共重合体の如き合成
親水性高分子物質等の親水性コロイドも用いるこができ
る。As the binder (or protective colloid) used in the silver halide photographic material of the present invention, gelatin is advantageously used, but gelatin derivatives, graft polymers of gelatin and other polymers, proteins, sugars, etc. Hydrophilic colloids such as derivatives, cellulose derivatives, synthetic hydrophilic polymeric materials such as single or copolymers may also be used.
本発明のハロゲン化銀写真感光材料には、ざらに硬膜剤
、色濁り防止剤1画像安定剤、可塑剤、ラテックス、界
面活性剤、マット剤、滑剤、帯電防止剤等の添加剤を必
要に応じて用いることができる。The silver halide photographic material of the present invention requires additives such as a hardening agent, a color clouding prevention agent, an image stabilizer, a plasticizer, a latex, a surfactant, a matting agent, a lubricant, and an antistatic agent. It can be used depending on the situation.
本発明のハロゲン化銀写真感光材料は、当業界公知の発
色現像処理を行うことにより画像を形成することができ
る。An image can be formed on the silver halide photographic material of the present invention by subjecting it to color development treatment known in the art.
[発明の効果] 本発明のハロゲン化銀写真感光材料によれば。[Effect of the invention] According to the silver halide photographic material of the present invention.
シアン色素画像の保存性特に暗退色性、光堅牢性及び光
黄色変が同時に改良されたハロゲン化銀写真感光材料を
提供することができる。It is possible to provide a silver halide photographic light-sensitive material in which cyan dye image storage stability, especially dark fading resistance, light fastness, and light yellowing are simultaneously improved.
[実施例コ
以下、本発明を実施例により具体的に説明するが、本発
明の実施の態様はこれらに限定されない。[Example 7] The present invention will be specifically explained below using Examples, but the embodiments of the present invention are not limited thereto.
実施例 l
シアンカプラー(C−1)60g8よびビス型フェノー
ル誘導体化合物(14) 32gを高沸点有機溶媒(D
OP)と酢酸エチルに溶解した溶液を、分散助剤(ドデ
シルベンゼンスルホン酸ナトリウム塩)を含む8%ゼラ
チン水溶液に添加しホモジナイザーにて分散した。得ら
れた分散液をISOOmiに仕上げ、40℃で3時間保
温した。この分散液を塗布用3%ゼラチン水溶液100
口■又に加え、更に赤感性塩臭化銀乳剤400g (臭
化銀80モル%含有)を添加し赤感性乳剤層用塗布液を
調整した。Example l 60g8 of cyan coupler (C-1) and 32g of bis-type phenol derivative compound (14) were dissolved in a high boiling point organic solvent (D
A solution of OP) and ethyl acetate was added to an 8% aqueous gelatin solution containing a dispersion aid (dodecylbenzenesulfonic acid sodium salt) and dispersed with a homogenizer. The resulting dispersion was finished into ISOOmi and kept at 40° C. for 3 hours. Apply this dispersion to a 3% aqueous gelatin solution for coating.
In addition to the above, 400 g of a red-sensitive silver chlorobromide emulsion (containing 80 mol % of silver bromide) was added to prepare a coating solution for a red-sensitive emulsion layer.
この塗布液を40°Cで2時間保温した。This coating solution was kept at 40°C for 2 hours.
同様にして、各層の塗布液を調整し、ポリエチレン被覆
紙支持体上に、下記構成となるよう毎分100mの塗布
速度で塗設した。Coating solutions for each layer were prepared in the same manner, and coated on a polyethylene-coated paper support at a coating speed of 100 m/min to have the following composition.
第1暦:青感性乳剤層
イエローカプラー(Y−1)を8B/ dm″、青感性
塩臭化銀乳剤(塩化銀20モル%、臭化銀80モル%含
有)を銀に換算して3B/dm”、高沸点有機溶媒(D
OP)を3111g/dm″及びゼラチンを16B/d
m″の塗布付量となるように塗設。First calendar: Blue-sensitive emulsion layer Yellow coupler (Y-1) is 8B/dm'', blue-sensitive silver chlorobromide emulsion (containing 20 mol% silver chloride and 80 mol% silver bromide) is 3B in terms of silver. /dm”, high boiling point organic solvent (D
OP) at 3111 g/dm'' and gelatin at 16 B/d.
