JPH04147134A - New photographic coupler - Google Patents
New photographic couplerInfo
- Publication number
- JPH04147134A JPH04147134A JP27098090A JP27098090A JPH04147134A JP H04147134 A JPH04147134 A JP H04147134A JP 27098090 A JP27098090 A JP 27098090A JP 27098090 A JP27098090 A JP 27098090A JP H04147134 A JPH04147134 A JP H04147134A
- Authority
- JP
- Japan
- Prior art keywords
- group
- coupler
- color
- present
- light
- 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
- 125000001424 substituent group Chemical group 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 2
- 230000008878 coupling Effects 0.000 abstract 1
- 238000010168 coupling process Methods 0.000 abstract 1
- 238000005859 coupling reaction Methods 0.000 abstract 1
- 230000003647 oxidation Effects 0.000 abstract 1
- 238000007254 oxidation reaction Methods 0.000 abstract 1
- -1 silver halide Chemical class 0.000 description 41
- 239000010410 layer Substances 0.000 description 27
- 239000000463 material Substances 0.000 description 24
- 239000000975 dye Substances 0.000 description 22
- 239000000839 emulsion Substances 0.000 description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- 229910052709 silver Inorganic materials 0.000 description 17
- 239000004332 silver Substances 0.000 description 17
- 239000000243 solution Substances 0.000 description 17
- 238000000034 method Methods 0.000 description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 13
- 108010010803 Gelatin Proteins 0.000 description 10
- 229920000159 gelatin Polymers 0.000 description 10
- 239000008273 gelatin Substances 0.000 description 10
- 235000019322 gelatine Nutrition 0.000 description 10
- 235000011852 gelatine desserts Nutrition 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 238000011161 development Methods 0.000 description 8
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 229910021607 Silver chloride Inorganic materials 0.000 description 6
- 229960000583 acetic acid Drugs 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- 125000000623 heterocyclic group Chemical group 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 6
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 6
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 238000004040 coloring Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 239000011241 protective layer Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- SJOOOZPMQAWAOP-UHFFFAOYSA-N [Ag].BrCl Chemical compound [Ag].BrCl SJOOOZPMQAWAOP-UHFFFAOYSA-N 0.000 description 4
- 125000004414 alkyl thio group Chemical group 0.000 description 4
- 238000004061 bleaching Methods 0.000 description 4
- 239000012362 glacial acetic acid Substances 0.000 description 4
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-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
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 125000004442 acylamino group Chemical group 0.000 description 3
- 125000004423 acyloxy group Chemical group 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 125000005110 aryl thio group Chemical group 0.000 description 3
- 125000004104 aryloxy group Chemical group 0.000 description 3
- 239000007844 bleaching agent Substances 0.000 description 3
- 125000001309 chloro group Chemical group Cl* 0.000 description 3
- 229940125904 compound 1 Drugs 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 150000002430 hydrocarbons Chemical group 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 230000000087 stabilizing effect Effects 0.000 description 3
- PHDIJLFSKNMCMI-ITGJKDDRSA-N (3R,4S,5R,6R)-6-(hydroxymethyl)-4-(8-quinolin-6-yloxyoctoxy)oxane-2,3,5-triol Chemical compound OC[C@@H]1[C@H]([C@@H]([C@H](C(O1)O)O)OCCCCCCCCOC=1C=C2C=CC=NC2=CC=1)O PHDIJLFSKNMCMI-ITGJKDDRSA-N 0.000 description 2
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 2
- HIHOEGPXVVKJPP-JTQLQIEISA-N 5-fluoro-2-[[(1s)-1-(5-fluoropyridin-2-yl)ethyl]amino]-6-[(5-methyl-1h-pyrazol-3-yl)amino]pyridine-3-carbonitrile Chemical compound N([C@@H](C)C=1N=CC(F)=CC=1)C(C(=CC=1F)C#N)=NC=1NC=1C=C(C)NN=1 HIHOEGPXVVKJPP-JTQLQIEISA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000004466 alkoxycarbonylamino group Chemical group 0.000 description 2
- 125000004397 aminosulfonyl group Chemical group NS(=O)(=O)* 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
- 229940101006 anhydrous sodium sulfite Drugs 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000005162 aryl oxy carbonyl amino group Chemical group 0.000 description 2
- 125000005161 aryl oxy carbonyl group Chemical group 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 125000000392 cycloalkenyl group Chemical group 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- UREBWPXBXRYXRJ-UHFFFAOYSA-N ethyl acetate;methanol Chemical compound OC.CCOC(C)=O UREBWPXBXRYXRJ-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 2
- 229940001482 sodium sulfite Drugs 0.000 description 2
- 235000010265 sodium sulphite Nutrition 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 150000003413 spiro compounds Chemical group 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 125000000475 sulfinyl group Chemical group [*:2]S([*:1])=O 0.000 description 2
- 229940124530 sulfonamide Drugs 0.000 description 2
- 150000003456 sulfonamides Chemical class 0.000 description 2
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 125000004149 thio group Chemical group *S* 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-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
- HBENZIXOGRCSQN-VQWWACLZSA-N (1S,2S,6R,14R,15R,16R)-5-(cyclopropylmethyl)-16-[(2S)-2-hydroxy-3,3-dimethylpentan-2-yl]-15-methoxy-13-oxa-5-azahexacyclo[13.2.2.12,8.01,6.02,14.012,20]icosa-8(20),9,11-trien-11-ol Chemical compound N1([C@@H]2CC=3C4=C(C(=CC=3)O)O[C@H]3[C@@]5(OC)CC[C@@]2([C@@]43CC1)C[C@@H]5[C@](C)(O)C(C)(C)CC)CC1CC1 HBENZIXOGRCSQN-VQWWACLZSA-N 0.000 description 1
- WLWNRAWQDZRXMB-YLFCFFPRSA-N (2r,3r,4r,5s)-n,3,4,5-tetrahydroxy-1-(4-phenoxyphenyl)sulfonylpiperidine-2-carboxamide Chemical compound ONC(=O)[C@H]1[C@@H](O)[C@H](O)[C@@H](O)CN1S(=O)(=O)C(C=C1)=CC=C1OC1=CC=CC=C1 WLWNRAWQDZRXMB-YLFCFFPRSA-N 0.000 description 1
- GVEYRUKUJCHJSR-UHFFFAOYSA-N (4-azaniumyl-3-methylphenyl)-ethyl-(2-hydroxyethyl)azanium;sulfate Chemical compound OS(O)(=O)=O.OCCN(CC)C1=CC=C(N)C(C)=C1 GVEYRUKUJCHJSR-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- HFZLSTDPRQSZCQ-UHFFFAOYSA-N 1-pyrrolidin-3-ylpyrrolidine Chemical compound C1CCCN1C1CNCC1 HFZLSTDPRQSZCQ-UHFFFAOYSA-N 0.000 description 1
- 125000001462 1-pyrrolyl group Chemical group [*]N1C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 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
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 description 1
- 125000002941 2-furyl group Chemical group O1C([*])=C([H])C([H])=C1[H] 0.000 description 1
- 125000000175 2-thienyl group Chemical group S1C([*])=C([H])C([H])=C1[H] 0.000 description 1
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 description 1
- ZJOJXRSMJNWWRN-UHFFFAOYSA-N 3-amino-6-[2-(4-aminophenyl)ethenyl]benzene-1,2-disulfonic acid Chemical compound C1=CC(N)=CC=C1C=CC1=CC=C(N)C(S(O)(=O)=O)=C1S(O)(=O)=O ZJOJXRSMJNWWRN-UHFFFAOYSA-N 0.000 description 1
- XFZGWACRWMVTJM-UHFFFAOYSA-N 3-heptadecylpyrrolidine-2,5-dione Chemical group CCCCCCCCCCCCCCCCCC1CC(=O)NC1=O XFZGWACRWMVTJM-UHFFFAOYSA-N 0.000 description 1
- DSVIHYOAKPVFEH-UHFFFAOYSA-N 4-(hydroxymethyl)-4-methyl-1-phenylpyrazolidin-3-one Chemical compound N1C(=O)C(C)(CO)CN1C1=CC=CC=C1 DSVIHYOAKPVFEH-UHFFFAOYSA-N 0.000 description 1
- 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 1
- CNGYZEMWVAWWOB-VAWYXSNFSA-N 5-[[4-anilino-6-[bis(2-hydroxyethyl)amino]-1,3,5-triazin-2-yl]amino]-2-[(e)-2-[4-[[4-anilino-6-[bis(2-hydroxyethyl)amino]-1,3,5-triazin-2-yl]amino]-2-sulfophenyl]ethenyl]benzenesulfonic acid Chemical compound N=1C(NC=2C=C(C(\C=C\C=3C(=CC(NC=4N=C(N=C(NC=5C=CC=CC=5)N=4)N(CCO)CCO)=CC=3)S(O)(=O)=O)=CC=2)S(O)(=O)=O)=NC(N(CCO)CCO)=NC=1NC1=CC=CC=C1 CNGYZEMWVAWWOB-VAWYXSNFSA-N 0.000 description 1
