JPH0566515A - Silver halide photographic sensitive material - Google Patents
Silver halide photographic sensitive materialInfo
- Publication number
- JPH0566515A JPH0566515A JP22602291A JP22602291A JPH0566515A JP H0566515 A JPH0566515 A JP H0566515A JP 22602291 A JP22602291 A JP 22602291A JP 22602291 A JP22602291 A JP 22602291A JP H0566515 A JPH0566515 A JP H0566515A
- Authority
- JP
- Japan
- Prior art keywords
- group
- silver halide
- atom
- alkyl group
- heterocycle
- 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.)
- Granted
Links
- -1 Silver halide Chemical class 0.000 title claims abstract description 85
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 68
- 239000004332 silver Substances 0.000 title claims abstract description 68
- 239000000463 material Substances 0.000 title claims description 39
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 43
- 239000000839 emulsion Substances 0.000 claims abstract description 40
- 125000000623 heterocyclic group Chemical group 0.000 claims abstract description 25
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 23
- 125000003118 aryl group Chemical group 0.000 claims abstract description 21
- 230000001235 sensitizing effect Effects 0.000 claims abstract description 19
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 14
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 12
- 239000002253 acid Substances 0.000 claims abstract description 10
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 9
- 150000001450 anions Chemical class 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims description 45
- 150000002678 macrocyclic compounds Chemical class 0.000 claims description 12
- 125000000304 alkynyl group Chemical group 0.000 claims description 11
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 9
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical group [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 7
- 229910052711 selenium Inorganic materials 0.000 claims description 7
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 6
- 125000004434 sulfur atom Chemical group 0.000 claims description 6
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 3
- 239000000975 dye Substances 0.000 abstract description 27
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 3
- 125000004122 cyclic group Chemical group 0.000 abstract description 3
- 239000011593 sulfur Substances 0.000 abstract description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract 1
- 229910052760 oxygen Inorganic materials 0.000 abstract 1
- 239000001301 oxygen Chemical group 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 description 31
- 239000000243 solution Substances 0.000 description 28
- 125000001424 substituent group Chemical group 0.000 description 27
- 239000010410 layer Substances 0.000 description 21
- 238000000034 method Methods 0.000 description 21
- 238000012545 processing Methods 0.000 description 19
- 239000002245 particle Substances 0.000 description 15
- 239000003381 stabilizer Substances 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 108010010803 Gelatin Proteins 0.000 description 11
- 229920000159 gelatin Polymers 0.000 description 11
- 239000008273 gelatin Substances 0.000 description 11
- 235000019322 gelatine Nutrition 0.000 description 11
- 235000011852 gelatine desserts Nutrition 0.000 description 11
- 230000035945 sensitivity Effects 0.000 description 11
- 125000003545 alkoxy group Chemical group 0.000 description 10
- 125000005843 halogen group Chemical group 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 238000011161 development Methods 0.000 description 9
- SJOOOZPMQAWAOP-UHFFFAOYSA-N [Ag].BrCl Chemical compound [Ag].BrCl SJOOOZPMQAWAOP-UHFFFAOYSA-N 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 8
- 229910021607 Silver chloride Inorganic materials 0.000 description 7
- 238000009835 boiling Methods 0.000 description 7
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 239000003960 organic solvent Substances 0.000 description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 7
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 7
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 7
- 230000003595 spectral effect Effects 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 6