Apply so that the coating amount is m''.
第218=中間層
ハイドロキノン誘導体(HQ−1)を0.45mg/d
ゴ、DOPを4mg/dゴ及びゼラチンを4mg/dゴ
の塗布付量となるように塗設。No. 218 = 0.45 mg/d of middle layer hydroquinone derivative (HQ-1)
The coating amount was 4 mg/d of DOP and 4 mg/d of gelatin.
第3層:緑感性乳剤層
マゼンタカプラー(M−1)を4mg/dm″、緑感性
塩臭化銀乳剤(塩化銀20モル%、臭化@[80モル%
含有)を銀に換算して軸g/dm″、高沸点*機溶媒(
DOP)を4mg/drn” 、退色防止剤AO−1を
2mg/drrf、AO−2を1mg/dm″及びゼラ
チンを16mg/dm″の塗布付量となるように塗設。3rd layer: green-sensitive emulsion layer magenta coupler (M-1) at 4 mg/dm'', green-sensitive silver chlorobromide emulsion (20 mol% silver chloride, 80 mol% bromide)
Contains) in terms of silver, axis g/dm'', high boiling point * mechanical solvent (
DOP) was applied at a coating amount of 4 mg/drn'', antifading agent AO-1 was applied at 2 mg/drrf, AO-2 was applied at 1 mg/dm'', and gelatin was applied at a coating amount of 16 mg/dm''.
第4層:中間層
紫外線吸収剤(U V−1)を3H/dm″、(υV−
2)を3mg/drn’、高沸点有機溶媒(DOP)を
4tag/drr?、ハイドロキノン誘導体(HQ−2
)を0.45mg/dゴ及びゼラチンを14mg/dm
’の塗布付量となるように塗設。4th layer: Intermediate layer ultraviolet absorber (UV-1) at 3H/dm'', (υV-
2) at 3 mg/drn' and high boiling point organic solvent (DOP) at 4 tag/drr? , hydroquinone derivative (HQ-2
) at 0.45mg/dm and gelatin at 14mg/dm
Apply the coating so that the coating amount is '.
第5層:赤感性乳剤層
シアンカプラー(C−1)を411g/dm″、高沸点
有機溶媒(DOP)を4+1g/drn’、ビス型フェ
ノール誘導体(14)を4B/dm″、赤感性塩臭化銀
乳剤(塩化銀20モル%、臭化@80モル%含有)を銀
に換算して3+++g/dm’及びゼラチンを14mg
/dm’の塗布付量となるように塗設。5th layer: red-sensitive emulsion layer cyan coupler (C-1) at 411 g/dm'', high boiling point organic solvent (DOP) at 4+1 g/drn', bis-type phenol derivative (14) at 4 B/dm'', red-sensitive salt Silver bromide emulsion (containing 20 mol% silver chloride and 80 mol% bromide) is converted to silver at 3+++ g/dm' and gelatin is 14 mg.
/dm' coating amount.
第6層:中間層
紫外線吸収剤(U V−3)を4rtrg/drrf、
高沸点有機溶媒(DOP)を2mg/drn’及びゼラ
チンを6B/drrr’の塗布付量となるように塗設。6th layer: Intermediate layer ultraviolet absorber (UV-3) 4rtrg/drrf,
High boiling point organic solvent (DOP) was applied at a coating amount of 2 mg/drn' and gelatin was applied at a coating amount of 6B/drrr'.
第7層:保護層
ゼラチンを91g/dm″の塗布付量となるように塗設
。7th layer: Protective layer Gelatin was coated at a coating weight of 91 g/dm''.
(試料作製に用いた化合物) DOP ニジオクチルフタレート I2 O−1 O−2 HQ−1 HQ−2 l じ2t15 υi tr*−1 H C,H,、(t) V−2 H V−3 H 2H5 この試料を試料lとした。(Compound used for sample preparation) DOP Nidioctyl phthalate I2 O-1 O-2 HQ-1 HQ-2 l 2t15 υi tr*-1 H C,H,,(t) V-2 H V-3 H 2H5 This sample was designated as sample 1.
