JPH0395545A - Silver halide color photographic sensitive material having color mixing preventive effect and excellent coating stability - Google Patents
Silver halide color photographic sensitive material having color mixing preventive effect and excellent coating stabilityInfo
- Publication number
- JPH0395545A JPH0395545A JP23327389A JP23327389A JPH0395545A JP H0395545 A JPH0395545 A JP H0395545A JP 23327389 A JP23327389 A JP 23327389A JP 23327389 A JP23327389 A JP 23327389A JP H0395545 A JPH0395545 A JP H0395545A
- Authority
- JP
- Japan
- Prior art keywords
- group
- layer
- silver halide
- coating
- sensitive material
- 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 116
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 57
- 239000004332 silver Substances 0.000 title claims abstract description 57
- 239000000463 material Substances 0.000 title claims abstract description 35
- 239000011248 coating agent Substances 0.000 title abstract description 56
- 238000000576 coating method Methods 0.000 title abstract description 56
- 238000002156 mixing Methods 0.000 title description 15
- 230000003449 preventive effect Effects 0.000 title 1
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 59
- 239000007788 liquid Substances 0.000 claims abstract description 34
- 108010010803 Gelatin Proteins 0.000 claims abstract description 30
- 229920000159 gelatin Polymers 0.000 claims abstract description 30
- 239000008273 gelatin Substances 0.000 claims abstract description 30
- 235000019322 gelatine Nutrition 0.000 claims abstract description 30
- 235000011852 gelatine desserts Nutrition 0.000 claims abstract description 30
- 239000000839 emulsion Substances 0.000 claims abstract description 29
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims description 24
- 239000000470 constituent Substances 0.000 claims description 10
- 238000009835 boiling Methods 0.000 abstract description 16
- 239000000203 mixture Substances 0.000 abstract description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 abstract description 12
- 239000010409 thin film Substances 0.000 abstract description 12
- 239000002904 solvent Substances 0.000 abstract description 10
- 239000011230 binding agent Substances 0.000 abstract description 3
- 239000004094 surface-active agent Substances 0.000 abstract description 3
- 230000002745 absorbent Effects 0.000 abstract 5
- 239000002250 absorbent Substances 0.000 abstract 5
- 239000010410 layer Substances 0.000 description 109
- 239000000243 solution Substances 0.000 description 24
- 125000003545 alkoxy group Chemical group 0.000 description 17
- 150000001875 compounds Chemical class 0.000 description 17
- 125000003342 alkenyl group Chemical group 0.000 description 16
- 125000003118 aryl group Chemical group 0.000 description 16
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 16
- 239000010408 film Substances 0.000 description 15
- 238000000034 method Methods 0.000 description 14
- 125000001424 substituent group Chemical group 0.000 description 11
- 125000004432 carbon atom Chemical group C* 0.000 description 9
- 239000003960 organic solvent Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000000975 dye Substances 0.000 description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 239000006096 absorbing agent Substances 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 238000011161 development Methods 0.000 description 7
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 7
- 238000012545 processing Methods 0.000 description 7
- 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
- 125000004104 aryloxy group Chemical group 0.000 description 6
- 206010070834 Sensitisation Diseases 0.000 description 5
- 239000000084 colloidal system Substances 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 125000005843 halogen group Chemical group 0.000 description 5
- 239000003112 inhibitor Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 230000008313 sensitization Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- SJOOOZPMQAWAOP-UHFFFAOYSA-N [Ag].BrCl Chemical compound [Ag].BrCl SJOOOZPMQAWAOP-UHFFFAOYSA-N 0.000 description 4
- 125000002252 acyl group Chemical group 0.000 description 4
- 125000000753 cycloalkyl group Chemical group 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 239000011241 protective layer Substances 0.000 description 4
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000009501 film coating Methods 0.000 description 3
- 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 3
- 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 3
- 125000005447 octyloxy 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])O* 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 230000002265 prevention Effects 0.000 description 3
- 239000005871 repellent Substances 0.000 description 3
- 230000002940 repellent Effects 0.000 description 3
- 239000002562 thickening agent Substances 0.000 description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- 102100020895 Ammonium transporter Rh type A Human genes 0.000 description 2
- 101100301844 Arabidopsis thaliana RH50 gene Proteins 0.000 description 2
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 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
- 101150107345 Rhag gene Proteins 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229960000583 acetic acid Drugs 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
- 125000005115 alkyl carbamoyl group Chemical group 0.000 description 2
- 125000005153 alkyl sulfamoyl group Chemical group 0.000 description 2
- 125000004390 alkyl sulfonyl group Chemical group 0.000 description 2
- 125000004422 alkyl sulphonamide group Chemical group 0.000 description 2
- 125000004414 alkyl thio 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
- 125000005161 aryl oxy carbonyl group Chemical group 0.000 description 2
- 125000004391 aryl sulfonyl group Chemical group 0.000 description 2
- 125000004421 aryl sulphonamide group Chemical group 0.000 description 2
- 125000005110 aryl thio group Chemical group 0.000 description 2
- 239000007844 bleaching agent Substances 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- UOCJDOLVGGIYIQ-PBFPGSCMSA-N cefatrizine Chemical group S([C@@H]1[C@@H](C(N1C=1C(O)=O)=O)NC(=O)[C@H](N)C=2C=CC(O)=CC=2)CC=1CSC=1C=NNN=1 UOCJDOLVGGIYIQ-PBFPGSCMSA-N 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 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 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 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 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 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
- 235000021317 phosphate Nutrition 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 125000005498 phthalate group Chemical class 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000004848 polyfunctional curative Substances 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000010186 staining Methods 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
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- ZRHUHDUEXWHZMA-UHFFFAOYSA-N 1,4-dihydropyrazol-5-one Chemical compound O=C1CC=NN1 ZRHUHDUEXWHZMA-UHFFFAOYSA-N 0.000 description 1
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-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
- 229940100484 5-chloro-2-methyl-4-isothiazolin-3-one Drugs 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 229920001174 Diethylhydroxylamine Polymers 0.000 description 1
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 1
- 241000257303 Hymenoptera Species 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
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- HOLVRJRSWZOAJU-UHFFFAOYSA-N [Ag].ICl Chemical compound [Ag].ICl HOLVRJRSWZOAJU-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000001204 arachidyl 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])C([H])([H])[H] 0.000 description 1
- 125000005116 aryl carbamoyl group Chemical group 0.000 description 1
- XNSQZBOCSSMHSZ-UHFFFAOYSA-K azane;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxymethyl)amino]acetate;iron(3+) Chemical compound [NH4+].[Fe+3].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O XNSQZBOCSSMHSZ-UHFFFAOYSA-K 0.000 description 1
- ZFSFDELZPURLKD-UHFFFAOYSA-N azanium;hydroxide;hydrate Chemical compound N.O.O ZFSFDELZPURLKD-UHFFFAOYSA-N 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid group Chemical group C(C1=CC=CC=C1)(=O)O WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- PBHVCRIXMXQXPD-UHFFFAOYSA-N chembl2369102 Chemical compound C1=CC(S(=O)(=O)O)=CC=C1C(C1=CC=C(N1)C(C=1C=CC(=CC=1)S(O)(=O)=O)=C1C=CC(=N1)C(C=1C=CC(=CC=1)S(O)(=O)=O)=C1C=CC(N1)=C1C=2C=CC(=CC=2)S(O)(=O)=O)=C2N=C1C=C2 PBHVCRIXMXQXPD-UHFFFAOYSA-N 0.000 description 1
- DHNRXBZYEKSXIM-UHFFFAOYSA-N chloromethylisothiazolinone Chemical compound CN1SC(Cl)=CC1=O DHNRXBZYEKSXIM-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- DROMNWUQASBTFM-UHFFFAOYSA-N dinonyl benzene-1,2-dicarboxylate Chemical compound CCCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCCC DROMNWUQASBTFM-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 108010025899 gelatin film Proteins 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000006038 hexenyl group Chemical group 0.000 description 1
- 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 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- 229910000378 hydroxylammonium sulfate Inorganic materials 0.000 description 1
- LOCAIGRSOJUCTB-UHFFFAOYSA-N indazol-3-one Chemical compound C1=CC=C2C(=O)N=NC2=C1 LOCAIGRSOJUCTB-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
- 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 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
- 125000001624 naphthyl group Chemical group 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
- 125000005064 octadecenyl group Chemical group C(=CCCCCCCCCCCCCCCCC)* 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000002958 pentadecyl 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])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 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
- 230000001681 protective effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 230000001235 sensitizing effect Effects 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
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000001043 yellow dye Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明はハロゲン化銀カラー写真感光材料に関し、更に
詳しくは、混色防止効果を有し、かつ、塗布安定性が優
れたハロゲン化銀カラー写真感光材料に関する。Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a silver halide color photographic light-sensitive material, and more specifically, a silver halide color photograph having an effect of preventing color mixture and having excellent coating stability. Regarding photosensitive materials.
［発明の背景］
一般にハロゲン化銀カラー写真感光材料は、支持体上に
親水性コロイドを含む写真構底層が複数設けられている
。それらの写真構成層は、感光層、中間層、表面保護層
等の種々の機能を有する層であり、これら各層は、高速
かつ薄膜にて多層同時塗布することができるものである
ことが要求されている。[Background of the Invention] Generally, a silver halide color photographic light-sensitive material has a plurality of photographic bottom layers containing a hydrophilic colloid provided on a support. These photographic constituent layers have various functions such as a photosensitive layer, an intermediate layer, and a surface protective layer, and each of these layers is required to be able to be coated simultaneously in multiple thin films at high speed. ing.
また、これらのハロゲン化銀カラー写真感光材料を発色
現像する際に、混色という好ましくない問題点があった
。Furthermore, when these silver halide color photographic materials are subjected to color development, there is an undesirable problem of color mixing.
この混色というのは、発色現像に劣り発生した発色現像
主薬酸化生成物が、発色現像処理工程中に、他のハロゲ
ン化銀乳剤層に拡散移動し、その層でその層のカプラー
とカップリングして発色するために起こる現象である。This color mixing is caused by the oxidation products of the color developing agent generated due to poor color development diffusing into other silver halide emulsion layers during the color development process and coupling with the couplers in that layer. This phenomenon occurs due to the color development.
この混色を防ぐ対策として、ハロゲン化銀乳剤層の間に
非拡散性のハイドロキノン系の化合物を添加した中間層
を設け、該中間層において拡散してくる現像主薬酸化生
威物を還元捕捉し、カップリング能を消失させるという
方法が広く採用されている。As a measure to prevent this color mixture, an intermediate layer containing a non-diffusible hydroquinone compound is provided between the silver halide emulsion layers, and the oxidized products of the developing agent that diffuse in the intermediate layer are reduced and captured. A widely used method is to eliminate the coupling ability.