- 239000004094 surface-active agent Substances 0.000 description 6
- 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 5
- 206010070834 Sensitisation Diseases 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- 230000008313 sensitization Effects 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- 102100033183 Epithelial membrane protein 1 Human genes 0.000 description 4
- 101000832225 Homo sapiens Stabilin-1 Proteins 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 102100024471 Stabilin-1 Human genes 0.000 description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 4
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 4
- 239000000084 colloidal system Substances 0.000 description 4
- 125000000753 cycloalkyl group Chemical group 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 108010008594 epithelial membrane protein-1 Proteins 0.000 description 4
- 150000002430 hydrocarbons Chemical group 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- AIGNCQCMONAWOL-UHFFFAOYSA-N 1,3-benzoselenazole Chemical compound C1=CC=C2[se]C=NC2=C1 AIGNCQCMONAWOL-UHFFFAOYSA-N 0.000 description 3
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical compound C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 description 3
- ZJOJXRSMJNWWRN-UHFFFAOYSA-N 3-amino-6-[2-(4-aminophenyl)ethenyl]benzene-1,2-disulfonic acid Chemical class C1=CC(N)=CC=C1C=CC1=CC=C(N)C(S(O)(=O)=O)=C1S(O)(=O)=O ZJOJXRSMJNWWRN-UHFFFAOYSA-N 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 125000004104 aryloxy group Chemical group 0.000 description 3
- AMTXUWGBSGZXCJ-UHFFFAOYSA-N benzo[e][1,3]benzoselenazole Chemical compound C1=CC=C2C(N=C[se]3)=C3C=CC2=C1 AMTXUWGBSGZXCJ-UHFFFAOYSA-N 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine group Chemical group N1=CCC2=CC=CC=C12 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000005070 ripening Effects 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 3
- 235000019345 sodium thiosulphate Nutrition 0.000 description 3
- 239000012463 white pigment Substances 0.000 description 3
- 125000006569 (C5-C6) heterocyclic group Chemical group 0.000 description 2
- ODIRBFFBCSTPTO-UHFFFAOYSA-N 1,3-selenazole Chemical compound C1=C[se]C=N1 ODIRBFFBCSTPTO-UHFFFAOYSA-N 0.000 description 2
- PYWQACMPJZLKOQ-UHFFFAOYSA-N 1,3-tellurazole Chemical compound [Te]1C=CN=C1 PYWQACMPJZLKOQ-UHFFFAOYSA-N 0.000 description 2
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 description 2
- 102100033176 Epithelial membrane protein 2 Human genes 0.000 description 2
- 108050009423 Epithelial membrane protein 2 Proteins 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- 125000004442 acylamino group Chemical group 0.000 description 2
- 125000004423 acyloxy group Chemical group 0.000 description 2
- 125000004414 alkyl thio group Chemical group 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- XYXNTHIYBIDHGM-UHFFFAOYSA-N ammonium thiosulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-UHFFFAOYSA-N 0.000 description 2
- 125000005110 aryl thio group Chemical group 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- KXNQKOAQSGJCQU-UHFFFAOYSA-N benzo[e][1,3]benzothiazole Chemical compound C1=CC=C2C(N=CS3)=C3C=CC2=C1 KXNQKOAQSGJCQU-UHFFFAOYSA-N 0.000 description 2
- WMUIZUWOEIQJEH-UHFFFAOYSA-N benzo[e][1,3]benzoxazole Chemical compound C1=CC=C2C(N=CO3)=C3C=CC2=C1 WMUIZUWOEIQJEH-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 2
- 238000004061 bleaching Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 150000003983 crown ethers Chemical class 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 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
- 238000009826 distribution Methods 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 238000007648 laser printing Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 239000004848 polyfunctional curative Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 description 2
- 235000019252 potassium sulphite Nutrition 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- DOGHJORLHLESLL-UHFFFAOYSA-N (4-methyl-2,3-diphenylphenyl) dihydrogen phosphate Chemical compound C=1C=CC=CC=1C=1C(C)=CC=C(OP(O)(O)=O)C=1C1=CC=CC=C1 DOGHJORLHLESLL-UHFFFAOYSA-N 0.000 description 1
- IRFSXVIRXMYULF-UHFFFAOYSA-N 1,2-dihydroquinoline Chemical compound C1=CC=C2C=CCNC2=C1 IRFSXVIRXMYULF-UHFFFAOYSA-N 0.000 description 1