次に試料1の第5Nのビス型フェノール誘導体及び高洟
点有機溶媒を表1に示すように代えた以外は試料1と同
様にした試料2〜16を作成した(ビス型フェノール誘
導体は試料1と等モル添加した。)、これらの試料に感
光針(コニカ社製KS−7型)を用いて赤色光て先後露
光を与えた後、次の処理を行った。Next, Samples 2 to 16 were prepared in the same manner as Sample 1 except that the 5N bis-type phenol derivative and the high point organic solvent of Sample 1 were changed as shown in Table 1 (the bis-type phenol derivative was used in Sample 1). ), these samples were exposed to red light using a photosensitive needle (Model KS-7, manufactured by Konica), and then subjected to the following treatment.
処理工程 処理温度 処理時間発色現像
32.8°03分30秒漂白定着 32.8
℃ 1分30秒水 洗 32.8℃
3分30秒[発色現像液組成]
硫酸塩 4.0gヒドロ
キシルアミン硫酸塩 2.0g炭酸カリウム
25.0g塩化ナトリウム
0.1g臭化カリウム
0.2g無水亜硫酸ナトリウム
2.0gベンジルアルコール
10.0m文ポリエチレングリコール
(平均重合度400 ) 3.0m
文水を加えて1fLとし、水酸化ナトリウムを用いて、
pH10,0に調整する。Processing process Processing temperature Processing time Color development
32.8°03 minutes 30 seconds bleach fixing 32.8
℃ Wash with water for 1 minute and 30 seconds 32.8℃
3 minutes 30 seconds [Color developer composition] Sulfate 4.0g Hydroxylamine sulfate 2.0g Potassium carbonate 25.0g Sodium chloride
0.1g potassium bromide
0.2g anhydrous sodium sulfite
2.0g benzyl alcohol
10.0m polyethylene glycol (average degree of polymerization 400) 3.0m
Add Bunsui to make 1fL, use sodium hydroxide,
Adjust the pH to 10.0.
[漂白定着液組成]
エチレンジアミン四酢酸鉄
ナトリウム塩 60.0gチオ
硫酸ナトリウム 100.0g重亜硫酸
ナトリウム 20.0gメタ重亜硫酸
ナトリウム 5.0g水を加えて141と
し、硫酸を用いてpH7,0に調整する。[Bleach-fix solution composition] Ethylenediaminetetraacetic acid sodium salt 60.0g Sodium thiosulfate 100.0g Sodium bisulfite 20.0g Sodium metabisulfite 5.0g Water was added to make 141, and the pH was adjusted to 7.0 using sulfuric acid. do.
処理後に得られた各試料について、シアン色画像の光堅
牢性、光黄色変及び暗退色性を以下の要領で評価した。For each sample obtained after processing, the light fastness, light yellowing, and dark fading of the cyan image were evaluated in the following manner.
[光堅牢性試験]
アンダーグラス屋外日光曝露台を用いて30日間太陽光
を曝射した時の初濃度D0= 1.0の残存率で示した
。(D=退色後の濃度)
[光黄色変試験コ
光堅牢性試験を行った各試料の未露光部における青色濃
度の値と試験前の値との差ΔD、で示した。[Light fastness test] The residual rate was shown as the initial concentration D0 = 1.0 when exposed to sunlight for 30 days using an underglass outdoor sunlight exposure table. (D=density after fading) [Light yellowing test] It was expressed as the difference ΔD between the blue density value in the unexposed area of each sample subjected to the light fastness test and the value before the test.