- 229940100484 5-chloro-2-methyl-4-isothiazolin-3-one Drugs 0.000 description 1
- 125000003341 7 membered heterocyclic group Chemical group 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 101100027969 Caenorhabditis elegans old-1 gene Proteins 0.000 description 1
- 229920002284 Cellulose triacetate Polymers 0.000 description 1
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- GNPHADHWEUDSJZ-UHFFFAOYSA-M S(=O)([O-])[O-].[Na+].S(=S)(=O)(O)O.[NH4+] Chemical compound S(=O)([O-])[O-].[Na+].S(=S)(=O)(O)O.[NH4+] GNPHADHWEUDSJZ-UHFFFAOYSA-M 0.000 description 1
- 229910021612 Silver iodide Inorganic materials 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- 229910052776 Thorium Inorganic materials 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- LJOOWESTVASNOG-UFJKPHDISA-N [(1s,3r,4ar,7s,8s,8as)-3-hydroxy-8-[2-[(4r)-4-hydroxy-6-oxooxan-2-yl]ethyl]-7-methyl-1,2,3,4,4a,7,8,8a-octahydronaphthalen-1-yl] (2s)-2-methylbutanoate Chemical compound C([C@H]1[C@@H](C)C=C[C@H]2C[C@@H](O)C[C@@H]([C@H]12)OC(=O)[C@@H](C)CC)CC1C[C@@H](O)CC(=O)O1 LJOOWESTVASNOG-UFJKPHDISA-N 0.000 description 1
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 1
- XCFIVNQHHFZRNR-UHFFFAOYSA-N [Ag].Cl[IH]Br Chemical compound [Ag].Cl[IH]Br XCFIVNQHHFZRNR-UHFFFAOYSA-N 0.000 description 1
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 125000005194 alkoxycarbonyloxy group Chemical group 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- 125000003806 alkyl carbonyl amino group Chemical group 0.000 description 1
- 125000004448 alkyl carbonyl group Chemical group 0.000 description 1
- 125000005196 alkyl carbonyloxy group Chemical group 0.000 description 1
- 125000005153 alkyl sulfamoyl group Chemical group 0.000 description 1
- 125000004644 alkyl sulfinyl group Chemical group 0.000 description 1
- 125000004390 alkyl sulfonyl group Chemical group 0.000 description 1
- 125000004656 alkyl sulfonylamino group Chemical group 0.000 description 1
- 125000005281 alkyl ureido group Chemical group 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000005116 aryl carbamoyl group Chemical group 0.000 description 1
- 125000004658 aryl carbonyl amino group Chemical group 0.000 description 1
- 125000005129 aryl carbonyl group Chemical group 0.000 description 1
- 125000005199 aryl carbonyloxy group Chemical group 0.000 description 1
- 125000005135 aryl sulfinyl group Chemical group 0.000 description 1
- 125000004657 aryl sulfonyl amino group Chemical group 0.000 description 1
- 125000004391 aryl sulfonyl group Chemical group 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
- ZFSFDELZPURLKD-UHFFFAOYSA-N azanium;hydroxide;hydrate Chemical compound N.O.O ZFSFDELZPURLKD-UHFFFAOYSA-N 0.000 description 1
- WZTQWXKHLAJTRC-UHFFFAOYSA-N benzyl 2-amino-6,7-dihydro-4h-[1,3]thiazolo[5,4-c]pyridine-5-carboxylate Chemical compound C1C=2SC(N)=NC=2CCN1C(=O)OCC1=CC=CC=C1 WZTQWXKHLAJTRC-UHFFFAOYSA-N 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 125000001951 carbamoylamino group Chemical group C(N)(=O)N* 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- DHNRXBZYEKSXIM-UHFFFAOYSA-N chloromethylisothiazolinone Chemical compound CN1SC(Cl)=CC1=O DHNRXBZYEKSXIM-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- VFGVNLNBQPXBKA-UHFFFAOYSA-N diazanium;dibromide Chemical compound [NH4+].[NH4+].[Br-].[Br-] VFGVNLNBQPXBKA-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- HTDKEJXHILZNPP-UHFFFAOYSA-N dioctyl hydrogen phosphate Chemical compound CCCCCCCCOP(O)(=O)OCCCCCCCC HTDKEJXHILZNPP-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- UCNNJGDEJXIUCC-UHFFFAOYSA-L hydroxy(oxo)iron;iron Chemical compound [Fe].O[Fe]=O.O[Fe]=O UCNNJGDEJXIUCC-UHFFFAOYSA-L 0.000 description 1
- 229910000378 hydroxylammonium sulfate Inorganic materials 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- PTFYQSWHBLOXRZ-UHFFFAOYSA-N imidazo[4,5-e]indazole Chemical compound C1=CC2=NC=NC2=C2C=NN=C21 PTFYQSWHBLOXRZ-UHFFFAOYSA-N 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- 150000004682 monohydrates Chemical class 0.000 description 1
- PJUIMOJAAPLTRJ-UHFFFAOYSA-N monothioglycerol Chemical compound OCC(O)CS PJUIMOJAAPLTRJ-UHFFFAOYSA-N 0.000 description 1
- AJDUTMFFZHIJEM-UHFFFAOYSA-N n-(9,10-dioxoanthracen-1-yl)-4-[4-[[4-[4-[(9,10-dioxoanthracen-1-yl)carbamoyl]phenyl]phenyl]diazenyl]phenyl]benzamide Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2NC(=O)C(C=C1)=CC=C1C(C=C1)=CC=C1N=NC(C=C1)=CC=C1C(C=C1)=CC=C1C(=O)NC1=CC=CC2=C1C(=O)C1=CC=CC=C1C2=O AJDUTMFFZHIJEM-UHFFFAOYSA-N 0.000 description 1
- CLJDCQWROXMJAZ-UHFFFAOYSA-N n-[2-(4-amino-n-ethyl-3-methylanilino)ethyl]methanesulfonamide;sulfuric acid Chemical compound OS(O)(=O)=O.CS(=O)(=O)NCCN(CC)C1=CC=C(N)C(C)=C1 CLJDCQWROXMJAZ-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 1
- 125000005740 oxycarbonyl group Chemical group [*:1]OC([*:2])=O 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000005499 phosphonyl group Chemical group 0.000 description 1
- YPCZIDDPJRHZIZ-UHFFFAOYSA-N phosphoric acid;decahydrate Chemical group O.O.O.O.O.O.O.O.O.O.OP(O)(O)=O YPCZIDDPJRHZIZ-UHFFFAOYSA-N 0.000 description 1
- 125000005543 phthalimide group Chemical group 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- KNCYXPMJDCCGSJ-UHFFFAOYSA-N piperidine-2,6-dione Chemical group O=C1CCCC(=O)N1 KNCYXPMJDCCGSJ-UHFFFAOYSA-N 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 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
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 description 1
- 229940116357 potassium thiocyanate Drugs 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- JEXVQSWXXUJEMA-UHFFFAOYSA-N pyrazol-3-one Chemical compound O=C1C=CN=N1 JEXVQSWXXUJEMA-UHFFFAOYSA-N 0.000 description 1
- MCSKRVKAXABJLX-UHFFFAOYSA-N pyrazolo[3,4-d]triazole Chemical compound N1=NN=C2N=NC=C21 MCSKRVKAXABJLX-UHFFFAOYSA-N 0.000 description 1
- 125000000246 pyrimidin-2-yl group Chemical group [H]C1=NC(*)=NC([H])=C1[H] 0.000 description 1
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 1
- 229940045105 silver iodide Drugs 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 125000003003 spiro group Chemical group 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical group O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical compound CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- ILJSQTXMGCGYMG-UHFFFAOYSA-N triacetic acid Chemical compound CC(=O)CC(=O)CC(O)=O ILJSQTXMGCGYMG-UHFFFAOYSA-N 0.000 description 1
- SOBHUZYZLFQYFK-UHFFFAOYSA-K trisodium;hydroxy-[[phosphonatomethyl(phosphonomethyl)amino]methyl]phosphinate Chemical compound [Na+].[Na+].[Na+].OP(O)(=O)CN(CP(O)([O-])=O)CP([O-])([O-])=O SOBHUZYZLFQYFK-UHFFFAOYSA-K 0.000 description 1
- 239000001043 yellow dye Substances 0.000 description 1
Landscapes
- 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］
本発明はカラー写真用素材として用いられる新規な写真
用カプラーに関し、詳しくは、熱・湿度および光に対す
る堅牢性の優れた色素画像を形成する写真用カプラーに
関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a novel photographic coupler used as a color photographic material, and more specifically, it forms a dye image with excellent fastness to heat, humidity, and light. Regarding photographic couplers.
［発明の背景］
ハロゲン化銀写真感光材料に露光を与えた後、発色現像
処理することにより、露光領域において、酸化された芳
香族第一級アミン発色現像主薬と色素形成カプラーとが
反応して色素が生成し、色画像が形成される。[Background of the Invention] After a silver halide photographic material is exposed to light and then subjected to color development processing, the oxidized aromatic primary amine color developing agent and the dye-forming coupler react in the exposed area. Pigments are produced and a color image is formed.
一般に、この写真方法においては減色法による色再現法
が使われ、イエロー、マゼンタおよびシアンの色画像が
形成される。Generally, this photographic method uses a subtractive color reproduction method to form yellow, magenta and cyan color images.