これら混色防止の目的に用いることができる非拡散性ハ
イドロキノン系化合物は、例えば米国特許第２，３３６
，８２７号明細書、同第２，３６０，２９０号明細書、
同第２，３８４，６５８号明細書、同第２，６７５，５
３１号明細書、同第２，７２８，６５９号明細書、同第
２，７３２，３００号明細書、同第３，７００，４５３
号明細書、特公昭５６− ４０８１８号公報、同５３−
３４０４号公報に記載されている。These non-diffusible hydroquinone compounds that can be used for the purpose of preventing color mixture include, for example, U.S. Patent No. 2,336
, Specification No. 827, Specification No. 2,360,290,
Specification No. 2,384,658, No. 2,675,5
Specification No. 31, Specification No. 2,728,659, Specification No. 2,732,300, Specification No. 3,700,453
specification, Japanese Patent Publication No. 56-40818, No. 53-
It is described in Publication No. 3404.
しかし、これら従来の方法では、前記非拡散性のハイド
ロキノン系化合物を含有する乳化分散物が不安定で、数
時間の保存で分散粒子の粗大化及び含有非拡散性ハイド
ロキノン系化合物の結晶化が起こるという問題があった
。However, in these conventional methods, the emulsified dispersion containing the non-diffusible hydroquinone compound is unstable, and the dispersed particles become coarse and the contained non-diffusible hydroquinone compound crystallizes after several hours of storage. There was a problem.
この問題点を改良するために、特開昭８１− ２９１７
４４号公報には２位、５位に第３級アルキル基を有する
ハイドロキノン系化合物と２位に第２級アルキル基を有
するハイドロキノン系化合物を用いることが提案されて
いる。In order to improve this problem, Japanese Patent Application Laid-Open No. 81-2917
No. 44 proposes the use of a hydroquinone compound having a tertiary alkyl group at the 2nd and 5th positions and a hydroquinone compound having a secondary alkyl group at the 2nd position.
しかしながら、これらの方法によれば高い混色防止効果
が得られるが、近来、ハロゲン化銀カラー写真感光材料
に要求されている写真構成層を高速かつ薄膜にて塗布す
るということを満足するには充分ではなかった。However, although these methods can provide a high color mixing prevention effect, they are not sufficient to satisfy the recent demands for coating the photographic constituent layer in a thin film at high speed for silver halide color photographic light-sensitive materials. It wasn't.
また、欧州特許公開第５７１６０号、特開昭５８− ２
１４１５２号公報、同ＢＯ− ２２２８５２号公報、特
願昭ｆｉｌ−２９０９２４号公報、同６Ｌ− ２９１２
７６号公報、同６ｌ−９５０２２号公報には、常温で液
体状の紫外線吸収剤を用いることが記載されている。Also, European Patent Publication No. 57160, Japanese Patent Application Publication No. 58-2
No. 14152, BO-222852, Japanese Patent Application No. Shofil-290924, No. 6L-2912
No. 76 and No. 6l-95022 describe the use of ultraviolet absorbers that are liquid at room temperature.
しかしながら、これら常温で液体状の紫外線吸収剤を使
用しても、高速かつ薄膜にて塗布する場合に充分な塗布
安定性は得られない。However, even when these ultraviolet absorbers that are liquid at room temperature are used, sufficient coating stability cannot be obtained when coating in a thin film at high speed.
更に、ハロゲン化銀カラー写真感光材料において、支持
体に最も近いハロゲン化銀乳剤層のゼラチン付量を少な
くし、また、低粘度のゼラチンを使用することが知られ
ている。例えば特開昭５２１１５２１４号公報には、支
持体に最も近いハロゲン化３
銀乳剤層に用いるゼラチンの粘度をｉ〜８ｃｐとし、該
層の塗布液の塗布量を２〜１２ｃｍ３／ｒｒ？とするこ
とが記載され、また、特開昭５８− １０８５［ｉ６号
公報には、支持体に最も近いハロゲン化銀乳剤層に用い
るゼラチンの粘度の許容範囲が記載されているが、高速
かつ薄膜にて塗布する場合に充分な塗布安定性は得られ
ない。Furthermore, in silver halide color photographic light-sensitive materials, it is known to reduce the amount of gelatin applied to the silver halide emulsion layer closest to the support and to use gelatin of low viscosity. For example, JP-A-52115214 discloses that the viscosity of gelatin used in the silver halide emulsion layer closest to the support is i~8 cp, and the coating amount of the coating liquid for this layer is 2~12 cm3/rr? In addition, JP-A-58-1085 [i6] describes the permissible range of viscosity of gelatin used in the silver halide emulsion layer closest to the support. Sufficient coating stability cannot be obtained when coating with .
以上の通り、高速かつ薄膜にて塗布することができ、ま
た、高速かつ薄膜にて塗布した場合でも、混色を起こす
ことがないハロゲン化銀カラー写真感光材料は未だ知ら
れていないのが現状であり、近来このようなハロゲン化
銀カラー写真感光材料を得ることが強く望まれていた。As mentioned above, there is currently no known silver halide color photographic material that can be coated at high speed and in a thin film, and which does not cause color mixture even when coated at high speed and in a thin film. Recently, it has been strongly desired to obtain such silver halide color photographic materials.
［発明の目的］
本発明の目的は、充分な塗布安定性をもって、高速で薄
膜塗布を行なうことができるハロゲン化銀カラー写真感
光材料を提供することにある。[Object of the Invention] An object of the present invention is to provide a silver halide color photographic material that has sufficient coating stability and can be coated in a thin film at high speed.
また本発明の他の目的は、混色を起こさないハロゲン化
銀カラー写真感光材料を提供することにある。Another object of the present invention is to provide a silver halide color photographic material that does not cause color mixing.
４
またさらに本発明の他の目的は、塗布液の安定性が優れ
たハロゲン化銀カラー写真感光材料を提供することにあ
る。4. Still another object of the present invention is to provide a silver halide color photographic material whose coating solution has excellent stability.
［発明の構成］
本発明の上記目的は、支持体上に、少なくとも１層のハ
ロゲン化銀乳剤層および少なくとも１層の非感光性層か
ら構成される写真構成層を有するハロゲン化銀カラー写
真感光材料において、前記写真構成層の少なくともｌ層
に常温にて液体状の紫外線吸収剤を含有させ、かつ、少
なくとも１層に２位に第２級アルキル基を有するハイド
ロキノン系化合物を含有させると共に、支持体に最も近
いハロゲン化銀乳剤層のゼラチンを１８■／ｄｍ２以下
としたことを特徴とするハロゲン化銀カラー写真感光材
料によって達成された。[Structure of the Invention] The above-mentioned object of the present invention is to provide a silver halide color photographic material having a photographic constituent layer composed of at least one silver halide emulsion layer and at least one non-photosensitive layer on a support. In the material, at least one of the photographic constituent layers contains an ultraviolet absorber that is liquid at room temperature, and at least one layer contains a hydroquinone compound having a secondary alkyl group at the 2-position, and This was achieved by a silver halide color photographic light-sensitive material characterized in that the gelatin in the silver halide emulsion layer closest to the body was 18 .mu./dm2 or less.
［発明の具体的な構ａ１
本発明に用いられる常温にて液体状の紫外線吸収剤（以
下、本発明の液状紫外線吸収剤という。）は、単一の化
合物であっても、混合物であってもよく、混合物として
は構造異性体群から構成されるものを好ましく用いるこ
とができる。（構造異性体については、米国特許第４，
５８７．３４６号明細書等に記載されている。）
本発明の液状紫外線吸収剤はいかなる化学構造のもので
あってもよいか、光堅牢性の点から下記一般式［ａｌで
示される２− （２’ −ヒドロキシフエニル）ペンゾ
トリアゾール系化合物か好ましい。[Specific structure of the invention a1 The ultraviolet absorber that is liquid at room temperature (hereinafter referred to as the liquid ultraviolet absorber of the present invention) used in the present invention may be a single compound or a mixture. As a mixture, one composed of a group of structural isomers can be preferably used. (For structural isomers, see U.S. Pat.
It is described in the specification of No. 587.346. ) The liquid ultraviolet absorber of the present invention may have any chemical structure, but from the viewpoint of light fastness, it may be a 2-(2'-hydroxyphenyl)penzotriazole compound represented by the following general formula [al]. Or preferable.
一般式［ ａ． ］
Ｒ２
上記一般式［ａ］において、Ｒ１、Ｒ２およびＲ３はそ
れぞれ水素原子、アルキル基、アリール基、アルコキシ
基、アリールオキシ基、アルケニル基、ニトロ基または
ヒドロキシル基を表わす。General formula [ a. ] R2 In the above general formula [a], R1, R2 and R3 each represent a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkenyl group, a nitro group or a hydroxyl group.
Ｒ１、Ｒ２およびＲ３て表わされるアルキル基、アルコ
キシ基としては、炭素数ｔ〜３０のものか好ましく、ま
たアルケニル基としては、炭素数２〜３０のものが好ま
しい。これらの基は直鎖でも、分岐でもよい。The alkyl group and alkoxy group represented by R1, R2 and R3 preferably have t to 30 carbon atoms, and the alkenyl group preferably has 2 to 30 carbon atoms. These groups may be linear or branched.
また、これらアルキル基、アルケニル基、アルコキシ基
は、さらに置換基を有してもよい。Moreover, these alkyl groups, alkenyl groups, and alkoxy groups may further have a substituent.
アルキル基、アルケニル基、アルコキシ基の具体例とし
ては、例えばメチル基、エチル基、イソプロビル基、ｔ
−ブチル基、ｓｅｃ−ブチル基、ｎブチル基、ｎ−アミ
ル基、ｓｅｃ−アミル基、ｔ一アミル基、オクチル基、
ノニル基、ドデシル基、エイコシル基、α，α−ジメチ
ルベンジル基、オクチルオキシカルボニルエチル基、メ
トキシ基、エトキシ基、オクチルオキシ基、アリル基が
挙げられる。Specific examples of alkyl groups, alkenyl groups, and alkoxy groups include methyl groups, ethyl groups, isoprobyl groups, t
-butyl group, sec-butyl group, n-butyl group, n-amyl group, sec-amyl group, t-amyl group, octyl group,
Examples include nonyl group, dodecyl group, eicosyl group, α,α-dimethylbenzyl group, octyloxycarbonylethyl group, methoxy group, ethoxy group, octyloxy group, and allyl group.
Ｒ， 、Ｒ２およびＲ３で表わされるアリール基、了り
ールオキシ基としては、例えばフエニル基、フエニルオ
キシ基が特に好ましく、置換基を有していてもよい。具
体的には、例えばフェニル基、４−ｔ−プチルフエニル
基、２，４−ジーｔ−アミルフエニル基が挙げられる。As the aryl group and the aryloxy group represented by R, , R2 and R3, for example, a phenyl group and a phenyloxy group are particularly preferable, and they may have a substituent. Specific examples include phenyl group, 4-t-butylphenyl group, and 2,4-di-t-amyl phenyl group.