[暗退色性試験]
暗所にて70”C140XR)lにて2週間保存した後
の退色性を、上記光堅牢性と同様に残存率として求めた
。[Dark Fading Resistance Test] The fading property after being stored for 2 weeks in the dark in 70" C140
表1の結果から試、!41及び2の試料において、比較
シアンカプラー(C−1)との組合せにおいて、本発明
のビス型フェノール誘導体は暗退色性には若干の改良効
果があるものの未だ不充分であり、光堅牢性については
、わずか5%の改良にすぎず、光黄色変には改良効果が
ない、また試料3において、本発明のシアンカプラーは
暗退色性の点ては非常に優れた性能を有するが、光堅牢
性及び光黄色変の点では劣り実用上問題となるレベルで
あることがわかる。しかし本発明の組合せである試料4
〜11は暗退色性も良好であり、かつ光堅牢性及び光黄
色変の点て十分な改良がなされていることがわかる。こ
の効果は従来の知見からは予測し得ないものである。ま
たシアンカプラーとして[I]及び[II]の併用によ
る試料13〜16ては暗退色性の向上も見られ更に良好
な性能を有することかわかる。Try from the results in Table 1! In samples No. 41 and 2, in combination with the comparative cyan coupler (C-1), although the bis-type phenol derivative of the present invention had a slight improvement effect on dark fading resistance, it was still insufficient, and the light fastness was In sample 3, the cyan coupler of the present invention has excellent performance in terms of dark fading resistance, but has poor light fastness. It can be seen that the properties and optical yellowing were inferior and were at a level that would pose a practical problem. However, sample 4, which is a combination of the present invention,
It can be seen that Samples No. 1 to 11 had good dark fading properties and were sufficiently improved in terms of light fastness and light yellowing. This effect cannot be predicted from conventional knowledge. Further, in Samples 13 to 16, where the cyan couplers [I] and [II] were used in combination, an improvement in dark fading resistance was observed, indicating that they had even better performance.
実施例 2
実施例1に使用した各ハロゲン化銀乳剤に代えて塩化銀
99.5モル%の塩臭化銀乳剤を使用し、シアンカプラ
ー及びビス型フェノール誘導体を表2に示すように変化
させた以外は実施例1の試料1と同様の各試料(試料1
7〜25)を作製した。各試料を常法に従って赤色光で
先後露光後、以下に示す処理を行った。Example 2 A silver chlorobromide emulsion containing 99.5 mol % of silver chloride was used in place of each silver halide emulsion used in Example 1, and the cyan coupler and bis-type phenol derivative were changed as shown in Table 2. Each sample (Sample 1) was the same as Sample 1 of Example 1 except that
7 to 25) were prepared. Each sample was exposed to red light in a conventional manner and then subjected to the following treatments.
処理工程 処理温度 処理時間発色現像
34.7±0.3℃ 50秒漂白定着 3
4.7±0.5℃ 50秒安定化 30〜34
°C90秒
乾 燥 60〜80℃ 6
0秒各処理工程において、使用した処理液組成は下記の
如くである。Processing process Processing temperature Processing time Color development
34.7±0.3℃ 50 seconds bleach fixing 3
4.7±0.5℃ Stabilized for 50 seconds 30-34
Dry for 90 seconds at °C 60-80 °C 6
The composition of the treatment liquid used in each treatment step is as follows.
[発色現像液コ
エチレングリコール 1.Om文N、
N−ジエチルヒドロキシルアミン 10nl塩化カ
リウム 2gテトラポリ燐酸
ナトリウム 2g炭酸カリウム
30g蛍光増白剤(4,4’−ジアミノ
スチルベンズスルホン酸誘導体)
1.0g純水を加えて全量を1文とし、 pH10,0
8に調整する。[Color developer coethylene glycol 1. Om sentence N,
N-diethylhydroxylamine 10nl Potassium chloride 2g Sodium tetrapolyphosphate 2g Potassium carbonate
30g optical brightener (4,4'-diaminostilbenzsulfonic acid derivative)
Add 1.0g of pure water to make one sentence, pH 10.0
Adjust to 8.
[漂白定着液]
エチレンジアミン四酢酸第2鉄
アンモニウム2水塩 60gエチレンジ
アミン四酢酸 3gチオ硫酸アンモニウム
(70%溶液) 100mM亜硫酸アンモニウム(4
0%溶液) 27.5■交水を加えて1文とし、
炭酸カリウム又は氷酢酸でpH7,1に調整する。[Bleach-fix solution] Ferric ammonium ethylenediaminetetraacetic acid dihydrate 60g ethylenediaminetetraacetic acid 3g ammonium thiosulfate (70% solution) 100mM ammonium sulfite (4
0% solution) 27.5■ Add water to make one sentence,
Adjust the pH to 7.1 with potassium carbonate or glacial acetic acid.