上記のイエロー色画像を形成させφために用いられる写
真用カプラーとしては、例えばアシルアセトアニリド系
カプラーがあり、また、マゼンタ色画像形成用のカプラ
ーとしては例えばピラゾロン、ピラゾロベンズイミダゾ
ール、ピラゾロトリアゾールまたはインダシロン系カプ
ラーが知られており、さらにシアン色画像形成用のカプ
ラーとしては、例えばフェノールまたはナフトール系カ
プラーが一般的に用いられる。Examples of photographic couplers used to form the above-mentioned yellow image include acylacetanilide couplers, and examples of couplers for forming magenta images include pyrazolone, pyrazolobenzimidazole, pyrazolotriazole, and Indacylon couplers are known, and as couplers for forming cyan images, for example, phenol or naphthol couplers are generally used.
このようにして得られる色素画像は、長時間光に曝され
ても、高温、高湿下に保存されても変褪色しないことが
望まれている。It is desired that the dye image obtained in this way does not change color or fade even if it is exposed to light for a long time or stored under high temperature and high humidity.
しかしながら、シアン色素を形成する為のカプラーとし
て、研究が進められてきたフェノール系カプラーおよび
ナフトール系カプラーは、形成されたシアン色素画像の
分光吸収特性、耐熱性、耐湿性および耐光性等の点で今
一つ不十分であり、この改良をめざして、置換基の工夫
をはじめとし、種々の提案がなされているが、これらを
すべて満足するような化合物は未だ得られていない。However, phenolic couplers and naphthol couplers, which have been studied as couplers for forming cyan dyes, have poor spectral absorption characteristics, heat resistance, moisture resistance, light resistance, etc. of the formed cyan dye images. This is still unsatisfactory, and various proposals have been made to improve this, including devising substituents, but a compound that satisfies all of these has not yet been obtained.
そこで本発明者等は、前記の点につき、更に研究を進め
た結果、熱・湿度および光に対して色相変化を起さない
シアン色素画像を形成しつる写真用カプラーを発見し、
本発明を完成するに至った。As a result of further research into the above points, the present inventors discovered a photographic coupler that forms a cyan dye image that does not change in hue due to heat, humidity, or light.
The present invention has now been completed.
［発明の目的］
本発明の第１の目的は、カラー写真用素材として用いら
れる新規な写真用カプラーを提供することにある。[Object of the Invention] The first object of the present invention is to provide a novel photographic coupler that can be used as a color photographic material.
本発明の第２の目的は、熱・湿度および光に対し色相の
変化を起こさないシアン色素画像を形成する写真用カプ
ラーを提供することにある。A second object of the present invention is to provide a photographic coupler that forms a cyan dye image that does not change in hue due to heat, humidity, or light.
［発明の構成］
本発明の上記目的は一般式［１］で表わされる写真用カ
プラーによって達成された。[Structure of the Invention] The above objects of the present invention have been achieved by a photographic coupler represented by the general formula [1].
［式中、Ｒ，、Ｒ２，Ｉｔ３およびＹは水素原子または
置換基を表わし、Ｒ２とＲ３は結合して環を形成しても
よい。Ｘは水素原子または発色現像主薬の酸化体との反
応により、離脱する置換基を表わす。］以下、より具体
的に本発明を説明する。[In the formula, R,, R2, It3 and Y represent a hydrogen atom or a substituent, and R2 and R3 may be combined to form a ring. X represents a hydrogen atom or a substituent that is eliminated upon reaction with an oxidized product of a color developing agent. ] Hereinafter, the present invention will be explained in more detail.
−能代［Ｉ］におけるＲ、、１１．およびＲ３は水素原
子または置換基を表わし、Ｒ，、Ｒ，およびＲ３の表わ
す置換基としては、特に制限はないが、代表的には、ア
ルキル、アリール、アニリノ、アシルアミノ、スルホン
アミド、アルキルチオ、アリールチオ、アルケニル、シ
クロアルキル等の８基が挙げられるが、この他にハロゲ
ン原子及びシクロアルケニル、アルキニル、複素環、ス
ルボニル、スルフィニル、ポスボニル、アシル、カルバ
モイル、スルファモイル、シアノ、アルコキシ、スルボ
ニルオキシ、アリールオキシ、複素環オキシ、シロキシ
、アシルオキシ、カルバモイルオキシ、アミノ、アルキ
ルアミノ、イミド、ウレイド、スルファモイルアミノ、
アルコキシカルボニルアミノ、アリールオキシカルボニ
ルアミノ、フルコキシカルボニル、アリールオキシカル
ボニル、複素環チオ、チオウレイド、カルボキシ、ヒド
ロキシ、メルカプト、ニトロ、スルホン酸等の８基、な
らびにスピロ化合物残基、有橋炭化水素化合物残基等も
挙げられる。-R in Noshiro [I], 11. and R3 represent a hydrogen atom or a substituent, and the substituents represented by R, R, and R3 are not particularly limited, but typically include alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, and arylthio. , alkenyl, cycloalkyl, etc.; in addition, halogen atoms and cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl, posubonyl, acyl, carbamoyl, sulfamoyl, cyano, alkoxy, sulfonyloxy, aryloxy , heterocyclicoxy, siloxy, acyloxy, carbamoyloxy, amino, alkylamino, imide, ureido, sulfamoylamino,
Eight groups such as alkoxycarbonylamino, aryloxycarbonylamino, flukoxycarbonyl, aryloxycarbonyl, heterocyclic thio, thioureido, carboxy, hydroxy, mercapto, nitro, and sulfonic acid, as well as spiro compound residues and bridged hydrocarbon compound residues. Also mentioned are groups.
Ｒ１，Ｒ２およびＲ３の表わす置換基のうち、アルキル
基としては、炭素数１〜３２のものが好ましく、直鎮で
も分岐でもよい。Among the substituents represented by R1, R2 and R3, the alkyl group preferably has 1 to 32 carbon atoms, and may be straight or branched.
アリール基としては、フェニル基が好ましい。As the aryl group, a phenyl group is preferred.
アシルアミノ基としては、アルキルカルボニルアミノ基
、アリールカルボニルアミノ基等が挙げられる。Examples of the acylamino group include an alkylcarbonylamino group and an arylcarbonylamino group.
スルポンアミド基としては、アルキルスルボニルアミノ
基、アリールスルボニルアミノ基等が挙げられる。Examples of the sulponamide group include an alkylsulfonylamino group and an arylsulfonylamino group.
アルキルチオ基、アリールチオ基におけるアルキル成分
、アリール成分は上記Ｒ１，Ｒ２およびＲ１で表される
アルキル基、アリール基が挙げられる。Examples of the alkyl component and aryl component in the alkylthio group and arylthio group include the alkyl group and aryl group represented by R1, R2 and R1 above.
アルケニル基としては、炭素数２〜３２のもの、シクロ
アルキル基としては炭素数３〜１２、特に５〜７のもの
が好ましく、アルケニル基は直鎮でも分岐でもよい。The alkenyl group preferably has 2 to 32 carbon atoms, and the cycloalkyl group preferably has 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms, and the alkenyl group may be straight or branched.
シクロアルケニル基としては、炭素数３〜１２、特に５
〜７のものが好ましい。The cycloalkenyl group has 3 to 12 carbon atoms, especially 5
-7 is preferred.