Ｒ１およびＲ２で表わされる基としては、水素原子、ア
ルキル基、アルコキシ基およびアリール基が好ましく、
特に水素原子、アルキル基およびアルコキシ基か好まし
い。The groups represented by R1 and R2 are preferably a hydrogen atom, an alkyl group, an alkoxy group and an aryl group,
Particularly preferred are hydrogen atoms, alkyl groups and alkoxy groups.
Ｒ３で表わされる基としては、特に水素原子、アルキル
基、アルコキシ基が好ましい。The group represented by R3 is particularly preferably a hydrogen atom, an alkyl group, or an alkoxy group.
上記化合物が常温で液体となるためには、Ｒ１、Ｒ２お
よびＲ３て表わされる基の少なくとも１つがアルキル基
であることが好ましく、更に少なくとも２つがアルキル
県であること好ましくい。In order for the above compound to become liquid at room temperature, it is preferable that at least one of the groups represented by R1, R2 and R3 is an alkyl group, and it is further preferable that at least two of the groups are alkyl groups.
Ｒ１、Ｒ２およびＲ３で表わされるアルキル基は、いか
なるアルキル基てあってもよいが、少なくとも１つは第
３級アルキル基または第２級アルキル基であることか好
ましい。特にＲ１およびＲ２で表わされるアルキル基の
少なくとも一方が第３級アルキル基または第２級アルキ
ル基であることが好ましい。The alkyl groups represented by R1, R2 and R3 may be any alkyl group, but it is preferred that at least one is a tertiary alkyl group or a secondary alkyl group. In particular, it is preferred that at least one of the alkyl groups represented by R1 and R2 is a tertiary alkyl group or a secondary alkyl group.
以下に本発明の波状紫外線吸収剤の代表的具体例を示す
。Typical specific examples of the wavy ultraviolet absorber of the present invention are shown below.
以下余白
８
ｌ ０
（続き）
以下余白
前記本発明の液状紫外線吸収剤の添加量は、特に制限は
なくいかなる添加量であってもよいが、該紫外線吸収剤
を含有する写真構成層のバインダーに対して重量で０．
１〜３００％の範囲で用いることができ、好ましくはｌ
〜２００％、更に好ましくは５〜１００％の範囲で用い
ることができる。また塗布量としては０．０１〜１００
■／ＬＯＯｃ♂が好ましく、更１： ０．１〜５０ｍｇ
／ ｌ ０ ０ｃｔ ，特に０．５ 〜３０ｍｇ ／
１ ０ ０ｃＪで用いるのが好ましい。Margin below 8 l 0 (Continued) Margin below The amount of the liquid ultraviolet absorber of the present invention to be added is not particularly limited and may be any amount; On the other hand, the weight is 0.
It can be used in the range of 1 to 300%, preferably l
It can be used in a range of 200% to 200%, more preferably 5 to 100%. The coating amount is 0.01 to 100.
■/LOOc♂ is preferable, and further 1: 0.1 to 50 mg
/ l 0 0 ct, especially 0.5 to 30 mg /
It is preferable to use 100 cJ.
本発明の液状紫外線吸収剤は常温で液状であるため、そ
のままあるいは必要に応じて酢酸エチル等の低沸点溶媒
を用いてゼラチン水溶液などの親水性バインダー中に界
面活性剤を用いて微分散することができる。Since the liquid ultraviolet absorber of the present invention is liquid at room temperature, it can be finely dispersed as it is or, if necessary, in a hydrophilic binder such as an aqueous gelatin solution using a low boiling point solvent such as ethyl acetate using a surfactant. I can do it.
また、必要に応じてフェノール誘導体、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、トリメシン酸
エステル等の高沸点溶媒を併用してもよい。In addition, high boiling point solvents such as phenol derivatives, phthalic esters, phosphoric esters, citric esters, benzoic esters, alkylamides, fatty acid esters, and trimesic esters may be used in combination, if necessary.
更に、本発明の液状紫外線吸収剤は、常温にて１１
固体状の紫外線吸収剤を併用することができるが、この
場合も前記の添加方法が適用できる。Furthermore, the liquid ultraviolet absorber of the present invention can be used in combination with a solid ultraviolet absorber at room temperature, and the above-mentioned addition method can also be applied in this case.
上記併用することができる常温にて固体状の紫外線吸収
剤（以下、固体状紫外線吸収剤という。）は、常温（２
５℃）において固体であればいがなる化学構造のもので
あってもよいが、光堅牢性の点から、特に下記一般式［
ｂ］で示される固体状の２− （２’−ヒドロキシフエ
ニル）ペンゾトリアゾール系化合物が好ましい。The ultraviolet absorber that is solid at room temperature (hereinafter referred to as solid ultraviolet absorber) that can be used in combination with the above is
It may have a chemical structure that is solid as long as it is solid at 5℃), but from the viewpoint of light fastness, the following general formula [
A solid 2-(2'-hydroxyphenyl)penzotriazole compound represented by b] is preferred.
一般式［ｂ］
Ｋ５
上記一般式［ｂ］において、Ｒ４、Ｒ，およびＲ６はそ
れぞれ水素原子、ハロゲン原子、アルキル基、アリール
基、アルコキシ基、アリールオキシ基、アルケニル基、
ニトロ基またはヒドロキシル基を表わす。General formula [b] K5 In the above general formula [b], R4, R, and R6 are each a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkenyl group,
Represents a nitro group or a hydroxyl group.
Ｒ４、Ｒ５およびＲ６で表わされるハロゲン原１ ２
子としては、例えば弗素原子、塩素原子、臭素原子等が
挙げられ、特に塩素原子が好ましい。Examples of the halogen atom represented by R4, R5 and R6 include fluorine atom, chlorine atom, bromine atom and the like, with chlorine atom being particularly preferred.
Ｒ４、Ｒ，およびＲ６で表わされるアルキル基、アルコ
キシ基としては、炭素数ｌ〜３０のものが好ましく、ま
たアルケニル基としては、炭素数２〜３０のものが好ま
しい。これらの基は直鎖でも、分岐でもよい。The alkyl group and alkoxy group represented by R4, R, and R6 preferably have 1 to 30 carbon atoms, and the alkenyl group preferably has 2 to 30 carbon atoms. These groups may be linear or branched.
また、これらアルキル基、アルケニル基、アルコキシ基
は、さらに置換基を有してもよい。Moreover, these alkyl groups, alkenyl groups, and alkoxy groups may further have a substituent.
アルキル基、アルケニル基、アルコキシ基の具体例とし
ては、例えばメチル基、エチル基、イソプロビル基、ｔ
−ブチル基、ｓｅｅ−ブチル基１ｎブチル基、ｎ−アミ
ル基、ＳｅＣ−アミル基、ｔアミル基、α，α−ジメチ
ルベンジル基、オクチルオキシ力ルポニルエチル基、メ
トキシ基、エトキシ基、オクチルオキシ基、アリル基が
挙げられる。Specific examples of alkyl groups, alkenyl groups, and alkoxy groups include methyl groups, ethyl groups, isoprobyl groups, t
-butyl group, see-butyl group, n-butyl group, n-amyl group, SeC-amyl group, t-amyl group, α,α-dimethylbenzyl group, octyloxy group, methoxy group, ethoxy group, octyloxy group, Examples include allyl groups.
Ｒ４、Ｒ，およびＲ６で表わされるアリール基、アリー
ルオキシ基としては、例えばフエニル基、フエニルオキ
シ基が特に好ましく、置換基を有していでもよい。具体
的には、例えばフエニル基、４−ｔ−プチルフェニル基
、２，４−ジーｔ−アミルフェニル基が挙げられる。As the aryl group and aryloxy group represented by R4, R, and R6, for example, a phenyl group and a phenyloxy group are particularly preferable, and they may have a substituent. Specific examples include phenyl group, 4-t-butylphenyl group, and 2,4-di-t-amylphenyl group.
Ｒ４およびＲ，で表わされる基としては、水素原子、ア
ルキル基、アルコキシ基およびアリール基が好ましく、
特に水素原子、アルキル址およびアルコキシ基が好まし
い。The groups represented by R4 and R are preferably a hydrogen atom, an alkyl group, an alkoxy group, or an aryl group,
Particularly preferred are hydrogen atoms, alkyl groups and alkoxy groups.
Ｒ６で表わされる基としては、特に水素原子、ハロゲン
原子、アルキル基、アルコキシ基が好ましい。The group represented by R6 is particularly preferably a hydrogen atom, a halogen atom, an alkyl group, or an alkoxy group.
以下に固体状紫外線吸収剤の代表的具体例を示す。Typical examples of solid ultraviolet absorbers are shown below.
以下余白
１
５
以下余白
１ ６
本発明のハロゲン化銀カラー写真感光材料が多色カラー
写真感光材料でる場合、具体的な層構成としては、支持
体上に、支持体側から順次、イエローカプラー含有ハロ
ゲン化銀乳剤層、第１中間層、マゼンタカプラー含有ハ
ロゲン化銀乳剤層、第２中間層、シアンカプラー含有ハ
ロゲン化銀乳剤層、第３中間層、保護層と配列したもの
が特に好ましい。The following margin is 1 5 The following is a margin 1 6 When the silver halide color photographic light-sensitive material of the present invention is a multicolor color photographic light-sensitive material, the specific layer structure is such that yellow coupler-containing halogen is sequentially formed on the support from the support side. Particularly preferred is a structure in which a silver halide emulsion layer, a first intermediate layer, a magenta coupler-containing silver halide emulsion layer, a second intermediate layer, a cyan coupler-containing silver halide emulsion layer, a third intermediate layer, and a protective layer are arranged.
本発明の液状紫外線吸収剤は写真構成層の任意の層に含
有することができるが、本発明のハロゲン化銀カラー写
真感光材料が特に上記の層構戊よりなる場合には、本発
明の液状紫外線吸収剤は少なくとも第２中間層及び第３
中間層に含有することが好ましい。またこの場合、第３
中間層に含有される紫外線吸収剤の総量と、第３中間層
よりも支持体に近い側の層に含有される紫外線吸収剤の
総量との比率は、イエロー、マゼンタ及びシアン色素画
像の耐光性のバランスや物理特性等を考慮し、いかなる
比率でもかまわないが、好ましくは０．１＋１０〜ｉｏ
ｌ１，更に好ましくはＩ．：ＬＯ〜５：１
７
１ ８
ｉの範囲で用いることができる。なお、ここで紫外線吸
収剤の総量とは、本発明の液状紫外線吸収剤のみを用い
る場合にはその総量であり、また本発明の液状紫外線吸
収剤に例えば固体状紫外線吸収剤を併用する場合にはこ
れらの総量である。The liquid ultraviolet absorber of the present invention can be contained in any layer of the photographic constituent layers, but when the silver halide color photographic light-sensitive material of the present invention has the above-mentioned layer structure, the liquid ultraviolet absorber of the present invention The ultraviolet absorber is present in at least the second intermediate layer and the third intermediate layer.