[安定化液]
5−クロロ−2−メチル−4−イソチアゾリン−3−オ
ン 1g水を加えてlfL
とし、硫酸又は水酸化カリウムでpH7,0に調整する
。[Stabilizing liquid] 5-chloro-2-methyl-4-isothiazolin-3-one Add 1 g of water and lfL
and adjust the pH to 7.0 with sulfuric acid or potassium hydroxide.
処理後の各試料の光堅牢性、光黄色変及び暗退色性を実
施例1と同様に評価した。その結果を表2に示す。The light fastness, light yellowing, and dark fading of each sample after treatment were evaluated in the same manner as in Example 1. The results are shown in Table 2.
また試料23のシアンカプラー■−1の代わりにn−4
、U−5、ll−8,ll−10,ll−14゜U−1
1i、n−19、U−20を用いた場合も本発明の効果
が認められた。Also, instead of the cyan coupler ■-1 of sample 23, n-4
, U-5, ll-8, ll-10, ll-14゜U-1
The effects of the present invention were also observed when 1i, n-19, and U-20 were used.
表2の結果からも、本発明の試料で光堅牢性、光黄色変
及び及び暗退色性が同時に改良されたことがわかる。The results in Table 2 also show that the light fastness, light yellowing and dark fading properties were simultaneously improved in the samples of the present invention.
実施例 3
実施例2に使用したシアンカプラー、ビス型フェノール
誘導体及び高沸点有機溶媒を表3に示すように変化させ
たこと以外は同じ試料26〜33を作製し、同じ露光処
理の後に光堅牢性、光黄色変及び及び焙退色性について
の評価を行った。その結果を表3に示す。Example 3 Samples 26 to 33, which were the same as those used in Example 2 except that the cyan coupler, bis-type phenol derivative, and high-boiling organic solvent were changed as shown in Table 3, were prepared, and after the same exposure treatment, the light fastness was Evaluations were made regarding color, yellowing, and fading. The results are shown in Table 3.
表3の結果から、本発明の効果は誘電率が低い(6,0
以下)高沸点有機溶媒との組合せで更に良好なものとな
ることがわかる。From the results in Table 3, the effect of the present invention is that the dielectric constant is low (6,0
(below) It can be seen that the combination with a high boiling point organic solvent results in even better results.
試料28の高沸点有機溶媒DOPの代わりに高沸点有機
溶媒S−1、S−5、S−6,5−11,5−12,5
−18,5−19,5−22を用いた場合、又、試料3
0のシアンカプラーl−42の代わりに1−10、ニー
17、l−18、■−20、l−21゜ニー27、ニー
28、ニー36、■−38、ニー43、ニー44、l−
46を用いた場合も本発明の効果が認められた。High boiling point organic solvents S-1, S-5, S-6, 5-11, 5-12, 5 instead of high boiling point organic solvent DOP of sample 28
-18, 5-19, 5-22, and sample 3
0 cyan coupler l-42 instead of 1-10, knee 17, l-18, ■-20, l-21° knee 27, knee 28, knee 36, ■-38, knee 43, knee 44, l-
The effect of the present invention was also observed when No. 46 was used.
実施例 4
両面をポリエチレンコートした紙支持体上に、以下の第
1層から第12層を設けてカラー反転感光材料試料を作
製した。各成分の塗布量はg/m′で示ス、但し、ハロ
ゲン化銀については、銀に換算した塗布量で示す。Example 4 A color reversal photosensitive material sample was prepared by providing the following 1st to 12th layers on a paper support coated with polyethylene on both sides. The coating amount of each component is expressed in g/m'; however, for silver halide, the coating amount is expressed in terms of silver.