スルホニル基としてはアルキルスルホニル基、アリール
スルホニル基等；
スルフィニル基としてはアルキルスルフィニル基、アリ
ールスルフィニル基等；
ホスホニル基としてはアルキルホスホニル基、アルコキ
シホスホニル基、アリールオキシホスホニル基、アリー
ルホスホニル基環；
アシル基としてはアルキルカルボニル基、アリールカル
ボニル基等；
カルバモイル基としてはアルキルカルバそイル基、アリ
ールカルバモイル基等；
スルファモイル基としてはアルキルスルファモイル基、
アリールスルファモイル基等；アシルオキシ基としては
アルキルカルボニルオキシ基、アリールカルボニルオキ
シ基等；カルバモイルオキシ基としてはアルキルカルバ
モイルオキシ基、アリールカルバモイルオキシ基等；
ウレイド基としてはアルキルウレイド基、アリールウレ
イド基等；
スルファモイルアミノ基としてはアルキルスルファモイ
ルアミノ基、アリールスルファモイルアミノ基等；
複素環基としては５〜７員のものが好ましく、具体的に
は２−フリル基、２−チエニル基、２−ピリミジニル基
、２−ベンゾチアゾリル基、１−ピロリル基、１−テト
ラゾリル基環：
複素環オキシ基としては５〜７員の複素環を有するもの
が好ましく、例えば３，４．５．６−テトラヒドロピラ
ニル−２−オキシ基、１−フェニルテトラゾール−５−
オキシ基等；
複素環チオ基としては、５〜７員の複素環チオ基が好ま
しく、例えば２−ピリジルチオ基、２−ペンゾチアゾリ
ルチオ基、２．４−ジフェノキシ−１，３，５−トリア
ゾール−６一チオ基等：シロキシ基としてはトリメチル
シロキシ基、トリエチルシロキシ基、ジメチルブチルシ
ロキシ基等；
イミド基としてはコハク酸イミド基、３−ヘプタデシル
コハク酸イミド基、フタルイミド基、グルタルイミド基
等；
スピロ化合物残基としてはスピロ［３，３］へブタン−
１−イル等；
有橋炭化水素化合物残基としてはビシクロ［２，２，１
］ヘプタン−１−イル、トリシクロ［３，：１，１．１
”］］デカンー１−イル７．７−シメチルービシクロ［
２，２，１］へブタン−１−イル等が挙げられる。Sulfonyl groups include alkylsulfonyl groups, arylsulfonyl groups, etc.; sulfinyl groups include alkylsulfinyl groups, arylsulfinyl groups, etc.; phosphonyl groups include alkylphosphonyl groups, alkoxyphosphonyl groups, aryloxyphosphonyl groups, and arylphosphonyl groups. Ring; As an acyl group, an alkylcarbonyl group, an arylcarbonyl group, etc.; As a carbamoyl group, an alkylcarbasoyl group, an arylcarbamoyl group, etc.; As a sulfamoyl group, an alkylsulfamoyl group,
Arylsulfamoyl groups, etc.; Acyloxy groups include alkylcarbonyloxy groups, arylcarbonyloxy groups, etc.; carbamoyloxy groups include alkylcarbamoyloxy groups, arylcarbamoyloxy groups, etc.; ureido groups include alkylureido groups, arylureido groups, etc. ; As the sulfamoylamino group, an alkylsulfamoylamino group, an arylsulfamoylamino group, etc.; as a heterocyclic group, a 5- to 7-membered one is preferable, and specifically, a 2-furyl group, a 2-thienyl group , 2-pyrimidinyl group, 2-benzothiazolyl group, 1-pyrrolyl group, 1-tetrazolyl group ring: The heterocyclic oxy group preferably has a 5- to 7-membered heterocycle, for example, 3,4.5.6- Tetrahydropyranyl-2-oxy group, 1-phenyltetrazole-5-
Oxy group, etc.; As the heterocyclic thio group, a 5- to 7-membered heterocyclic thio group is preferable, such as 2-pyridylthio group, 2-penzothiazolylthio group, 2.4-diphenoxy-1,3,5- Triazole-6 monothio group, etc.: Siloxy group includes trimethylsiloxy group, triethylsiloxy group, dimethylbutylsiloxy group, etc.; imide group includes succinimide group, 3-heptadecylsuccinimide group, phthalimide group, glutarimide group etc.; as a spiro compound residue, spiro[3,3]hebutane-
1-yl, etc.; As a bridged hydrocarbon compound residue, bicyclo[2,2,1
] heptan-1-yl, tricyclo[3,:1,1.1
”]]Decan-1-yl7,7-dimethyl-bicyclo[
2,2,1]hebutan-1-yl and the like.
Ｒ２およびＲ５は、前記置換基のうちでも、好ましくは
、例えばアルキル基、アリール基、カルボキシル基、オ
キシカルボニル基、シアノ基、ヒドロキシ基、アルキル
チオ、アリールオキシ基、アミノ基、アミド基およびス
ルポンアミド基、等の８基および水素原子、ハロゲン原
子等が挙げられる。Among the above substituents, R2 and R5 preferably represent, for example, an alkyl group, an aryl group, a carboxyl group, an oxycarbonyl group, a cyano group, a hydroxy group, an alkylthio group, an aryloxy group, an amino group, an amide group, and a sulponamide group, etc., hydrogen atoms, halogen atoms, etc.
またＲ７およびＲ３は、互いに結合して環を形成しても
よく、鎖環は、色和または不飽和の５員環、６員環、７
員環および８員環等が好ましく、具体的には、ベンゼン
、ピリジン環およびキノリン環等が挙げられる。Furthermore, R7 and R3 may be combined with each other to form a ring, and the chain ring may be a colored or unsaturated 5-membered ring, 6-membered ring, or 7-membered ring.
A membered ring, an 8-membered ring, etc. are preferred, and specific examples include benzene, pyridine ring, and quinoline ring.
上記の基は、更に長鎖炭化水素基やポリマー残基などの
耐拡散性基等の置換基を有していてもよい。The above group may further have a substituent such as a long-chain hydrocarbon group or a diffusion-resistant group such as a polymer residue.
Ｘの表す発色現像主薬の酸化体との反応により離脱しつ
る基としては、例えばハロゲン原子（塩素原子、臭素原
子、弗素原子等）及びアルコキシ、アリールオキシ、複
素環オキシ、アシルオキシ、スルホニルオキシ、アルコ
キシカルボニルオキシ、アリールオキシカルボニル、ア
ルキルオキザリルオキシ、アルコキシオキザリルオキシ
、アルキルチオ、アリールチオ、複素環チオ、アルキル
オキシチオカルボニルチオ、アシルアミノ、スルホンア
ミド、Ｎ原子で結合した含窒素複素環、アルキルオキシ
カルボニルアミノ、アリールオキシカルボニルアミノ、
カルボキシル、
（Ｒ１’、Ｒ２’、Ｒ３’及びＹ′は前記−能代［Ｉ］
中のＲ，、Ｒ２，Ｒ，およびＹと同義であり、Ｒａおよ
びＲｂは水素原子、アリール基、アルキル基又は複素環
基を表す、）
等の８基が挙げられるが、好ましくはハロゲン原子であ
る。これらのうち、Ｘで表わされる特に好ましいものは
、水素原子および塩素原子である。Examples of the group that is released by reaction with the oxidized product of the color developing agent represented by X include halogen atoms (chlorine atom, bromine atom, fluorine atom, etc.), alkoxy, aryloxy, heterocyclic oxy, acyloxy, sulfonyloxy, alkoxy Carbonyloxy, aryloxycarbonyl, alkyloxalyloxy, alkoxyoxalyloxy, alkylthio, arylthio, heterocyclic thio, alkyloxythiocarbonylthio, acylamino, sulfonamide, nitrogen-containing heterocycle bonded via N atom, alkyloxycarbonylamino , aryloxycarbonylamino,
carboxyl, (R1', R2', R3' and Y' are the above-Noshiro [I]
R, , R2, R, and Y in the above, and Ra and Rb represent a hydrogen atom, an aryl group, an alkyl group, or a heterocyclic group. be. Among these, particularly preferred ones represented by X are hydrogen atoms and chlorine atoms.
−能代［ＩＩにおいてＹは水素原子または置換基を表わ
し、Ｙが表わす置換基の好ましいものは、例えば、本発
明の化合物が、現像主薬酸化体と反応した後、前記化合
物から脱離するものであるが、例えばＹが表す置換基は
、特開昭６１−２２８４４４号等に記載されているよう
な、アルカリ条件下で、離脱しつる基や、特開昭５６−
１３３７３４号等に記載されているような現像主薬酸化
体との反応により、カップリング・オフする置換基等が
挙げられるが、好ましくはＹは水素原子である。- Noshiro [In II, Y represents a hydrogen atom or a substituent, and the preferred substituent represented by Y is, for example, one that is eliminated from the compound of the present invention after it reacts with the oxidized developing agent. However, for example, the substituent represented by Y may be a vine group that leaves under alkaline conditions as described in JP-A No. 61-228444, etc.
Examples include substituents that are coupled off by reaction with an oxidized developing agent as described in No. 133734, etc., and preferably Y is a hydrogen atom.
従って、−能代［１］で表わされる本発明の化合物は、
より好ましくは、−能代［ＩＩ ］で表わされる。Therefore, the compound of the present invention represented by -Noshiro [1] is:
More preferably, it is represented by -Noshiro [II].
＋１３
［式中、Ｒ３、Ｒ２、Ｒ３およびＸは一般式［１］で表
わされる化合物のＲ１、Ｒ２、Ｒ３およびＸと同義であ
る。］
次に本発明の代表的化合物例を以下に示すが、本発明は
これらに限定されるものではない。+13 [wherein R3, R2, R3 and X have the same meanings as R1, R2, R3 and X of the compound represented by general formula [1]. ] Next, typical compound examples of the present invention are shown below, but the present invention is not limited thereto.
以下余白
前記の本発明のカプラーは、ケミカル ア ンド ファ
ーマスティカル プルテン（Ｃｈｅｍ、ｐｈａｍ。The couplers of the present invention described above are chemical and pharmaceutical pluten (Chem, pham).
Ｂｕｌｌ ） １９８３年、第３１巻（８）、第２５４
０頁〜第２５５１頁に記載されている化合物を含み、か
つこれに記載された合成法に準じて容易に合成すること
ができる。Bull) 1983, Volume 31 (8), No. 254
It includes the compounds described on pages 0 to 2551, and can be easily synthesized according to the synthesis method described therein.
なお、上記引用文献には、該文献に記載された化合物が
カラー写真用のカプラーとして有用であることは全く記
載されていない。Incidentally, the above-mentioned cited document does not describe at all that the compound described in the document is useful as a coupler for color photography.
合成例（例示化合物１の合成） 例示化合物１は以下のスキームに従フて合成した。Synthesis example (synthesis of exemplified compound 1) Exemplary Compound 1 was synthesized according to the scheme below.