It is preferably contained in the intermediate layer. Also in this case, the third
The ratio of the total amount of ultraviolet absorbers contained in the intermediate layer to the total amount of ultraviolet absorbers contained in layers closer to the support than the third intermediate layer determines the light fastness of yellow, magenta, and cyan dye images. Any ratio may be used considering the balance and physical properties of
l1, more preferably I. :LO to 5:1718i. Note that the total amount of the ultraviolet absorber here refers to the total amount when only the liquid ultraviolet absorber of the present invention is used, and when the liquid ultraviolet absorber of the present invention is used in combination with, for example, a solid ultraviolet absorber. is the total amount of these.
次に、本発明に用いられる２位に第２級アルキル基を有
するハイドロキノン系化合物について説明する。Next, the hydroquinone compound having a secondary alkyl group at the 2-position used in the present invention will be explained.
本発明に用いられる２位に第２級アルキル基を有するハ
イドロキノン系化合物は、下記一般式［Ｉ］で表わすこ
とができる。The hydroquinone compound having a secondary alkyl group at the 2-position used in the present invention can be represented by the following general formula [I].
一般式［Ｉ］
０ｌｌ，
０Ｒｅ
式中、Ｒ７及びＲ８はそれぞれ水素原子、アルキル基、
アルケニル基、アリール基、゛アシル基、シクロアルキ
ル基または複素環基を表わし、Ｘは第２級アルキル基を
表わし、Ｒ９、Ｒｌ（ｌ及びＲ１，はそれぞれ水素原子
または置換基を表わす。General formula [I] 0ll, 0Re In the formula, R7 and R8 are each a hydrogen atom, an alkyl group,
It represents an alkenyl group, an aryl group, an acyl group, a cycloalkyl group, or a heterocyclic group, X represents a secondary alkyl group, and R9, R1 (l and R1 each represent a hydrogen atom or a substituent).
Ｒ９、Ｒ，ｏ及びＲ１１で表わされる置換基としては特
に限定はないが、例えばハロゲン原子、アルキル基、ア
ルケニル基、アリール基、シクロアルキル基、アルコキ
シ基、アリールオキシ基、アルキルチオ基、アリールチ
オ基、アシル基、アシルアミノ基、アルキルカルバモイ
ル基、アリールカルバモイル基、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、アルキルスルホニ
ル基、アリールスルホニル基、ニトロ基、シアノ基、ア
ルコキシカルボニル基、アリールオキシカルボニル基、
アシルオキシ基が挙げられる。The substituents represented by R9, R, o and R11 are not particularly limited, but include, for example, a halogen atom, an alkyl group, an alkenyl group, an aryl group, a cycloalkyl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, Acyl group, acylamino group, alkylcarbamoyl group, arylcarbamoyl group, alkylsulfonamide group, arylsulfonamide group, alkylsulfamoyl group, arylsulfamoyl group, alkylsulfonyl group, arylsulfonyl group, nitro group, cyano group, alkoxycarbonyl group, aryloxycarbonyl group,
Examples include acyloxy groups.
Ｒ９及びＲＩ４として特に好ましいものは水素原子であ
る。Particularly preferred as R9 and RI4 is a hydrogen atom.
Ｘで表わされる第２級アルキル基とは、ハイドロキノン
系化合物のベンゼン母核に結合する根元炭素原子が、水
素原子１個と炭素原子２個と結合している炭素原子、即
ち第２炭素原子であるアルキル基である。The secondary alkyl group represented by It is a certain alkyl group.
１ つ
Ｘで表わされる第２級アルキル基としては、特に炭素原
子数３〜３２のものが好ましく用いられる。As the secondary alkyl group represented by one X, those having 3 to 32 carbon atoms are particularly preferably used.
前記一般式［Ｉ．］で表わされる化合物のうち、下記一
般式［．Ｌ−ａ］で表わされる化合物が好ましい。The general formula [I. ] Among the compounds represented by the following general formula [. Compounds represented by [L-a] are preferred.
一般式［Ｉ−ａｌ
０Ｈ
２０
０Ｈ
ＵＨ
式中、Ｘは一般式［Ｉ］におけるＸと同義であり、Ｒ１
２は水素原子またはアルキル基を表わす。General formula [I-al 0H 20 0H UH In the formula, X has the same meaning as X in general formula [I], and R1
2 represents a hydrogen atom or an alkyl group.
Ｒ１２で表わされるアルキル基は炭素数１〜３２のアル
キル基が好ましく、第１級アルキル基、第２級アルキル
基または第３級アルキル基のいずれであってもかまわな
い。The alkyl group represented by R12 is preferably an alkyl group having 1 to 32 carbon atoms, and may be any of a primary alkyl group, a secondary alkyl group, and a tertiary alkyl group.
以下に一般式［Ｉ］で表わされる化合物の代表的具体例
を示す。Typical specific examples of the compound represented by general formula [I] are shown below.
以下余白
（続き）
以下余白
これらのハイドロキノン系化合物は、スティン防止剤と
いう名称で、リサーチ・ディスクロージャー誌（Ｒｅｓ
ｅａｒｃｈ Ｄｉｓｃｌｏｓｕｒｅ） 、１ ７ ６号
（１９７８年）の１７８４３項の■のＩに記載されてい
る。その他、米国特許第２，７３２，３００号明細書、
同第３．７００４５３号明細書、特開昭５８− ８７０
４０号公報、同５８２４１４１号公報、同５９− １４
９３４８号公報、特公昭５３−３４０４３号公報、同５
［１− ４０８１９号公報等にも記載されている。Margin below (Continued) Margin below These hydroquinone compounds are known as anti-staining agents,
Disclosure), No. 176 (1978), Section 17843, Section I. Others, U.S. Patent No. 2,732,300,
Specification No. 3.700453, JP-A-58-870
Publication No. 40, Publication No. 5824141, Publication No. 59-14
Publication No. 9348, Japanese Patent Publication No. 53-34043, No. 5
[Also described in Publication No. 1-40819, etc.
本発明に用いられる２位に第２級アルキル基を有するハ
イドロキノン系化合物は、下記一般式［１Ｎ］で表わさ
れる２位と５位に第３級アルキル基を有するハイドロキ
ノン系化合物と併用することができる。The hydroquinone compound having a secondary alkyl group at the 2-position used in the present invention can be used in combination with a hydroquinone compound having a tertiary alkyl group at the 2- and 5-positions represented by the following general formula [1N]. can.
一般式［ｎ］
式中、Ｒｌ３及びＲ１４はそれぞれ水素原子、アル２３
キル基、アルケニル基、アリール基、アシル基、シクロ
アルキル基または複素環基を表わし、Ｘ及びＹはそれぞ
れ第３級アルキル基を表わし、Ｒ１，及びＲ１６はそれ
ぞれ水素原子または置換基を表わす。General formula [n] In the formula, R13 and R14 each represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an acyl group, a cycloalkyl group, or a heterocyclic group, and X and Y each represent a tertiary alkyl group. , and R1 and R16 each represent a hydrogen atom or a substituent.
ＲＩ３及びＲ１４としては水素原子が特に好ましい。Hydrogen atoms are particularly preferred as RI3 and R14.
Ｒ１，及びＲ１６で表わされる置換基としては特に限定
はないが、例えばハロゲン原子、アルキル基、アルケニ
ル基、アリール基、シクロアルキル基、アルコキシ基、
アリールオキシ基、アルキルチオ基、アリールチオ基、
アシル基、アシルアミノ基、アルキルカルバモイル基、
アリール力ルバモイル基、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、アルキルスルホニル基、
アリールスルホニル基、ニトロ基、シアノ基、アルコキ
シカルボニル基、アリールオキシカルボニル基、アシル
オキシ基が挙げられる。The substituents represented by R1 and R16 are not particularly limited, but include, for example, a halogen atom, an alkyl group, an alkenyl group, an aryl group, a cycloalkyl group, an alkoxy group,
Aryloxy group, alkylthio group, arylthio group,
Acyl group, acylamino group, alkylcarbamoyl group,
Aryl group, rubamoyl group, alkylsulfonamide group,
Arylsulfonamide group, alkylsulfamoyl group, arylsulfamoyl group, alkylsulfonyl group,
Examples include an arylsulfonyl group, a nitro group, a cyano group, an alkoxycarbonyl group, an aryloxycarbonyl group, and an acyloxy group.
Ｒ１，及びＲ１６として特に好ましいものは水素原子で
ある。Particularly preferred as R1 and R16 is a hydrogen atom.
２４
Ｘ及びＹで表わされる第３級アルキル基とは、ハイドロ
キノン系化合物のベンゼン母核に結合する根元炭素原子
が、炭素原子３個と結合している炭素原子、即ち第３炭
素原子であるアルキル基である。24 The tertiary alkyl group represented by It is the basis.
Ｘ及びＹで表わされる第３級アルキル基としては、特に
炭素原子４〜３０のものが好ましく用いられ、具体的に
はｔ−ブチル基、ｔ−ベンチル基、ｔ−オクチル基、ｔ
−ドデシル基等が挙げられる。As the tertiary alkyl group represented by
-dodecyl group and the like.
この第３級アルキル基は、アリール基、アルコキシ基、
アルキルアミノ基、アルコキシ力ルボニル基、カルバモ
イル基等の置換基を有していてもよい。This tertiary alkyl group includes an aryl group, an alkoxy group,
It may have a substituent such as an alkylamino group, an alkoxycarbonyl group, or a carbamoyl group.
前記一般式［■］で表わされる化合物のうち、下記一般
式［ｎ−ａ］で表わされる化合物が好ましい。Among the compounds represented by the general formula [■], the compounds represented by the following general formula [na] are preferred.
一般式［ＩＩ−ａ］
ＯＨ
ｔＪＨ
２ ６
式中、Ｘ及びＹは一般式［１１］におけるＸ及びＹと同
義である。General formula [II-a] OH tJH 2 6 In the formula, X and Y have the same meanings as X and Y in general formula [11].
以下に一般式［ｎ］で表わされる化合物の代表的具体例
を示す。Typical specific examples of the compound represented by the general formula [n] are shown below.
以下余白
２
７
２ ８
本発明に用いられるハイドロキノン系化合物の添加量は
、単用及び併用する少なくとも２種のハイドロキノン系
化合物の総和として、いかなる量をもとりうるが、ｌ
ｘ １０−６− ］． ｘ １０−２モル／ｄが好まし
く、さらに好ましくは５ Ｘ １０−６〜５ Ｘ ｔｏ
−３モル／ボの範囲である。Margin below 2 7 2 8 The amount of the hydroquinone compound used in the present invention can be any amount as the sum of at least two hydroquinone compounds used alone or in combination.
x 10-6- ]. x 10-2 mol/d is preferable, more preferably 5 x 10-6 to 5 x to
-3 mol/vo range.