第1層(ゼラチン層)
ゼラチン 1・40第2層
(ハレーション防止層)
黒色コロイド銀 0.10ゼラチ
ン 0.60第3層(第1
赤感性層)
シアンカプラーll−10,07
シアンカプラー1−42 0.14ビス
型フ工ノール誘導体(7) 0.20高沸点溶
媒(、S −12) 0.06赤色増
感色素(D−1、D−2)で分光増感されたAgBr1
(Ag13.0モル%、平均粒径0.4pm )0.1
4
ゼラチン 1・0第4層(
第2赤感性層)
シアンカプラーII −10,10
シアンカプラーl−420,20
高沸点溶媒(S −12) 0.10
ビス型フェノール誘導体(7) 0.300.
16
ゼラチン 1・0第5ff
(第1中間層)
ゼラチン 1.0混色防止
剤(AN−1) 0.08第6層(第1
緑感性層)
ビス型フェノール誘導体(7) 0.14マゼ
ンタカプラー(M−2) 0.14高沸点溶
媒(’S −2)−0,15
緑色増感色素(D−3)で分光増感されたAgBr1(
Agl 3.0モル%、平均粒径0.4gm )0.1
5
ゼラチン 1.0第7層(
第2緑感性層)
ビス型フェノール誘導体(7’) 0.14マ
ゼンタカプラー(M −2) 0.14高沸
点溶媒(S −2) 0.150.1
5
ゼラチン 1・0第8層(
第2中間層)
黄色コロイド銀 0.15混色防
止剤(AN−1) 0.08ゼラチン
1・0第9層(第1青感性
層)
イエローカプラー前記(Y−1) 0.40高沸
点溶媒(S −2) 0.100.1
5
とス覆フェノール誘導体(7) 0.40ゼラ
チン 0.70第10層(
第2青感性M)
イエローカプラー前記(Y−1) 0.80高沸
点溶媒(S −2) 0.200.2
0
ビス型フェノール誘導体(7) 0.80ゼラ
チン 1・3第11層(紫
外線吸収層)
紫外線吸収剤1) −10,2
紫外線吸収剤U+ 2 0.2紫外線
吸収剤U −30,2
紫外線吸収剤U −40,2
ゼラチン 20口t512
層(保護層)
ゼラチン 1.0但し、以
上の他に退色防止剤、界面活性剤、硬膜剤、イラジェー
ション防止染料を含有する。1st layer (gelatin layer) Gelatin 1.40 2nd layer (antihalation layer) Black colloidal silver 0.10 Gelatin 0.60 3rd layer (1st layer)
Red-sensitive layer) Cyan coupler ll-10,07 Cyan coupler 1-42 0.14 Bis-type phenol derivative (7) 0.20 High boiling point solvent (S-12) 0.06 Red sensitizing dye (D- 1, AgBr1 spectrally sensitized with D-2)
(Ag 13.0 mol%, average particle size 0.4 pm) 0.1
4 Gelatin 1.0 4th layer (
2nd red sensitive layer) Cyan coupler II -10,10 Cyan coupler l-420,20 High boiling point solvent (S -12) 0.10
Bis-type phenol derivative (7) 0.300.
16 Gelatin 1.0 No. 5ff
(1st intermediate layer) Gelatin 1.0 Color mixing inhibitor (AN-1) 0.08 6th layer (1st
Green-sensitive layer) Bis-type phenol derivative (7) 0.14 Magenta coupler (M-2) 0.14 High boiling point solvent ('S-2) -0.15 Spectral sensitization with green sensitizing dye (D-3) AgBr1 (
Agl 3.0 mol%, average particle size 0.4 gm) 0.1
5 Gelatin 1.0 7th layer (
Second green-sensitive layer) Bis-type phenol derivative (7') 0.14 Magenta coupler (M-2) 0.14 High-boiling solvent (S-2) 0.150.1
5 Gelatin 1.0 8th layer (
2nd intermediate layer) Yellow colloidal silver 0.15 Color mixing inhibitor (AN-1) 0.08 Gelatin
1.0 9th layer (first blue sensitive layer) Yellow coupler (Y-1) 0.40 High boiling point solvent (S-2) 0.100.1
5 Sub-covered phenol derivative (7) 0.40 Gelatin 0.70 10th layer (
Second blue-sensitive M) Yellow coupler (Y-1) 0.80 High boiling point solvent (S-2) 0.200.2
0 Bis-type phenol derivative (7) 0.80 Gelatin 1.3 11th layer (ultraviolet absorption layer) Ultraviolet absorber 1) -10,2 Ultraviolet absorber U+ 2 0.2 Ultraviolet absorber U -30,2 Ultraviolet absorption Agent U-40,2 Gelatin 20 mouths t512
Layer (protective layer) Gelatin 1.0 However, in addition to the above, it contains an anti-fading agent, a surfactant, a hardening agent, and an anti-irradiation dye.