ｌａ ｌｂ
１）化合物ＩＣの合成
化合物１ａを１０ ｇ （０，１モル）と化合物１ｂを
２９ｇ（０，２モル）とをナトリウムメトキサイドの２
８重量％メタノール溶液９６．５ｍｌに溶解し、５時間
煮沸還流させた０反応終了後、１０％塩酸で中和し、水
、クロロホルムを加え、クロロホルム層を抽出した。la lb 1) Synthesis of compound IC 10 g (0.1 mol) of compound 1a and 29 g (0.2 mol) of compound 1b were mixed with 2 of sodium methoxide.
It was dissolved in 96.5 ml of 8% by weight methanol solution and boiled and refluxed for 5 hours. After completion of the reaction, it was neutralized with 10% hydrochloric acid, water and chloroform were added, and the chloroform layer was extracted.
さらにこの溶液を濃縮しメタノール−酢酸エチルで再結
晶して化合物１ｃを１３．６ｇ（収率７５％）得た。融
点１９６℃〜１９７℃
２）化合物１ｄの合成
化合物ＩＣの１８．１ｇ（０，１モル）に１８１１のオ
キシ塩化リンを加え、９０℃で１．５時間反応させる。Further, this solution was concentrated and recrystallized from methanol-ethyl acetate to obtain 13.6 g (yield 75%) of Compound 1c. Melting point: 196°C to 197°C 2) Synthesis of Compound 1d To 18.1g (0.1 mol) of Compound IC is added 1811 phosphorus oxychloride, and the mixture is reacted at 90°C for 1.5 hours.
反応終了後、過剰のオキシ塩化リンを減圧留去し、残漬
を氷水に注ぎ、炭酸カリで中和した後、クロロホルムで
抽出した。その後溶媒を留去しカラムクロマトグラフィ
を用いて精製し化合物１ｄを１３．３ｇ（収率７３％）
得た。After the reaction was completed, excess phosphorus oxychloride was distilled off under reduced pressure, the residue was poured into ice water, neutralized with potassium carbonate, and then extracted with chloroform. After that, the solvent was distilled off and purified using column chromatography to obtain 13.3 g of compound 1d (yield 73%).
Obtained.
３）例示化合物１の合成
１０％塩酸２５０１を９．１ｇ（０，０５モル）の化合
物１ｃのジオキサン溶液に加え、４時間煮沸還流サセる
。ついで１０％水酸化ナトリウム水溶液で中和した後、
溶媒を留去し少量の水を加えて結析させ、濾過して粗結
晶を得る。3) Synthesis of Exemplified Compound 1 Add 10% hydrochloric acid 2501 to a dioxane solution of 9.1 g (0.05 mol) of Compound 1c, and boil and reflux for 4 hours. Then, after neutralizing with a 10% aqueous sodium hydroxide solution,
The solvent is distilled off, a small amount of water is added to cause crystallization, and the mixture is filtered to obtain crude crystals.
さらにこの粗結晶をメタノール−酢酸エチルで再結晶し
て目的とする例示化合物１を３．９ｇ（収率４８％）得
た。融点２６５℃〜２６８℃この化合物の構造は、ＮＭ
Ｒ，ＩＲ，ＭＡＳＳにより確認した。Furthermore, the crude crystals were recrystallized from methanol-ethyl acetate to obtain 3.9 g (yield: 48%) of the target exemplary compound 1. Melting point: 265°C to 268°C The structure of this compound is NM
Confirmed by R, IR, and MASS.
以下余白
本発明のカプラーは通常ハロゲン化銀１モル当りＩ Ｘ
１０−３モル〜１モル、好ましくはｌＸｌ０−”モル
〜８ Ｘ １０−’モルの範囲で用いることができる。The couplers of the present invention usually contain IX per mole of silver halide.
It can be used in a range of 10-3 mol to 1 mol, preferably 1X10-'' mol to 8 X 10-' mol.
また本発明のカプラーは他の種類のシアンカプラーと併
用することもできる。The coupler of the present invention can also be used in combination with other types of cyan couplers.
本発明のカプラーには、通常の色素形成カプラーにおい
て用いられる方法および技術が、同様に適用される。The methods and techniques used in conventional dye-forming couplers apply similarly to the couplers of the invention.
本発明のカプラーには、いかなる発色法によるカラー写
真形成用素材としても用いることができるが、具体的に
は、外式発色法および内式発色法が挙げられる。外式発
色法として用いられる場合、本発明のカプラーはアルカ
リ水溶液あるいは有機溶媒（例えばアルコールなど）に
溶解して、現像処理液中に添加し使用することができる
。The coupler of the present invention can be used as a material for forming color photographs by any coloring method, and specific examples include external coloring method and internal coloring method. When used as an external coloring method, the coupler of the present invention can be dissolved in an alkaline aqueous solution or an organic solvent (for example, alcohol) and added to a developing solution.
本発明のカプラーを内式発色法によるカラー写真形成用
素材として用いる場合、本発明のカプラーは写真感光材
料中に含有させて使用する。When the coupler of the present invention is used as a material for forming a color photograph by an internal coloring method, the coupler of the present invention is incorporated into a photographic light-sensitive material.
典型的には、本発明のカプラーをハロゲン化銀乳剤に配
合し、この乳剤を支持体上に塗布してカラー感光材料を
形成する方法が好ましく用いられる。本発明のカプラー
は、例えばカラーのネガ及びポジフィルム並びにカラー
印画紙などのカラー写真感光材料に用いられる。Typically, a method is preferably used in which the coupler of the present invention is blended into a silver halide emulsion and this emulsion is coated on a support to form a color light-sensitive material. The coupler of the present invention is used, for example, in color photographic materials such as color negative and positive films and color photographic paper.
このカラー印画紙を初めとする本発明のカプラーを用い
た感光材料は、単色用のものでも多色用のものでもよい
、多色用感光材料では、本発明のカプラーはいかなる層
に含有させてもよいが、通常は赤色感光性ハロゲン化銀
乳剤層に含有させる。多色用感光材料はスペクトルの３
原色領域のそれぞれに感光性を有する色素画像形成構成
単位を有する。各構成単位は、スペクトルのある一定領
域に対して感光性を有する単層または多層乳剤層から成
ることができる０画像形成構成単位の層を含めて感光材
料の構成層は、当業界で知られているように種々の順序
で配列することができる。The photosensitive materials using the coupler of the present invention, including this color photographic paper, may be monochromatic or multicolor. In multicolor photosensitive materials, the coupler of the present invention may not be contained in any layer. However, it is usually contained in the red-sensitive silver halide emulsion layer. Multicolor photosensitive materials are spectral 3
Each of the primary color regions has a photosensitive dye image forming unit. The constituent layers of the light-sensitive material, including layers of image-forming constituent units, each of which may consist of a single or multiple emulsion layer sensitive to a certain region of the spectrum, are known in the art. They can be arranged in various orders as shown below.
典型的な多色用感光材料は、少なくとも１つのシアンカ
プラーを含有する少なくとも１つの赤感光性ハロゲン化
銀乳剤層からなるシアン色素画像形成構成単位（シアン
カプラーの少なくとも１つは本発明のシアンカプラーで
ある。）、少なくとも１つのマゼンタカプラーを含有す
る少なくとも１つの縁感光性ハロゲン化銀乳剤層からな
るマゼンタ色素画像形成構成単位、少なくとも１つのイ
エローカプラーを含有する少なくとも１つの青感光性ハ
ロゲン化銀乳剤層からなるイエロー色素画像形成構成単
位を支持体上に担持させたものからなる。A typical multicolor light-sensitive material is a cyan dye image-forming unit consisting of at least one red-sensitive silver halide emulsion layer containing at least one cyan coupler (at least one of the cyan couplers is the cyan coupler of the present invention). ), a magenta dye image-forming unit consisting of at least one edge-sensitive silver halide emulsion layer containing at least one magenta coupler, at least one blue-sensitive silver halide emulsion layer containing at least one yellow coupler. It consists of a yellow dye image-forming structural unit consisting of an emulsion layer supported on a support.
感光材料は、追加の層たとえばフィルター層、中間層、
保護層、下塗り層等を有することができる０本発明のカ
プラーを乳剤に含有せしめるには、従来公知の方法に従
えばよい０例えばトリクレジルホスフェート、ジブチル
フタレート等の沸点す月７５℃以上の高沸点有機溶媒ま
たは酢酸ブチル、プロピオン酸ブチル等の低沸点溶媒の
それぞれ単独にまたは必要に応じてそれらの混合液に本
発明のカプラーを単独でまたは併用して溶解した後、界
面活性剤を含むゼラチン水溶液と混合し、次に高速度回
転ミキサーまたはコロイドミルで乳化した後、ハロゲン
化銀に添加して本発明に使用するハロゲン化銀乳剤を調
製することができる。The photosensitive material may contain additional layers such as filter layers, interlayers,
In order to incorporate the coupler of the present invention into an emulsion, a conventionally known method may be followed. The coupler of the present invention is dissolved in a high boiling point organic solvent or a low boiling point solvent such as butyl acetate, butyl propionate, etc. alone or in a mixture thereof as necessary, and then a surfactant is added. It can be mixed with an aqueous gelatin solution, then emulsified in a high-speed rotary mixer or colloid mill, and then added to silver halide to prepare the silver halide emulsion used in the present invention.