この場合、一般式［Ｉ］で表わされる化合物と一般式［
ＩＩ］で表わされる化合物の併用比率は１００： １〜
｛：５０、好ましくは５０：１〜１：２０、さらに好ま
しくはＩＯ，１〜１ ５である。In this case, the compound represented by the general formula [I] and the general formula [
The combination ratio of the compounds represented by II] is 100:1 to
{:50, preferably 50:1 to 1:20, more preferably IO,1 to 15.
一般式［Ｉ］で表わされる化合物及び／又は一般式［Ｉ
Ｉ］で表わされる化合物（以下、本発明に係るハイドロ
キノン系化合物という。）を写真構戊層中に含有させる
には、本発明に係るハイドロキノン系化合物を、必要に
応じて高沸点有機溶媒及び／又は低沸点有機溶媒に溶解
し、ゼラチン水溶液の如き分散媒中に乳化剤を用いて乳
化分散し、目的とする親水性コロイド層中へ添加すれば
よい。A compound represented by the general formula [I] and/or a compound represented by the general formula [I]
I] (hereinafter referred to as the hydroquinone compound according to the present invention) in the photographic structure layer, the hydroquinone compound according to the present invention is optionally mixed with a high boiling point organic solvent and/or Alternatively, it may be dissolved in a low boiling point organic solvent, emulsified and dispersed in a dispersion medium such as an aqueous gelatin solution using an emulsifier, and then added to the desired hydrophilic colloid layer.
このとき本発明に係るハイドロキノン系化合物と有機溶
媒を別々に乳化分散し、その後にゼラチン水溶波中で混
合することもてきる。At this time, the hydroquinone compound according to the present invention and the organic solvent may be separately emulsified and dispersed, and then mixed in an aqueous gelatin solution.
本発明に係るハイドロキノン系化合物を乳化分散する際
に用いることのできる高沸点有機溶媒としては、誘電率
が６．０以下のものが好ましく、１．９〜６．０の範囲
のものが特に好ましい。The high boiling point organic solvent that can be used when emulsifying and dispersing the hydroquinone compound according to the present invention preferably has a dielectric constant of 6.0 or less, particularly preferably one in the range of 1.9 to 6.0. .
例えば誘電率６，０以下のフタル酸エステル、リン酸エ
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り、フタル酸エステル類、リン酸エ
ステル類か好ましい。Examples include esters such as phthalates and phosphates having a dielectric constant of 6.0 or less, organic acid amides, ketones, and hydrocarbon compounds, with phthalates and phosphates being preferred.
中でも、１００°Ｃにおける蒸気圧が０．５ｍｍＨｇ以
下の高沸点有機溶媒が好ましい。Among these, high boiling point organic solvents having a vapor pressure of 0.5 mmHg or less at 100°C are preferred.
有機溶媒は２種以上の混合物であってもよい。The organic solvent may be a mixture of two or more.
この場合、混合物の誘電率が８．０以下であればよい。In this case, it is sufficient if the dielectric constant of the mixture is 8.0 or less.
上記誘電率は３０℃における誘電率である。The above dielectric constant is a dielectric constant at 30°C.
フタル酸エステルは下記一般式［ＨＡ］で示される。Phthalate ester is represented by the following general formula [HA].
以下余白
３１
一般式［ＨＡ］
？中、Ｒ．およびＲ１．２はそれぞれアルキル基、アル
ケニル基またはアリール基を表わす。但し、Ｒ■１およ
びＲ，，２で表わされる基の炭素原子数の総和は９〜３
２である。Below is the margin 31 General formula [HA]? In, R. and R1.2 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 R,,2 is 9 to 3.
It is 2.
ＲＨＩおよびＲＨ２で表わされる基の炭素原子数の総和
が｛６〜２４てあるものか好ましい。It is preferable that the total number of carbon atoms of the groups represented by RHI and RH2 is {6 to 24.
ＲＨ１およびＲＨ２で表わされるアルキル基は直鎖でも
分岐でもよく、例えばブチル基、オクチル基、ノニル基
、Ｆデシル基、テトラデシル基、ヘキサデシル基、ヘプ
タデシル基、オクタデシル基である。The alkyl group represented by RH1 and RH2 may be linear or branched, and includes, for example, a butyl group, an octyl group, a nonyl group, an F-decyl group, a tetradecyl group, a hexadecyl group, a heptadecyl group, and an octadecyl group.
ＲＨ１およびＲＨ２で表わされるアリール基はフエニル
基、ナフチル基等であり、また、アルヶニル基はへキセ
ニル基、ヘプテニル基、オクタデセニル基等である。The aryl group represented by RH1 and RH2 is a phenyl group, naphthyl group, etc., and the alganyl group is a hexenyl group, heptenyl group, octadecenyl group, etc.
これらのアルキル基、アルケニル基およびアリ３ ２ ？ル基は置換基を有するものも含む。These alkyl groups, alkenyl groups and ants 32 ? The group also includes those having substituents.
Ｒ■１およびＲＨ２として好ましいものはアルキル基で
あり、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一ノニル基が挙
げられる。Preferred examples of R1 and RH2 are alkyl groups, such as 2-ethylhexyl, 3,5.5-trimethylhexyl, n-octyl, and n-nonyl groups.
リン酸エステルは下記一般式［ＨＢ］で示される。The phosphoric acid ester is represented by the following general formula [HB].
一般式［ＨＢ］
Ｏ
Ｉ
ＲＨ５０ Ｐ ＯＲＨ３
ＯＲＨ４
？中、Ｒ．．３、Ｒ，，４およびＲＨ５はそれぞれアル
キル基、アルケニル基またはアリール基を表わす。General formula [HB] O I RH50 P ORH3 ORH4? In, R. ．． 3, R, , 4 and RH5 each represent an alkyl group, an alkenyl group or an aryl group.
但し、ＲＨ３、Ｒ＋｛４およびＲ＋｛５で表わされる基
の炭素原子数の総和は２４〜５４である。However, the total number of carbon atoms of the groups represented by RH3, R+{4 and R+{5 is 24 to 54.
ＲＨ３、Ｒ，■４およびＲＨ，で表わされるアルキル基
は直鎖でも分岐でもよく、例えばブチル基、ペンチル基
、ヘキシル基、オクチル基、ノニル基、ドデシル基、ペ
ンタデシル基、ヘキサデシル基、オクタデシル基、ノナ
デシル基である。The alkyl group represented by RH3, R, ■4 and RH, may be linear or branched, such as butyl group, pentyl group, hexyl group, octyl group, nonyl group, dodecyl group, pentadecyl group, hexadecyl group, octadecyl group, It is a nonadecyl group.
これらのアルキル基、アルケニル基またはアリール基は
置換基を有するものも含む。These alkyl groups, alkenyl groups, and aryl groups include those having substituents.
ＲＨ３、ＲＨ４およびＲＨ，として好ましいものはアル
キル基であり、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、ｓｅＣ−デシル基、ｓｅＣ−ドデ
シル基、ｔ−オクチル基が挙げられる。Preferred as RH3, RH4 and RH are alkyl groups, such as 2-ethylhexyl group, n-octyl group, 3,5.5-trimethylhexyl group, n-nonyl group, n-decyl group, seC-decyl group. , seC-dodecyl group, and t-octyl group.
以下に有機溶媒の具体例を示すが、本発明はこれらに限
定されるものではない。Specific examples of organic solvents are shown below, but the present invention is not limited thereto.
以下余白
３
５
ＲＨ５０
０
１１
Ｐ−ＯＲ＋｛３
Ｈ−２１
ＯＲＨ４
Ｈ−２２
Ｈ−１９
Ｈ−２０
３
７
３ ６
３８
上記高沸点有機溶媒の添加量は、特に制限はなくいかな
る添加量であってもよいが、好ましくは本発明に係るハ
イドロキノン系化合物に対して、０．１〜２０００重量
％であり、特にｔＯ〜５００重量％か好ましい。Below margin 3 5 RH50 0 11 P-OR+{3 H-21 ORH4 H-22 H-19 H-20 3 7 3 6 38 The amount of the above-mentioned high boiling point organic solvent to be added is not particularly limited and may be any amount. However, it is preferably 0.1 to 2000% by weight, particularly preferably tO to 500% by weight, based on the hydroquinone compound according to the present invention.
上記の高沸点有機溶媒には、本発明に係るハイドロキノ
ン系化合物の他にカプラー、紫外線吸収剤、変褪色防止
剤、蛍光増白剤、着色染料等の化合物を同時に添加する
ことができるが、本発明に係るハイドロキノン系化合物
の量を超さないことが好ましい。In addition to the hydroquinone compound according to the present invention, compounds such as couplers, ultraviolet absorbers, anti-fading agents, optical brighteners, and colored dyes can be added to the above-mentioned high-boiling organic solvent at the same time. It is preferred not to exceed the amount of hydroquinone compound according to the invention.
本発明に係るハイドロキノン系化合物は、写真構成層の
任意の層に含有させることができるが、特に２つのハロ
ゲン化銀乳剤層の間の中間層に含有させるのが好ましい
。The hydroquinone compound according to the present invention can be contained in any layer of the photographic constituent layers, but it is particularly preferably contained in an intermediate layer between two silver halide emulsion layers.
なお、本明細書中でいう写真構成層とは、ハロゲン化銀
乳剤層および、例えば中間層、保護層等の非感光性層を
意味する。In this specification, the photographic constituent layer means a silver halide emulsion layer and non-photosensitive layers such as an intermediate layer and a protective layer.
本発明のハロゲン化銀カラー写真感光材料が多色カラー
写真感光材料でる場合、具体的な層構成としでは、支持
体」二に、支持体側から順次、イエローカプラー含有ハ
ロゲン化銀乳剤層、第１中間層、マゼンタカプラー含有
ハロゲン化銀乳剤層、第２中間層、シアンカプラー含有
ハロゲン化銀乳剤層、第３中間層、保護層と配列したも
のが特に好ましい。When the silver halide color photographic light-sensitive material of the present invention is a multicolor color photographic light-sensitive material, the specific layer structure includes a support, a yellow coupler-containing silver halide emulsion layer, a first layer, and a silver halide emulsion layer containing a yellow coupler. Particularly preferred is an arrangement consisting of an intermediate layer, a silver halide emulsion layer containing a magenta coupler, a second intermediate layer, a silver halide emulsion layer containing a cyan coupler, a third intermediate layer, and a protective layer.
本発明に係るハイドロキノン系化合物は、写真構威層の
任意の層に含有させることができるが、本発明のハロゲ
ン化銀カラー写真感光材料が特に上記の層構成よりなる
場合には、本発明に係るハイドロキノン系化合物は第１
中間層及び／又は第２中間層に含有させることが好まし
い。The hydroquinone compound according to the present invention can be contained in any layer of the photographic structure layer, but when the silver halide color photographic light-sensitive material of the present invention has the above-mentioned layer composition, the hydroquinone compound according to the present invention The hydroquinone compound is the first
It is preferable to include it in the intermediate layer and/or the second intermediate layer.