尚、第3層、第4層、第6層、第7層、第9層及び第1
0層においてビス型フェノール誘導体はカプラーと共に
高沸点溶媒に溶解し、分散添加した。In addition, the third layer, the fourth layer, the sixth layer, the seventh layer, the ninth layer, and the first layer
In the 0 layer, the bis-type phenol derivative was dissolved together with the coupler in a high boiling point solvent and added in a dispersed manner.
Cσ
i2
硬膜剤
紫外線吸収剤
OH
RI
RI Ri Rs
U −1(t)CJs (t)CJs HU
−2(t)C,Hs OH,CIU −3(t)
C4H* 、 (t)C4H! CIU−4
(t)CsH++ (t)CsHs* H混色
防止剤(AN−1)
前記試料に対して、下記処理工程を用いた他は実施例1
と同様にして評価したところ、実施例1と同様な本発明
の効果が確認された。Cσ i2 Hardener UV absorber OH RI RI Ri Ri Rs U -1(t)CJs (t)CJs HU
-2(t)C,Hs OH,CIU -3(t)
C4H*, (t)C4H! CIU-4
(t) CsH++ (t) CsHs* H color mixing inhibitor (AN-1) Example 1 except that the following treatment steps were used for the sample.
When evaluated in the same manner as in Example 1, the same effects of the present invention as in Example 1 were confirmed.
第1現像(モノクロ現像) 1分15秒(38°C)第
1水洗 1分30秒光かぶり
1001ux以上 1秒以上第2現像(発色現像)
2分15秒(38℃)第2水洗
45秒漂白定着 2分 (38
°C)第3水洗 2分15秒使用した
処理液の組成は以下の通りである。1st development (monochrome development) 1 minute 15 seconds (38°C) 1st water wash 1 minute 30 seconds Light fogging
1001ux or more 1 second or more 2nd development (color development)
2 minutes 15 seconds (38℃) 2nd water wash
45 seconds bleach fixing 2 minutes (38
°C) Third water washing 2 minutes and 15 seconds The composition of the treatment solution used is as follows.
[第1現像液]
亜硫酸カリウム 3・0gチオシ
アン酸ナトリウム 160g臭化ナトリウ
ム 2・4g沃化カリウム
8.0mg水酸化/’IF ’
) ’) ム(48%) 6.21f
L炭酸カリウム 14g炭酸水
素ナトリウム 12gハイドロキノン
モノスルホネート23.3g水を加えて1交とし、pH
9,65とする。[First developer] Potassium sulfite 3.0g Sodium thiocyanate 160g Sodium bromide 2.4g Potassium iodide
8.0mg hydroxide/'IF'
) ') Mu (48%) 6.21f
L Potassium carbonate 14g Sodium hydrogen carbonate 12g Hydroquinone monosulfonate 23.3g Add water to make 1 mixture, pH
9.65.
[発色現像液]
ベンジルアルコール 14・6mA−
エチレングリコール 12.6m立炭
酸カリウム(無水)26g
水酸化ナトリウム 1.4g亜硫酸
ナトリウム 1.6g3.6−シチ
アオクタンー1.8−ジオール 0.24gヒドロキ
シルアミン硫酸塩 2.6gセスキサルフェ
ート5.0g
水を加えて1文とする。[Color developer] Benzyl alcohol 14.6mA-
Ethylene glycol 12.6m Potassium carbonate (anhydrous) 26g Sodium hydroxide 1.4g Sodium sulfite 1.6g 3.6-cythiaoctane-1.8-diol 0.24g Hydroxylamine sulfate 2.6g Sesquisulfate 5.0g Add water It is one sentence.