本発明のカプラーを用いた感光材料に好ましく用いられ
るハロゲン化銀組成としては、塩化銀、塩臭化銀または
塩沃臭化銀がある。また更に、塩化銀と臭化銀の混合物
等の組合せ混合物であフてもよい、即ち、ハロゲン化銀
乳剤がカラー用印画紙に用いられる場合には、特に速い
現像性が求められるので、ハロゲン化銀のハロゲン組成
として塩素原子を含むことが好ましく、少なくとも１％
の塩化銀を含有する塩化銀、塩臭化銀または塩沃臭化銀
であることが特に好ましい。Silver halide compositions preferably used in the light-sensitive material using the coupler of the present invention include silver chloride, silver chlorobromide, and silver chloroiobromide. Furthermore, a combination mixture such as a mixture of silver chloride and silver bromide may also be used. It is preferable that the halogen composition of silveride contains chlorine atoms, and at least 1%
It is particularly preferable to use silver chloride, silver chlorobromide or silver chloroiodobromide containing silver chloride.
ハロゲン化銀乳剤は、常法により化学増感される。また
、所望の波長域に光学的に増感できる。The silver halide emulsion is chemically sensitized by conventional methods. Furthermore, it can be optically sensitized to a desired wavelength range.
ハロゲン化銀乳剤には、感光材料の製造工程、保存中、
あるいは写真処理中のカブリの防止、及び／又は写真性
能を安定に保つことを目的として写真業界においてカブ
リ防止剤または安定剤として知られている化合物を加え
ることができる。Silver halide emulsions are used during the manufacturing process of photosensitive materials, during storage,
Alternatively, compounds known as antifoggants or stabilizers in the photographic industry may be added for the purpose of preventing fog during photographic processing and/or keeping photographic performance stable.
本発明のカプラーを用いたカラー感光材料には、通常感
光材料に用いられる色カブリ防止剤、色素画像安定化剤
、紫外線防止剤、帯電防止剤。Color light-sensitive materials using the coupler of the present invention include color antifoggants, dye image stabilizers, ultraviolet light inhibitors, and antistatic agents that are commonly used in light-sensitive materials.
マット剤、界面活性剤等を用いることができる。A matting agent, a surfactant, etc. can be used.
これらについては、例えばリサーチ・ディスクロージｗ
−（Ｒｅｓｅａｒｃｈ Ｄｉｓｃｌｏｓｕｒｅ） １
７８巻、２２〜３１頁（１９７８年１２月）の記載を参
考にすることができる。Regarding these, for example, Research Disclosure w
-(Research Disclosure) 1
The description in Vol. 78, pp. 22-31 (December 1978) can be referred to.
本発明のカプラーを用いたカラー写真感光材料は、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 a color photographic material using the coupler of the present invention by subjecting it to a color development treatment known in the art.
本発明に係るカプラーを用いたカラー写真感光材料は、
親木性コロイド層中に発色現像主薬を発色現像主薬その
ものとして、あるいはそのプレカーサーとして含有し、
アルカリ性の活性化浴により処理することもできる。The color photographic material using the coupler according to the present invention is
A color developing agent is contained in the wood-philic colloid layer as the color developing agent itself or as its precursor,
Treatment can also be carried out using an alkaline activation bath.
本発明のカプラーを用いたカラー写真感光材料は、発色
現像後、漂白処理、定着処理を施される。漂白処理は定
着処理と同時に行ってもよい。A color photographic material using the coupler of the present invention is subjected to a bleaching treatment and a fixing treatment after color development. Bleaching treatment may be performed simultaneously with fixing treatment.
定着処理の後は、通常は水洗処理が行われる。After the fixing process, a washing process is usually performed.
また水洗処理の代替えとして安定化処理を行フてもよい
し、両者を併用してもよい。Furthermore, a stabilization treatment may be performed as an alternative to the water washing treatment, or both may be used in combination.
［実施例］
次に本発明を実施例によフて具体的に説明するが、本発
明はこれらに限定されるものではない。[Examples] Next, the present invention will be specifically explained with reference to Examples, but the present invention is not limited thereto.
実施例１
ポリエチレンで両面ラミネートした紙支持体上に下記の
各層を支持体側より順次塗設し、赤色感光性カラー感光
材料試！＄４１を作製した。尚、化合物の添加量は特に
断りのない限りｌｌ１２当りを示す（ハロゲン化銀は銀
換算値）。Example 1 The following layers were coated sequentially from the support side onto a paper support laminated on both sides with polyethylene, and a red-sensitive color photosensitive material was prepared. I made $41. Note that the amount of the compound added is per 112 unless otherwise specified (silver halide is a silver equivalent value).
第１層：乳剤層
ゼラチン１．２ ｇ、赤感性塩臭化銀乳剤（塩化銀９６
モル％含有） ０．３０ｇおよびジオクチルホスフェー
ト１．３５ｇに溶解した比較シアンカプラーａ ９．Ｉ
Ｘ １０−’モルからなる赤感性乳剤層。1st layer: Emulsion layer 1.2 g of gelatin, red-sensitive silver chlorobromide emulsion (silver chloride 96
Comparative cyan coupler a dissolved in 0.30 g (containing mol %) and 1.35 g of dioctyl phosphate 9. I
A red-sensitive emulsion layer consisting of X 10-' moles.
第２層：保護層
ゼラチンｏ、ｓｏｇを含む保護層、尚、硬膜剤として２
．４−ジクロロ−６−ヒドロキシ−Ｓ−トリアジンナト
リウム塩をゼラチン１ｇ当り０．０１７ ｇになるよう
添加した。2nd layer: Protective layer containing gelatin o, sog, and 2 as a hardening agent.
．． 4-dichloro-6-hydroxy-S-triazine sodium salt was added at 0.017 g per gram of gelatin.
次に、試料１において比較カプラーａを表１に示すカプ
ラー（添加量は比較カプラーａと同モル量）に代えた以
外は、全く同様にして、本発明の試料２〜８を作製した
。Next, Samples 2 to 8 of the present invention were prepared in exactly the same manner as in Sample 1, except that comparative coupler a was replaced with the coupler shown in Table 1 (the amount added was the same molar amount as comparative coupler a).
上記で得た試料１〜８は、それぞれ常法に従ってウェッ
ジ露光を与えた後、次の工程で現像処理を行った。Samples 1 to 8 obtained above were each subjected to wedge exposure according to a conventional method, and then developed in the next step.
く現像処理工程）
発色現像 ３８℃ ３分３０秒漂白定着
３８℃ １分３０秒安定化処理／または水
洗処理
２５℃〜３０℃ ３分
乾 燥 ７５℃〜８０℃ ２分各処理
工程において使用した処理液組成は、下記の如くである
。(Development process) Color development 38℃ 3 minutes 30 seconds Bleach fixing
Stabilization treatment at 38°C for 1 minute and 30 seconds/or washing treatment at 25°C to 30°C for 3 minutes Drying at 75°C to 80°C for 2 minutes The composition of the treatment liquid used in each treatment step is as follows.
（発色現像液）
ベンジルアルコール １５ ｃａｌ
ｌエチレングリコール １５ ｔａ
ｎ亜硫酸カリウム ２．０ｇ臭
化カリウム ０．７８塩化ナ
トリウム ０．２８炭酸カリウ
ム ３０・０ｇヒドロキシル
アミン硫酸塩 ３．０ｇポリ燐酸（ＴＰＰ
Ｓ） ２．５３３−メチル−４−ア
ミノ−Ｎ−エチル−Ｎ−（β−メタンスルホンアミドエ
チル）
アニリン硫酸塩 ５．５ｇ蛍光増
白剤（４，４’−ジアミノスチルベンジスルボン酸銹導
体） １．０ｇ水酸化カリウム
２．０ｇ水を加えて全量をｔＩＬとし、ｐＨ１０
，２０に調整する。(Color developer) Benzyl alcohol 15 cal
l ethylene glycol 15 ta
n Potassium sulfite 2.0g Potassium bromide 0.78 Sodium chloride 0.28 Potassium carbonate 30.0g Hydroxylamine sulfate 3.0g Polyphosphoric acid (TPP
S) 2.533-Methyl-4-amino-N-ethyl-N-(β-methanesulfonamidoethyl) Aniline sulfate 5.5g Fluorescent brightener (4,4'-diaminostilbendisulfonic acid rust conductor) 1.0g potassium hydroxide
Add 2.0g water to bring the total volume to tIL, pH 10
,20.
（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 ６０ ｇ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）１００ｍ１亜硫酸アンモニウム（
４０％溶液） ２７．５ａ＋＃炭酸カリウムまたは
氷酢酸でｐ）Ｉ ７．１に調整し、水を加えて全量をＩ
ＪＺとする。(Bleach-fix solution) Ferric ammonium ethylenediaminetetraacetic acid dihydrate 60 g Ethylenediaminetetraacetic acid 3 g Ammonium thiosulfate (70% solution) 100 ml Ammonium sulfite (
40% solution) 27.5a+# Adjust p)I to 7.1 with potassium carbonate or glacial acetic acid, add water to bring the total volume to I
Let's call it JZ.
（安定化液）
５−クロロ−２−メチル−４−
イソチアゾリン−３−オン １．０ｇエチレン
グリコール １０ ｇ水を加えて１
１とする。(Stabilizing liquid) 5-chloro-2-methyl-4-isothiazolin-3-one 1.0 g Ethylene glycol 10 g Add water to 1
Set to 1.