本発明において、支持体に最も近いハロゲン化銀乳剤層
のゼラチンはｔ８■／ｄｍ２以下であることが必要であ
る。In the present invention, the gelatin in the silver halide emulsion layer closest to the support must have a t8/dm2 or less.
該層のゼラチンとしては、当業界で使用されているゼラ
チンであればいずれのものでも使用することができる。As the gelatin for this layer, any gelatin used in the art can be used.
該層のゼラチンは、ゼラチン単独でもよく、また、ゼラ
チン誘導体、ゼラチンを幹とするグラフ３つ
トポリマー、蛋白質、糖誘導体、セルロース誘導体、合
戊親水性高分子物質（単一あるいは共重合体）等の親水
性コロイドと併用したものであってもよい。The gelatin in this layer may be gelatin alone, or may include gelatin derivatives, graphite polymers with gelatin as the backbone, proteins, sugar derivatives, cellulose derivatives, synthetic hydrophilic polymer substances (single or copolymers), etc. It may also be used in combination with a hydrophilic colloid.
ゼラチンを単独で使用したときでも、また、上記化合物
と併用したときでもゼラチンとしての付量がｌ８■／ｄ
ｍ２以下であることが必要である。Even when gelatin is used alone or in combination with the above compounds, the amount of gelatin applied is 18■/d.
It is necessary that it is less than m2.
ゼラチン付量は１〜１８ｍｇ／ｄｍ２が好ましく、より
好ましくは５〜１５ｍｇ／ｄｍ２である。The amount of gelatin applied is preferably 1 to 18 mg/dm2, more preferably 5 to 15 mg/dm2.
ゼラチン付量が１８ｍｇ／ｄｍ２を越えると、高速薄膜
塗布した場合、微細な塗布ハジキか発生する。If the amount of gelatin applied exceeds 18 mg/dm2, fine coating repellency will occur during high-speed thin film coating.
また、ｌｍｇ／ｄｍ２未満ではゼラチン膜のセット能力
が不十分となり好ましくない。Further, if it is less than lmg/dm2, the setting ability of the gelatin film will be insufficient, which is not preferable.
本発明において、高速塗布とは塗布スピードが１００ｍ
／ｍｉｎを越える塗布速度での塗布をいい、薄膜とは写
真構成層の膜厚の総量が１５０μ以下のものをいう。In the present invention, high-speed coating means a coating speed of 100 m.
The term "thin film" refers to a coating at a coating speed exceeding 1/min, and the term "thin film" refers to one in which the total thickness of the photographic constituent layers is 150 .mu.m or less.
支持体に最も近いハロゲン化銀乳剤層の塗布’ｔｒｌの
粘度には特に限定はないが、１５ｃｐ以下であることが
好ましく、ｌ−１０ｃｐの範囲にあることが４０
より好ましい。The coating viscosity of the silver halide emulsion layer closest to the support is not particularly limited, but it is preferably 15 cp or less, and more preferably 1-10 cp.
本発明のハロゲン化銀カラー写真感光材料に用いられる
色素画像形成カプラーは特に限定されるものではなく、
種々の色素画像形或カプラーを用いることができる。The dye image-forming coupler used in the silver halide color photographic light-sensitive material of the present invention is not particularly limited.
A variety of dye image types or couplers can be used.
イエロー色素画像形成カプラーとしては、アシルアセト
アミド型、ベンゾイルメタン型カプラーが、マゼンタ色
素画像形成カブラーとしては、５ピラゾロン系、ビラゾ
ロトリアゾール系、ビラゾロベンツイミダゾール系、イ
ンダゾロン系、シアノアセチル系カプラーがまたシアン
色素画像形成カプラーとしては、フェノール系、ナフト
ール系カプラーか代表的である。Yellow dye image-forming couplers include acylacetamide-type and benzoylmethane-type couplers, and magenta dye image-forming couplers include 5-pyrazolone, virazolotriazole, virazolobenzimidazole, indazolone, and cyanoacetyl couplers. Typical cyan dye image-forming couplers include phenol and naphthol couplers.
本発明のハロゲン化銀カラー写真感光材料に用いられる
ハロゲン化銀としては、臭化銀、沃臭化銀、沃塩化銀、
塩臭化銀、塩化銀等、通常の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 used in the silver halide color photographic light-sensitive material of the present invention includes silver bromide, silver iodobromide, silver iodochloride,
Any material used in ordinary silver halide emulsions, such as silver chlorobromide and silver chloride, 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４１
４ ２
法など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,
Chemical sensitization is performed by selenium sensitization method, reduction sensitization method, noble metal sensitization method, 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カラー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、
ゼラチンを斡とするグラフトポリマー、蛋白質、糖誘導
体、セルロース誘導体、合成親水性高分子物質（単一あ
るいは共重合体）等の親水性コロイドも用いることがで
きる。As the binder (or protective colloid) used in the silver halide color photographic light-sensitive material of the present invention, it is advantageous to use gelatin, but gelatin derivatives,
Hydrophilic colloids such as gelatin-based graft polymers, proteins, sugar derivatives, cellulose derivatives, and synthetic hydrophilic polymeric substances (single or copolymers) can also be used.
本発明のハロゲン化銀カラー写真感光材料には、硬膜剤
、画像安定化剤、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。In the silver halide color photographic light-sensitive material of the present invention, additives such as hardeners, image stabilizers, plasticizers, latex, surfactants, matting agents, lubricants, antistatic agents, etc. may be used as necessary. I can do it.
本発明のハロゲン化銀カラー写真感光材料は、当業界公
知の発色現像処理を行なうことにより画像を形成するこ
とができる。The silver halide color photographic light-sensitive material of the present invention can form an image by subjecting it to a color development treatment known in the art.
［実施例コ
以下に具体的な実施例を示して本発明を更に詳細に説明
するが本発明はこれらに限定されるものではない。[Example] The present invention will be explained in more detail by referring to specific examples below, but the present invention is not limited thereto.
実施例１
ポリエチレン被覆紙上に、表−１に示した第１層乃至第
７層を、表−２に示した塗布スピードで、総膜厚（塗布
液の湿順状態でのを表わす。以下同じ。）が表−２に示
した膜厚になるように形成し試料ｔ〜９ （比較試料）
を作威した。上記第１層乃至第７層の塗布液は、各層の
層構成が表−１に示した層構成になるように調製した。Example 1 The first to seventh layers shown in Table 1 were coated on polyethylene coated paper at the coating speed shown in Table 2, and the total film thickness (represents the wet state of the coating liquid. The same applies hereinafter) ) was formed to have the film thickness shown in Table 2, and samples t~9 (comparative sample)
was created. The coating liquids for the first to seventh layers were prepared so that each layer had the layer structure shown in Table 1.
なお、表−１の（ ）内の数値は、総膜厚１８０μの時
の塗布量を表わす。総膜厚が１４０μ、ＩＯＯμの時は
第７層を除き、成分割合を変えずに相対的に薄膜化を行
なった。The numbers in parentheses in Table 1 represent the coating amount when the total film thickness is 180μ. When the total film thickness was 140μ and IOOμ, the film was relatively thinned without changing the component ratio except for the seventh layer.
また、各層の層構戊が、表−１に示した第１層のゼラチ
ン量２．０ｇ ／ボを１．５ｇ／ｒ＋ｆ （上記と同様
に総膜厚１８０μの時の塗布量を表わす。）に変更し、
第２層のステイン防止剤ＡＳ−１をＩ−８に、高沸点溶
媒ジブチルフタレー｝ （ＤＢＰ）をＨ−３に変更し、
第４層及び第６層の紫外線吸収′−４３
剤７Ｓを１５Ｌに変更した層構成になるように各層の塗
布液を調製し、ポリエチレン被覆紙上に、第１層乃至第
７層を、表−２に示した塗布スピードで、総膜厚が表−
２に示した膜厚になるように形成し試料１０−１２（本
発明試料）を作成した。In addition, the layer structure of each layer is 1.5 g/r+f (the amount of gelatin applied in the first layer is 2.0 g/bo as shown in Table 1) (Similar to the above, this represents the coating amount when the total film thickness is 180 μm). Change it to
The stain inhibitor AS-1 in the second layer was changed to I-8, and the high boiling point solvent dibutyl phthalate (DBP) was changed to H-3.
Coating liquids for each layer were prepared so that the layer structure was obtained by changing the ultraviolet absorbing agent 7S to 15L in the fourth and sixth layers, and the first to seventh layers were coated on polyethylene-coated paper. At the coating speed shown in 2, the total film thickness is
Sample 10-12 (sample of the present invention) was prepared by forming the film to have the film thickness shown in 2.
以下余白 ４ ４ 表 １ （１） 表 １− （２） ４ ７ マゼンタカプラー Ｍ １ ＣＩ しＩ シアンカプラー Ｃ １ し１ 硬膜剤 Ｈ−１ Ｃ（ＣＨ２ＳＯ２ＣＨ：ＣＨｘ）４ ○Ｎａ 増粘剤 Ｖ−］ ＣＯＯＮｇ 用いた化合物を以下に示す。Margin below 4 4 table 1 (1) table 1- (2) 4 7 magenta coupler M 1 C.I. I cyan coupler C 1 1 Hardener H-1 C(CH2SO2CH:CHx)4 ○Na thickener V-] COONg The compounds used are shown below.
ステイン防止剤 ＡＳ−１ ０Ｈ ｏＨ 混色防止剤 ＤＳ−１ イエロ カプラ Ｙ−１ ＣＩ ４ ８ 表−２ 塗布スピー ド；スライ ドホッパー峡による ｔ分間 の走行スピ ドを表わす。anti-stain agent AS-1 0H oH Color mixing prevention agent DS-1 yellow coupler Y-1 C.I. 4 8 Table-2 Application speed Do; Sly By Dohopper Gorge t minutes driving speed Represents C.
総膜厚； 塗布膜の混状態での厚さを表わす。Total film thickness; It represents the thickness of the coating film in a mixed state.
以下余白
得られた試料ｔ〜｛２について、感光計（コニカ株式会
社製 ＯＳ−１型）により干渉フィルタを用いて青色光
（ ４７０ｎｍ） 、緑色光（５５０ｎｍ）にて露光し
、下記の処理をした。The sample t~{2 obtained in the following margin was exposed to blue light (470 nm) and green light (550 nm) using an interference filter using a sensitometer (Konica Corporation OS-1 model), and the following processing was performed. did.