[漂白定着液]
エチレンジアミン四酢酸塩二鉄錆体の
アンモニウム塩の1.56モル溶液 115mJ
lメタ重亜硫酸ナトリウム 15.4gチ
オ硫酸アンモニウム(58%) 126iJ1
1.2.4−トリアゾール−3−チオール 0.4
g水を加えてl!;Lとし、pH5,5とする。[Bleach-fix solution] 1.56 molar solution of ammonium salt of ethylenediaminetetraacetate diiron rust 115 mJ
l Sodium metabisulfite 15.4g Ammonium thiosulfate (58%) 126iJ1
1.2.4-triazole-3-thiol 0.4
g Add water and l! ;L and pH 5.5.
特許出願人 コ ニ カ 株 式 会 社代 理 人
弁理士 坂口信昭
手続補正書岨鋤
昭和63年1月5日
特許庁長官 小川邦夫 殿 、;。Patent Applicant Konica Co., Ltd. Representative Patent Attorney Nobuaki Sakaguchi Procedural Amendment Letter January 5, 1988 Mr. Kunio Ogawa, Commissioner of the Patent Office;
l 事件の表示
特願昭62−303892号
2 発明の名称
ハロゲン化銀写真感光材料
3 補正をする者
事件との関係 出願人
名 称 (127)コニカ株式会社
4代理人 刊60
住 所 東京都新宿区西新宿七丁目10番11号第
2イト−ビル5階
6 補正により増加する発明の数
7 補正の対象
明細書(発明の詳細な説明の欄)
8 補正の内容
(1)明細書中第43頁第7〜10行を削除する。l Indication of the case Japanese Patent Application No. 1983-303892 2 Name of the invention Silver halide photographic light-sensitive material 3 Person making the amendment Relationship to the case Applicant name (127) Konica Co., Ltd. 4 Agent Publication 60 Address Shinjuku-ku, Tokyo Nishi-Shinjuku 7-10-11, 2nd Building, 5th floor 6 Number of inventions increased by amendment 7 Specification subject to amendment (detailed description of invention column) 8 Contents of amendment (1) No. 43 in the specification Delete lines 7 to 10 of the page.
(2)同書第53頁第11行に「フロージットミキサー
」とあるを「フロージェットミキサー」と補正する。(2) In the same book, page 53, line 11, the phrase "flow jet mixer" is corrected to "flow jet mixer."
Claims (1)
るハロゲン化銀写真感光材料において、該乳剤層の少な
くとも一層が2,5−ジアシルアミノフェノール系シア
ンカプラー及び一方のフェノール性水酸基が置換されて
おり、かつ少なくとも一方のフェノール環が置換基を有
するビス型フェノール誘導体を同一高沸点有機溶媒油滴
中に含有することを特徴とするハロゲン化銀写真感光材
料。In a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, at least one of the emulsion layers is substituted with a 2,5-diacylaminophenol cyan coupler and one of the phenolic hydroxyl groups. , and a bis-type phenol derivative in which at least one phenol ring has a substituent group is contained in the same high-boiling organic solvent oil droplet.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP30389287A JPH01144050A (en) | 1987-11-30 | 1987-11-30 | Silver halide photographic sensitive material |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP30389287A JPH01144050A (en) | 1987-11-30 | 1987-11-30 | Silver halide photographic sensitive material |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH01144050A true JPH01144050A (en) | 1989-06-06 |
Family
ID=17926519
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP30389287A Pending JPH01144050A (en) | 1987-11-30 | 1987-11-30 | Silver halide photographic sensitive material |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH01144050A (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH03132655A (en) * | 1989-10-19 | 1991-06-06 | Fuji Photo Film Co Ltd | Silver halide color photographic sensitive material |
JP2002102352A (en) * | 2000-09-21 | 2002-04-09 | Smiths Group Plc | Ventilator for patient |
-
1987
- 1987-11-30 JP JP30389287A patent/JPH01144050A/en active Pending
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH03132655A (en) * | 1989-10-19 | 1991-06-06 | Fuji Photo Film Co Ltd | Silver halide color photographic sensitive material |
JP2002102352A (en) * | 2000-09-21 | 2002-04-09 | Smiths Group Plc | Ventilator for patient |
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