上記で処理された試料１〜８について、濃度計（コニカ
株式会社製ＫＤ−７型）を用いて濃度を測定し、さらに
、上記各処理済試料を高温・高温（６０℃、８０％旧１
）雰囲気下に１４日間放置し、色素画像の耐熱・耐湿性
を調べた。The concentrations of Samples 1 to 8 treated above were measured using a densitometer (Model KD-7 manufactured by Konica Corporation), and each of the above-treated samples was measured at high temperature (60℃, 80% old 1
) The dye image was left in an atmosphere for 14 days, and the heat resistance and moisture resistance of the dye image were examined.
また、各試料をキセノンフェードメーターで１０日間照
射した後、濃度を測定して、耐光性を調べた。結果を表
−１に示す、但し色素画像の耐熱性、耐湿性および耐光
性は初濃度１．０に対する耐熱、耐湿および耐光試験後
の色素残留パーセントで表す。Further, each sample was irradiated with a xenon fade meter for 10 days, and then the density was measured to examine light resistance. The results are shown in Table 1, provided that the heat resistance, humidity resistance and light resistance of the dye image are expressed as the percentage of dye remaining after the heat resistance, humidity resistance and light resistance tests with respect to the initial density of 1.0.
表−１
表−１の結果から明らかなように、本発明のカプラーを
用いた試料は、比較カプラーを用いた試料に比べて、い
ずれも色素残存率が高く、耐熱・耐湿性および耐光性に
優れており堅牢であることがわかる。Table 1 As is clear from the results in Table 1, the samples using the coupler of the present invention had a higher dye residual rate than the samples using the comparative coupler, and had poor heat resistance, moisture resistance, and light resistance. It can be seen that it is excellent and robust.
実施例２
下引済のトリアセテートフィルム上に、下記の各層を支
持体側より順次塗設し、赤色感光性カラー感光材料（試
料９）を作成した。尚、化合物の添加量は、特に断りの
ない限り、１鳳２当りを示す（ハロゲン化銀は銀換算値
）。Example 2 A red-sensitive color photosensitive material (sample 9) was prepared by sequentially coating the following layers on a subbed triacetate film from the support side. Incidentally, unless otherwise specified, the amount of the compound added is based on 1/2 ounces (silver halide is a silver equivalent value).
第１層：乳剤層
ゼラチン１．４ｇ、赤感性沃臭化銀乳剤（沃化銀４モル
％含有） １．５ ｇおよびトリクレジルホスフェート
１．１ｇに溶解し比較シアンカプラーｂ８、ＯＸｌ０−
’モルからなる赤感性乳剤層。1st layer: Emulsion layer Dissolved in 1.4 g of gelatin, 1.5 g of red-sensitive silver iodobromide emulsion (containing 4 mol% silver iodide) and 1.1 g of tricresyl phosphate, and prepared with comparative cyan coupler b8, OXl0-
'A red-sensitive emulsion layer consisting of moles.
第２Ｗｉ：保護層
ゼラチン１．５ｇを含む保護層、尚、硬膜剤として２．
４−ジクロロ−６−ヒドロキシ−Ｓ−トリアジンナトリ
ウム塩をゼラチン１ｇ当り、０．０１７ ｇになるよう
添加した。2nd Wi: Protective layer A protective layer containing 1.5 g of gelatin, and 2.5 g as a hardening agent.
4-dichloro-6-hydroxy-S-triazine sodium salt was added in an amount of 0.017 g per gram of gelatin.
次に、試料９において、比較シアンカプラーｂを表−２
に示すカプラー（添加量は比較カプラーｂと同モル量）
に代えた以外は、全く同様にして、本発明の試料ｌＯ〜
１６を作製した。Next, for sample 9, the comparison cyan coupler b is shown in Table-2.
The coupler shown in (the amount added is the same molar amount as comparative coupler b)
The samples of the present invention were prepared in exactly the same manner except that
No. 16 was produced.
得られたフィルム試料は、通常の方法でウェッジ露光し
、下記のカラー用処理工程に従いカラー現像を行なった
。The obtained film samples were wedge exposed in a conventional manner and color developed according to the color processing steps described below.
比較カプラーｂ
［処理工程］ （ＩＡ埋湿温度３８℃ＩＡ理時間発色
現像 ３分１５秒漂 白
６分３０秒水 洗
３分１５秒定
着 ６分３０秒水
洗 ３分１５
秒安定化 １分３０秒乾
燥
各処理工程において使用した処理液組成は下記の如くで
ある。Comparative coupler b [Processing process] (IA humidity temperature 38°C IA color development time 3 minutes 15 seconds bleaching
Rinse with water for 6 minutes and 30 seconds, set for 3 minutes and 15 seconds
Arrive 6 minutes 30 seconds Wash 3 minutes 15
Stabilized for seconds, dried for 1 minute and 30 seconds
The composition of the processing liquid used in each drying process is as follows.
［発色現像液］
４−アミノ−３−メチル−Ｎ−エチル−Ｎ−（β−ヒド
ロキシエチル）アニリン硫酸塩４．７５ｇ
無水亜硫酸ナトリウム ４．２５３ヒド
ロキシアミン１／２
無水炭酸カリウム
臭化ナトリウム
ニトリロ三酢酸・３ナトリウム
硫酸塩
水酸化カリウム
水を加えて１にとし、水酸化す
いてｐ １１１０ 、６に調整する。[Color developer] 4-amino-3-methyl-N-ethyl-N-(β-hydroxyethyl)aniline sulfate 4.75g Anhydrous sodium sulfite 4.253 Hydroxyamine 1/2 Anhydrous potassium carbonate Sodium bromide Nitrilotrichloride Aqueous acetic acid/trisodium sulfate and potassium hydroxide were added to bring the solution to 1, and then hydroxylated to adjust to p 1110 and 6.
［漂白液］ エチレンジアミン四酢酸鉄 アンモニウム塩 エチレンジアミン四酢酸 ２アンモニウム塩 臭化アンモニウム 氷酢酸 水を加えて１にとし、 ｐｕａ、ｏに調整する。[Bleach solution] Iron ethylenediaminetetraacetate ammonium salt Ethylenediaminetetraacetic acid 2 ammonium salt ammonium bromide glacial acetic acid Add water to make it 1, Adjust to pua, o.
［定着液］
チオ硫酸アンモニウム
無水亜硫酸ナトリウム
２．０ ｇ
３７．５ ｇ
Ｊ ｇ
１水塩）
２．５ｇ
１．０ ｇ
トリウムな用
アンモニア水を用いて
１００．０ｇ
１０．０ｇ
１５０．０ｇ
１０．０ｇ
１７５．０ｇ
８．６ｇ
メタ亜硫酸ナトリウム ２．３ｇ水を
加えてＩｋとし、酢酸を用いてｐ＋＋ｉｔ、ｏに調整す
る。[Fixer] Ammonium thiosulfate anhydrous sodium sulfite 2.0 g 37.5 g J g monohydrate) 2.5 g 1.0 g Using thorium aqueous ammonia 100.0 g 10.0 g 150.0 g 10.0 g 175.0g 8.6g Sodium metasulfite 2.3g Add water to obtain Ik, and adjust to p++it, o using acetic acid.
［安定化液］
ホルマリン（３７％水溶液） １．５＋
ａｊコニダツクス ７．５＋
＋４！（コニカ株式会社製）
水を加えて１ｊとする。[Stabilizing liquid] Formalin (37% aqueous solution) 1.5+
aj conidax 7.5+
+4! (manufactured by Konica Corporation) Add water to make 1j.
上記で処理された試料９〜１６について、濃度計（小西
六写真工業株式会社製ＫＤ−７Ｒ、型）を用いて透過濃
度を測定し、さらに、上記各処理済試料を高温・高温（
６０℃、８０％Ｒ１１）雰囲気下に１４日間放置し、色
素画像の耐熱・耐湿性を調べたまた、各試料をキセノン
フェードメーターで１０日間照射して、耐光性を調べた
。結果を表−２に示す、但し色素画像の耐熱性、耐湿性
および耐光性は初濃度１．０に対する耐熱・耐湿および
耐光試験後の色素残留パーセントで表す。For Samples 9 to 16 treated above, the transmission density was measured using a densitometer (model KD-7R, manufactured by Konishiroku Photo Industry Co., Ltd.), and each of the above-treated samples was measured at high temperature/high temperature (
The dye images were left in a 60° C., 80% R11) atmosphere for 14 days to examine their heat resistance and moisture resistance. Each sample was also irradiated with a xenon fade meter for 10 days to examine its light resistance. The results are shown in Table 2, provided that the heat resistance, humidity resistance and light resistance of the dye image are expressed as the percentage of dye remaining after the heat resistance, humidity resistance and light resistance tests with respect to the initial density of 1.0.
表−２
表−２の結果から明らかなように、本発明のカプラーを
用いた試料は、比較カプラーを用いた試料に比べて、い
づれも色素残存率が高く、耐熱・耐湿性および耐光性に
優れており堅牢であることがわかる。Table 2 As is clear from the results in Table 2, the samples using the coupler of the present invention had a higher dye residual rate than the samples using the comparative coupler, and had poor heat resistance, moisture resistance, and light resistance. It can be seen that it is excellent and robust.