く処理工程〉
発色現像 ３８℃ ３分３０秒漂白定着
３３℃ ｌ分３０秒水 洗
２５〜３０℃ ３分乾 燥
７５〜８０℃ 約 ２分〈処理液組成〉
（発色現像液）
ベンジルアルコール １５ｍｌエチ
レングリコール １５ｍｌ亜硫酸カリ
ウム ２．０ｇ臭化カリウム
０．７ｇ塩化ナトリウム
０．２ｇ炭酸カリウム
３０．０ｇヒドロキシルアミン硫酸塩
３．０ｇポリリン酸（ ＴＰＰＳ ）
２．５ｇ３−メチル−４−アミノーＮ−
エチルーＮ一（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
スチルベンジスルホン酸誘導体） １．０ｇ水酸
化カリウム ２．０ｇ水を加えて全
量をＬρとし、ｐＨ １０．２０に調整する。Processing process> Color development 38℃ 3 minutes 30 seconds Bleach fixing 33℃ 1 minute 30 seconds Washing with water
Dry for 3 minutes at 25-30℃
75-80℃ for about 2 minutes <Processing solution composition> (Color developer) Benzyl alcohol 15ml Ethylene glycol 15ml Potassium sulfite 2.0g Potassium bromide
0.7g sodium chloride
0.2g potassium carbonate
30.0g hydroxylamine sulfate
3.0g polyphosphoric acid (TPPS)
2.5g 3-methyl-4-amino-N-ethyl-N-(β-methanesulfonamidoethyl)aniline sulfate 5.5g optical brightener (4.4'-diaminostilbendisulfonic acid derivative) 1.0g potassium hydroxide Add 2.0 g of water to bring the total amount to Lρ, and adjust the pH to 10.20.
（漂白定着液）
エチレンジアミンテトラ酢酸第２鉄
アンモニウム２水塩 ６０ｇエチレン
ジアミンテトラ酢酸 ３ｇチオ硫酸アンモニウ
ム（７０％溶液） １００ｍｌ亜硫酸アンモニウム
（４０％溶液） ２７．５ｍｌ炭酸カリウムまたは
氷酢酸でｐＨ７．．１に調整し、水を加えて全量をｌｇ
とする。(Bleach-fix solution) Ferric ammonium ethylenediaminetetraacetate dihydrate 60g ethylenediaminetetraacetic acid 3g ammonium thiosulfate (70% solution) 100ml ammonium sulfite (40% solution) 27.5ml Potassium carbonate or glacial acetic acid to pH 7. ．． 1 and add water to bring the total amount to lg.
shall be.
得られた黄色発色試料について、青濃度（Ｄ ａ）２．
０の点での緑濃度（Ｄ６）の大きさを比較することによ
り第１層から第３層への混色の程度がわかる。また、マ
ゼンタ発色試料について、緑濃度（ＤＧ）２．０の点で
の青濃度（Ｄ Ｂ）の大きさを５１
比較することにより第３層から第１層への混色の程度が
わかる。Regarding the obtained yellow colored sample, the blue density (D a) 2.
By comparing the magnitude of the green density (D6) at point 0, the degree of color mixing from the first layer to the third layer can be determined. Furthermore, by comparing the magnitude of the blue density (D B) at the green density (DG) of 2.0 for the magenta colored sample, the degree of color mixing from the third layer to the first layer can be determined.
各濃度はコニカ株式会社製 ＰＤＡ−６５型濃度測定器
により測定した。Each concentration was measured using a PDA-65 type concentration meter manufactured by Konica Corporation.
以下余白
５ ２
表−３
５ ４
表−３から本発明の試料１０〜１２は比較の試料Ｌ〜９
より混色が少ないことがわかる。Below margin 5 2 Table-3 5 4 From Table-3, samples 10 to 12 of the present invention are comparative samples L to 9.
It can be seen that there is less color mixing.
また、黄色発色試料、マゼンタ発色試料共、膜厚の薄い
ほど混色が大きい。Furthermore, for both the yellow and magenta colored samples, the thinner the film, the greater the color mixture.
次に、各試料を巾Ｌｍ，長さ３ ０ ｃｍに切断し、オ
メガ社製 クロメガＤ − ５５００引き伸し機により
、それぞれ青色光、緑色光、白色光により露光し、前記
処理条件にて処理をし、膜面状態を観察し、試料（巾ｌ
ｍ，長さ３０ｃｍ）中に発生した微細塗布ハジキ数を数
えた。Next, each sample was cut into pieces Lm wide and 30 cm long, exposed to blue light, green light, and white light using an Omega Cromega D-5500 enlarger, and processed under the processing conditions described above. , observe the film surface condition, and measure the sample (width l).
The number of finely coated repellents that occurred within a length of 30 cm was counted.
結果を表−４に示す。The results are shown in Table 4.
以下余白
表−４
△；３０点以内 ×；３０点以上表−４から明
らかなように、一般に、塗布速度が高速となるほど、ま
た、薄膜となるほど塗布／’％ジキの発生数が増加する
が、本発明のノ＼ロゲン化銀カラー写真感光材料では高
速薄膜塗布した場合でも塗布ハジキは発生しない。Margin Table-4 below: △; 30 points or less ×; 30 points or more In the silver halide color photographic light-sensitive material of the present invention, coating repellency does not occur even when high-speed thin film coating is performed.
次に、第２層塗布７夜、第４層塗布液及び第６層塗布液
の安定性を検討する目的で次の試験を行な５ ５
つた〇
各塗布液（乳化分散物）は下記の手順で調製した。Next, after 7 nights of coating the second layer, the following tests were conducted to examine the stability of the fourth and sixth layer coating solutions. Prepared according to the procedure.
第２層塗布液
（ａ）ステイン防止剤、高沸点溶媒及び高沸点溶媒の倍
の量の酢酸エチルを混合し、約６０℃に加熱して溶解す
る。（ステイン防止剤及び高沸点溶媒は第２層塗布岐に
なるような量で使用する。）（ｂ）写真用ゼラチンＬ５
ｇ，純水２ ０ ０ ｍｌを室温で混合し、２０分間膨
脹させる。次に約６０℃に加熱し溶解させた後、アルカ
ノールＢ（デュポン社製）の５％水溶液を２０ｍｌ添加
し均一に攪拌する。Second layer coating solution (a) A stain inhibitor, a high boiling point solvent, and ethyl acetate twice the amount of the high boiling point solvent are mixed and heated to about 60° C. to dissolve. (The stain inhibitor and high boiling point solvent are used in amounts that are suitable for coating the second layer.) (b) Photographic gelatin L5
g. Mix 200 ml of pure water at room temperature and inflate for 20 minutes. Next, after heating to about 60° C. to dissolve, 20 ml of a 5% aqueous solution of Alkanol B (manufactured by DuPont) is added and stirred uniformly.
（Ｃ）上記（ａ）及び（ｂ）にて得られた各溶液を混合
し、超音波分散機にて２０分間分散し、分散ｌ夜を得た
。これを純水にて３００ｍｌに仕上げた。(C) The solutions obtained in (a) and (b) above were mixed and dispersed for 20 minutes using an ultrasonic disperser to obtain a dispersed mixture. This was made up to 300 ml with pure water.
第４層塗布岐及び第６層塗布液
紫外線吸収剤、ステイン防止剤及び高沸点溶媒を第４層
塗布液及び第６層塗布液になるような量で使用した以外
は第２塗布岐と同様にして調製した。4th layer coating solution and 6th layer coating solution Same as the 2nd coating solution except that the ultraviolet absorber, anti-staining agent and high boiling point solvent were used in the amounts necessary to form the 4th layer coating solution and the 6th layer coating solution. It was prepared as follows.
５６
得られた各塗布液を容器に入れ栓をし、４０℃でｉ時間
及び２４時間保存し、保存によって生じた濁度の上昇（
ΔＴ）を測定した。56 Place each of the obtained coating solutions in a container, stopper it, and store it at 40°C for i hours and 24 hours to check the increase in turbidity (
ΔT) was measured.
濁度はポイック積分球式濁度計（日本精密光学株式会社
製 型式ＳＥＰ−ＰＴ−５０ＬＤ）を用イて測定した。The turbidity was measured using a Poick integrating sphere turbidity meter (model SEP-PT-50LD, manufactured by Nippon Seimitsu Kogaku Co., Ltd.).
濁度は分散粒子の粒径と相関がある。同一条件下ではこ
の値が小さいほど粒径が小さい。ΔＴが小さいというこ
とは、保存によって分散粒子の粗大化が起きていない、
即ち塗布液が安定であることを示している。Turbidity is correlated with the particle size of dispersed particles. Under the same conditions, the smaller this value is, the smaller the particle size is. A small ΔT means that the dispersed particles have not become coarser due to storage.
That is, it shows that the coating liquid is stable.
結果を表−５に示す。The results are shown in Table-5.
また、上記条件で１時間及び２４時間保存した後に生ず
る析出物の量を測定した。In addition, the amount of precipitate formed after storage under the above conditions for 1 hour and 24 hours was measured.
析出量は、塗布液をガラスフィルターで濾過し、これを
酢酸エチルで迅速に洗浄し、乾燥した後に得られた析出
物の量を測定することによって求めた。The amount of precipitate was determined by filtering the coating solution through a glass filter, quickly washing it with ethyl acetate, and measuring the amount of precipitate obtained after drying.
結果を表−５に示す。The results are shown in Table-5.
５ ７ ５ ８ 表−５ Ｉｌｌ，試料１〜９用の塗布液のものを示す。5 7 5 8 Table-5 Ill, coating liquids for samples 1 to 9 are shown.
本２；試料１０〜１２用の塗布液のものを示す。Book 2: Coating solutions for samples 10 to 12 are shown.
表−５から、比較の試料１〜９の作成に用いた塗布液は
、第２層、第４層、第６層とも、２４時間保存後、濁度
が上昇し、また、析出量が増加するのに対し、本発明の
試料１０〜１２の作成に用いた塗布液は、濁度の上昇が
少なく、また、析出量の増加も僅かであり、安定である
ことがわかる。From Table 5, the turbidity of the coating liquids used to create comparative samples 1 to 9 increased after 24 hours of storage for the 2nd, 4th, and 6th layers, and the amount of precipitation increased. On the other hand, the coating liquids used to prepare Samples 10 to 12 of the present invention show little increase in turbidity and only a slight increase in the amount of precipitate, indicating that they are stable.
実施例２
表−６に示すように第１層のゼラチン付量、第２層のス
ティン防止剤、高沸点溶媒、第４層の紫外線吸収剤、第
６層の紫外線吸収剤を変えた以外は実施例１と同様の層
構成を有する試料を作成した。但し、塗布速度は１５０
ｍ ／ ｍｉｎ 、塗布時の総膜厚は１００μである
。Example 2 As shown in Table 6, except that the amount of gelatin applied in the first layer, stain inhibitor, high boiling point solvent in the second layer, ultraviolet absorber in the fourth layer, and ultraviolet absorber in the sixth layer were changed. A sample having the same layer structure as in Example 1 was prepared. However, the coating speed is 150
m/min, and the total film thickness at coating is 100μ.