実施例３
トリアセチルセルロースフィルム支持体上に、下記の各
層を支持体側より順次塗設し、表−３に示すカプラーを
含有する赤感性カラー反転写真感光材料１７〜２２を作
成した。Example 3 The following layers were sequentially coated on a triacetyl cellulose film support from the support side to prepare red-sensitive color reversal photographic materials 17 to 22 containing the couplers shown in Table 3.
第１層：乳剤層
ゼラチン１．４ｇ、赤感性塩臭化銀乳剤（塩化銀９６モ
ル％含有）０．５ｇおよびジブチルフタレート１．５
ｇに溶解した表−３に示すカプラー９．１×１Ｏ−４モ
ルからなる赤感性乳剤層。1st layer: Emulsion layer 1.4 g of gelatin, 0.5 g of red-sensitive silver chlorobromide emulsion (containing 96 mol% silver chloride) and 1.5 g of dibutyl phthalate.
A red-sensitive emulsion layer consisting of 9.1 x 1 O-4 moles of the coupler shown in Table 3 dissolved in g.
第２層：保護層
ゼラチン０．５ ｇを含む保護層、尚、硬膜剤として２
．４−ジクロロ−６−ヒドロキシ−Ｓ−トリアジンナト
リウム塩をゼラチン１ｇ当り、０．０１７ ｇになるよ
う添加した。2nd layer: Protective layer Protective layer containing 0.5 g of gelatin, with 2 g of hardening agent
．． 4-dichloro-6-hydroxy-S-triazine sodium salt was added in an amount of 0.017 g per gram of gelatin.
上記で得た試料は、それぞれ常法に従フてウェッジ露光
を与えた後、次の工程で現像処理を行フた。The samples obtained above were each subjected to wedge exposure according to a conventional method, and then developed in the next step.
［反転処理工程］
工程 時間 温 度
第−現像 ６分 ３８℃
水 洗 ２分 ３８ ℃反
転 ２分 ３８ ℃発色現像
６分 ３８℃
調 整 ２分 ３８ ℃漂
白 ６分 ３８ ℃
定 着 ４分 ３８ ℃水
洗 ４分 ３８ ℃安
定 １分 ３８ ℃乾 燥
常 温ＩＡ埋液の組成は以
下のものを用いる。[Reversal process] Process Time Temperature - Development 6 minutes 38℃ Water washing 2 minutes 38℃ Incubation
Transfer 2 minutes 38℃ Color development 6 minutes 38℃ Adjustment 2 minutes 38℃ bleaching
White 6 minutes 38℃
Fixation 4 minutes 38℃ water
Wash 4 minutes at 38℃
Dry at 38℃ for 1 minute.
The composition of the room-temperature IA filling solution is as follows.
［第一現像液］
テトラポリリン酸ナトリウム ２ｇ亜硫酸ナ
トリウム ２０ ｇハイドロキ
ノン・モノスルフォネート ３０ ｇ炭酸ナトリウム
（ｌ水塩）３０ｇ
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 ２ｇ臭化カリウ
ム ２．５ｇチオシアン酸
カリウム １．２ｇヨウ化カリウム（
０，１％溶液） ２ ｍｊ水を加えて
１００（１＋＊ｊ［反転液］
ニトリロトリメチレンホスホン酸・
６ナトリウム塩 ３ｇ塩化第１ス
ズ（２水塩） Ｉｇｐ−アミノフェノ
ール Ｏ，１ｇ水酸化ナトリウム
５ｇ氷酢酸
１５ ｍＲ水を加えて
１０００ ｒａＲ［発色現像液］
テトラポリリン酸ナトリウム ２ｇ亜硫酸ナ
トリウム ７ｇ第３リン酸ナトリ
ウム（１２水塩）３６ｇ臭化カリウム
１ｇ沃化カリウム（０，１％溶溶液液
９０ ｍｔｌ水酸化ナトリウム
３ｇシトラジン酸
１．５ｇＮ−エチル−Ｎ−（β−メタンスル
ホンアミドエチル）−３−メチル
−４−アミノアニリン・硫酸塩 １１ ｇエチレ
ンジアミン ３ｇ水を加えて
［調整液］
亜硫酸ナトリウム
エチレンジアミンテトラ酢酸
ナトリウム（２水塩）
チオグリセリン
氷酢酸
水を加えて
［漂白液］
エチレンジアミン四酢酸
ナトリウム（２水塩）
エチレンジアミン四酢酸
鉄（ＩＩ＋ ）アンモニウム（２水塩）臭化カリウム
水を加えて
［定着液］
チオ硫酸アンモニウム
亜硫酸ナトリウム
重亜硫酸ナトリウム
水を加えて
■１
０．４ｍｊ
ａｌ
１０００ 菖２
２．０ｇ
１２０．０ｇ
１００．０ｇ
１００（） ｗ、１
８０．０ｇ
５．０ｇ
５．０ｇ
１０００ 曹Ｉ
［安定化液］
ホルマリン（３７重量％） ５．０ｍ
ｊコニダックス ５．０＋ｏ
ｊ（コニカ株式会社製）
水を加えて １０００ａ＋ｊ）
上記で処理された各試料について、実施例２と同様に色
素画像の耐熱・耐湿性および耐光性を調べた。その結果
を表−３に示す。[First developer] Sodium tetrapolyphosphate 2g Sodium sulfite 20g Hydroquinone monosulfonate 30g Sodium carbonate (l hydrate) 30g 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 2g Bromide Potassium 2.5g Potassium thiocyanate 1.2g Potassium iodide (
0.1% solution) Add 2 mj water
100 (1+*j [reversal solution] Nitrilotrimethylenephosphonic acid, hexasodium salt 3g stannous chloride (dihydrate) Igp-aminophenol O, 1g sodium hydroxide
5g glacial acetic acid
Add 15 mR water
1000 raR [Color developer] Sodium tetrapolyphosphate 2g Sodium sulfite 7g Sodium tertiary phosphate (decahydrate) 36g Potassium bromide
1g potassium iodide (0.1% solution)
90 mtl sodium hydroxide
3g citradinic acid
1.5 g N-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-4-aminoaniline sulfate 11 g ethylenediamine Add 3 g water [adjustment solution] Sodium sulfite ethylenediamine sodium tetraacetate (dihydrate) ) Thioglycerin Add glacial acetic acid water [Bleach solution] Sodium ethylenediaminetetraacetate (dihydrate) Ethylenediaminetetraacetate iron(II+) Ammonium (dihydrate) Add potassium bromide water [Fixer] Ammonium thiosulfate Sodium sulfite Add sodium bisulfite water and add ■1 0.4mj al 1000 Iris 2 2.0g 120.0g 100.0g 100() w, 1 80.0g 5.0g 5.0g 1000 Soda I [Stabilizing liquid] Formalin ( 37% by weight) 5.0m
j conidax 5.0+o
j (manufactured by Konica Corporation) Add water 1000a+j)
For each sample treated above, the heat resistance, moisture resistance, and light resistance of the dye image were examined in the same manner as in Example 2. The results are shown in Table-3.
表−３
表−３から明らかなように本発明のカプラーを用いた試
料は、比較カプラーを用いた試料に比べて、いづれも色
素残存率が高く、耐熱・耐湿性および耐光性に優れてお
り堅牢であることがわかる。Table 3 As is clear from Table 3, the samples using the coupler of the present invention all had higher dye residual rates and superior heat resistance, moisture resistance, and light resistance compared to samples using the comparative coupler. It can be seen that it is robust.
［発明の効果］
本発明のカプラーから形成された色素画像は、熱、湿度
および光に対して堅牢であることがわかった。Effects of the Invention Dye images formed from the couplers of the invention were found to be robust to heat, humidity and light.
Claims (1)
たは置換基を表わし、Ｒ＿２とＲ＿３は結合して環を形
成してもよい。Ｘは水素原子または発色現像主薬の酸化
体との反応により離脱する置換基を表わす。］[Claims] A photographic coupler represented by the general formula [I]. General formula [I] ▲ Numerical formula, chemical formula, table, etc.▼ [In the formula, R_1, R_2, R_3 and Y represent a hydrogen atom or a substituent, and R_2 and R_3 may be combined to form a ring. X represents a hydrogen atom or a substituent that is eliminated by reaction with an oxidized product of a color developing agent. ]
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27098090A JPH04147134A (en) | 1990-10-09 | 1990-10-09 | New photographic coupler |
| US07/771,447 US5208141A (en) | 1990-10-09 | 1991-10-04 | Silver halide color photographic light-sensitive material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27098090A JPH04147134A (en) | 1990-10-09 | 1990-10-09 | New photographic coupler |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04147134A true JPH04147134A (en) | 1992-05-20 |
Family
ID=17493716
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27098090A Pending JPH04147134A (en) | 1990-10-09 | 1990-10-09 | New photographic coupler |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04147134A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006508030A (en) * | 2002-05-09 | 2006-03-09 | サイトキネティクス・インコーポレーテッド | Pyrimidinone compounds, compositions and methods |
-
1990
- 1990-10-09 JP JP27098090A patent/JPH04147134A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006508030A (en) * | 2002-05-09 | 2006-03-09 | サイトキネティクス・インコーポレーテッド | Pyrimidinone compounds, compositions and methods |
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