なお、第１層塗布液の粘度を、増粘剤を用いて第１層の
ゼラチン付量が２５■／ｄｍ２のときには１５Ｃ ｐ％
１８ｍｇ／ ｄｍ２のときにはｌＯｃ ｐ ， １０
ｍｇ／ｄｍ２のときには７ｃｐとなるように調整した。In addition, the viscosity of the first layer coating liquid is 15C p% when the amount of gelatin applied in the first layer is 25 μ/dm2 using a thickener.
When 18 mg/dm2, lOc p , 10
It was adjusted to 7 cp when mg/dm2.
また、増粘剤を用いて第２層から上の層の塗布液の粘度
を２５ｃｐに調整した。Further, the viscosity of the coating liquid for the second and upper layers was adjusted to 25 cp using a thickener.
実施例１と同様にして、混色の程度及び塗布ハジキ数を
測定した。結果を表−７に示す。In the same manner as in Example 1, the degree of color mixing and the number of coating repellents were measured. The results are shown in Table-7.
以下余白
５つ
６０
表−６
表−７の結果から、本発明に係る試料はイエロー発色に
対するマセンタ混色が少なく、また、マゼンタ発色に対
するイエロー混色も少ない、即ち、色純度が高い感光材
料であることがわかる。また、塗布膜面状態も大幅に改
良されていることかわかる。5 blank spaces below 60 Table 6 From the results in Table 7, the sample according to the present invention has less magenta color mixing with yellow coloring, and less yellow color mixing with magenta coloring, that is, it is a photosensitive material with high color purity. I understand. It can also be seen that the surface condition of the coated film has been significantly improved.
次に、実施例１に記載の方法により、第２層、第４層及
び第６層の塗布液の安定性を試験した。Next, by the method described in Example 1, the stability of the coating liquids for the second, fourth, and sixth layers was tested.
結果を表−８に示す。The results are shown in Table-8.
以下余白
表
８
ＤＢＰ．ジブチルフタレート
ＤＮＰ ，ジノニルフタレート
表−８の結果から、本発明の塗布液の安定性は大巾に改
良されていることがわかる。Below is the margin table 8 DBP. Dibutyl phthalate DNP, dinonyl phthalate From the results in Table 8, it can be seen that the stability of the coating liquid of the present invention is greatly improved.
実施例３
表−９に示すように第１層の塩臭化銀乳剤及び６ ３
イエローカプラー、第３層の塩臭化銀乳剤及びマゼンタ
カプラー、第５層の塩臭化銀乳剤及びシアンカプラーを
変え、また、表−１０に示すように第１層のゼラチン付
量、第２層のステイン防止剤、高沸点溶媒、第４層の紫
外線吸収剤、第６層の紫外線吸収剤を変えた以外は実施
例１と同様の層構成を有する試料を作戊した。Example 3 As shown in Table 9, the silver chlorobromide emulsion and 6 3 yellow coupler in the first layer, the silver chlorobromide emulsion and magenta coupler in the third layer, and the silver chlorobromide emulsion and cyan coupler in the fifth layer. In addition, as shown in Table 10, the amount of gelatin applied in the first layer, the stain inhibitor, high boiling point solvent in the second layer, the ultraviolet absorber in the fourth layer, and the ultraviolet absorber in the sixth layer were changed. A sample having the same layer structure as Example 1 except for this was prepared.
処理工程及び処理液組戊を下記の通り変更した以外は実
施例１と同様にして、混色の程度及び塗布ハジキ数を測
定した。結果を表−１１に示す。The degree of color mixing and the number of coating repellents were measured in the same manner as in Example 1, except that the treatment process and treatment liquid composition were changed as described below. The results are shown in Table-11.
以下余白 表 ６ ４ ９ ６ ５ ６ ６ １ ０ マゼンタカプラ− Ｍ−２ 以下余白 イエローカプラー ２ ＣＪ シアンカプラー Ｃ−２ 下記シアンカプラー２種を重量にて１：１で用いた。Margin below table 6 4 9 6 5 6 6 1 0 magenta coupler M-2 Margin below yellow coupler 2 C.J. Cyan coupler C-2 The following two cyan couplers were used in a 1:1 ratio by weight.
６ ８
く処理工程〉
発色現像 ３４．７±０．３℃ ５０秒漂白定
着 ３４．７±０．５℃ ５０秒安定化 ３
０〜３４℃ ９０秒
乾 燥 ６０〜８０℃ ６０
秒く処理液組成〉
（発色現像液）
純水 ８ ０ ０ ｍｌ
エチレングリコール １０ｍｌＮ，Ｎ
−ジエチルヒドロキシルアミン ｌｏｇ塩化カリウム
２ｇＮ一エチルー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 ５ｇ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
スチルベンジスルホン酸誘導体）ｌｇ
水を加えて全量をｔＵとし、ｐＨ １０．０８に調整す
る。6 8 Processing process> Color development 34.7±0.3℃ 50 seconds Bleach fixing 34.7±0.5℃ 50 seconds stabilization 3
Dry for 90 seconds at 0-34℃ 60-80℃ 60
Second processing solution composition> (Color developer) Pure water 800 ml
Ethylene glycol 10mlN,N
-diethylhydroxylamine log potassium chloride
2g N-monoethyl-N-β-methanesulfonamidoethyl-3-methyl-4 aminoaniline sulfate 5g sodium tetrapolyphosphate 2g potassium carbonate
30g optical brightener (4.4'-diaminostilbendisulfonic acid derivative) 1g water is added to bring the total amount to tU, and the pH is adjusted to 10.08.
（漂白定着液）
エチレンジアミンテトラ酢酸第２鉄
アンモニウム２水塩 ６０ｇエチレン
ジアミンテ１・ラ酢酸 ３ｇチオ硫酸アンモニ
ウム（７０％溶液） １０ ０ ｍｌ亜硫酸アンモ
ニウム（４０％溶？＆） ２７．５ｍｌ水を加えて
全量を１１とし、゛炭酸カリウムまたは氷酢酸でｐＨ７
．１に調整する。(Bleach-fix solution) Ethylenediaminetetraacetic acid ferric ammonium dihydrate 60g Ethylenediaminetetraacetic acid 3g Ammonium thiosulfate (70% solution) 100ml Ammonium sulfite (40% solution?&) Add 27.5ml water to make the total volume 11 and pH 7 with potassium carbonate or glacial acetic acid.
．． Adjust to 1.
（安定化液）
５−クロロ−２−メチル−４
イソチアゾリン−３−オン １ｇ１−ヒドロ
キシエチリデン
１，１−ジホスホン酸 ２ｇ水を加えて
全量を１ｇとし、硫酸または水酸化カリウムででｐＨ７
．０に調整する。(Stabilizing liquid) 5-chloro-2-methyl-4 isothiazolin-3-one 1g 1-hydroxyethylidene 1,1-diphosphonic acid 2g Add water to bring the total amount to 1g, and adjust to pH 7 with sulfuric acid or potassium hydroxide.
．． Adjust to 0.
以下余白
７１
表−１１の結果から、本発明によれば、ハロゲン化銀乳
剤、カブラー及び処理工程か変っても同様に混色防止効
果が得られ、また、塗布ハジキの発生が著しく改良され
ることがわかる。Margin 71 below From the results in Table 11, it can be seen that according to the present invention, the same color mixing prevention effect can be obtained even if the silver halide emulsion, the fogger, and the processing process are changed, and the occurrence of coating repellency is significantly improved. I understand.
［発明の効果］
本発明のハロゲン化銀カラー写真感光材料は、混色を起
こすことが少なく、また、充分な塗布安定性をもって、
高速で薄膜塗布を行なうことができる。また、本発明の
ハロゲン化銀カラー写真感光材料を得るための塗布液は
、安定性が優れている。[Effects of the Invention] The silver halide color photographic light-sensitive material of the present invention hardly causes color mixing, has sufficient coating stability,
Thin film coating can be performed at high speed. Furthermore, the coating solution for obtaining the silver halide color photographic light-sensitive material of the present invention has excellent stability.
Claims (1)
び少なくとも１層の非感光性層から構成される写真構成
層を有するハロゲン化銀カラー写真感光材料において、
前記写真構成層の少なくとも１層に常温にて液体状の紫
外線吸収剤を含有させ、かつ、少なくとも１層に２位に
第２級アルキル基を有するハイドロキノン系化合物を含
有させると共に、支持体に最も近いハロゲン化銀乳剤層
のゼラチンを１８ｍｇ／ｄｍ＾２以下としたことを特徴
とするハロゲン化銀カラー写真感光材料。A silver halide color photographic light-sensitive material having, on a support, a photographic constituent layer consisting of at least one silver halide emulsion layer and at least one non-photosensitive layer,
At least one of the photographic constituent layers contains an ultraviolet absorber that is liquid at room temperature, and at least one layer contains a hydroquinone compound having a secondary alkyl group at the 2-position. A silver halide color photographic material characterized in that gelatin in a nearby silver halide emulsion layer is 18 mg/dm^2 or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23327389A JPH0395545A (en) | 1989-09-08 | 1989-09-08 | Silver halide color photographic sensitive material having color mixing preventive effect and excellent coating stability |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23327389A JPH0395545A (en) | 1989-09-08 | 1989-09-08 | Silver halide color photographic sensitive material having color mixing preventive effect and excellent coating stability |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0395545A true JPH0395545A (en) | 1991-04-19 |
Family
ID=16952504
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP23327389A Pending JPH0395545A (en) | 1989-09-08 | 1989-09-08 | Silver halide color photographic sensitive material having color mixing preventive effect and excellent coating stability |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0395545A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8325777B2 (en) | 2006-02-03 | 2012-12-04 | Ricoh Company, Ltd. | Surface-emitting laser device and surface-emitting laser array including same |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5429637A (en) * | 1977-08-09 | 1979-03-05 | Fuji Photo Film Co Ltd | Color photographic material |
| JPS62250433A (en) * | 1986-04-23 | 1987-10-31 | Konika Corp | Silver halide color photographic sensitive material |
| JPS62291646A (en) * | 1986-06-11 | 1987-12-18 | Konica Corp | Silver halide photographic sensitive material suitable for rapidly processing and capable of forming coloring matter image having excellent light fastness |
-
1989
- 1989-09-08 JP JP23327389A patent/JPH0395545A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5429637A (en) * | 1977-08-09 | 1979-03-05 | Fuji Photo Film Co Ltd | Color photographic material |
| JPS62250433A (en) * | 1986-04-23 | 1987-10-31 | Konika Corp | Silver halide color photographic sensitive material |
| JPS62291646A (en) * | 1986-06-11 | 1987-12-18 | Konica Corp | Silver halide photographic sensitive material suitable for rapidly processing and capable of forming coloring matter image having excellent light fastness |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8325777B2 (en) | 2006-02-03 | 2012-12-04 | Ricoh Company, Ltd. | Surface-emitting laser device and surface-emitting laser array including same |
| US8699540B2 (en) | 2006-02-03 | 2014-04-15 | Ricoh Company, Ltd. | Surface-emitting laser device and surface-emitting laser array including same |
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