- IPVORJLWOBDFGD-UHFFFAOYSA-N 1,3-selenazolidine Chemical compound C1C[Se]CN1 IPVORJLWOBDFGD-UHFFFAOYSA-N 0.000 description 1
- OGYGFUAIIOPWQD-UHFFFAOYSA-N 1,3-thiazolidine Chemical compound C1CSCN1 OGYGFUAIIOPWQD-UHFFFAOYSA-N 0.000 description 1
- YNGDWRXWKFWCJY-UHFFFAOYSA-N 1,4-Dihydropyridine Chemical compound C1C=CNC=C1 YNGDWRXWKFWCJY-UHFFFAOYSA-N 0.000 description 1
- ZRHUHDUEXWHZMA-UHFFFAOYSA-N 1,4-dihydropyrazol-5-one Chemical compound O=C1CC=NN1 ZRHUHDUEXWHZMA-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- USYCQABRSUEURP-UHFFFAOYSA-N 1h-benzo[f]benzimidazole Chemical compound C1=CC=C2C=C(NC=N3)C3=CC2=C1 USYCQABRSUEURP-UHFFFAOYSA-N 0.000 description 1
- JKTAIYGNOFSMCE-UHFFFAOYSA-N 2,3-di(nonyl)phenol Chemical compound CCCCCCCCCC1=CC=CC(O)=C1CCCCCCCCC JKTAIYGNOFSMCE-UHFFFAOYSA-N 0.000 description 1
- WOHLSTOWRAOMSG-UHFFFAOYSA-N 2,3-dihydro-1,3-benzothiazole Chemical compound C1=CC=C2SCNC2=C1 WOHLSTOWRAOMSG-UHFFFAOYSA-N 0.000 description 1
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-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
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- RSEBUVRVKCANEP-UHFFFAOYSA-N 2-pyrroline Chemical compound C1CC=CN1 RSEBUVRVKCANEP-UHFFFAOYSA-N 0.000 description 1
- XRZDIHADHZSFBB-UHFFFAOYSA-N 3-oxo-n,3-diphenylpropanamide Chemical class C=1C=CC=CC=1NC(=O)CC(=O)C1=CC=CC=C1 XRZDIHADHZSFBB-UHFFFAOYSA-N 0.000 description 1
- MVVFUAACPKXXKJ-UHFFFAOYSA-N 4,5-dihydro-1,3-selenazole Chemical compound C1CN=C[Se]1 MVVFUAACPKXXKJ-UHFFFAOYSA-N 0.000 description 1
- KJWMCPYEODZESQ-UHFFFAOYSA-N 4-Dodecylphenol Chemical compound CCCCCCCCCCCCC1=CC=C(O)C=C1 KJWMCPYEODZESQ-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
- OSCDSXOFFGCLQA-UHFFFAOYSA-N 4-n-ethyl-2-methylbenzene-1,4-diamine;sulfuric acid Chemical compound OS(O)(=O)=O.CCNC1=CC=C(N)C(C)=C1 OSCDSXOFFGCLQA-UHFFFAOYSA-N 0.000 description 1
- 229940100484 5-chloro-2-methyl-4-isothiazolin-3-one Drugs 0.000 description 1
- 125000004008 6 membered carbocyclic group Chemical group 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
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VOWAEIGWURALJQ-UHFFFAOYSA-N Dicyclohexyl phthalate Chemical compound C=1C=CC=C(C(=O)OC2CCCCC2)C=1C(=O)OC1CCCCC1 VOWAEIGWURALJQ-UHFFFAOYSA-N 0.000 description 1
- 229920001174 Diethylhydroxylamine Polymers 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- CWNSVVHTTQBGQB-UHFFFAOYSA-N N,N-Diethyldodecanamide Chemical compound CCCCCCCCCCCC(=O)N(CC)CC CWNSVVHTTQBGQB-UHFFFAOYSA-N 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910021612 Silver iodide Inorganic materials 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- GTVWRXDRKAHEAD-UHFFFAOYSA-N Tris(2-ethylhexyl) phosphate Chemical compound CCCCC(CC)COP(=O)(OCC(CC)CCCC)OCC(CC)CCCC GTVWRXDRKAHEAD-UHFFFAOYSA-N 0.000 description 1
- FJWGYAHXMCUOOM-QHOUIDNNSA-N [(2s,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6s)-4,5-dinitrooxy-2-(nitrooxymethyl)-6-[(2r,3r,4s,5r,6s)-4,5,6-trinitrooxy-2-(nitrooxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-3,5-dinitrooxy-6-(nitrooxymethyl)oxan-4-yl] nitrate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O)O[C@H]1[C@@H]([C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@@H](CO[N+]([O-])=O)O1)O[N+]([O-])=O)CO[N+](=O)[O-])[C@@H]1[C@@H](CO[N+]([O-])=O)O[C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O FJWGYAHXMCUOOM-QHOUIDNNSA-N 0.000 description 1
- JSMWLOHJXRPBRH-UHFFFAOYSA-N [4-(3-ethylheptanoyloxymethyl)cyclohexyl]methyl 3-ethylheptanoate Chemical compound CCCCC(CC)CC(=O)OCC1CCC(COC(=O)CC(CC)CCCC)CC1 JSMWLOHJXRPBRH-UHFFFAOYSA-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
- 238000005299 abrasion Methods 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 125000005194 alkoxycarbonyloxy group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000004397 aminosulfonyl group Chemical group NS(=O)(=O)* 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000000908 ammonium hydroxide Substances 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
- 229940121375 antifungal agent Drugs 0.000 description 1
- 239000003429 antifungal agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Substances [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 125000005200 aryloxy carbonyloxy group Chemical group 0.000 description 1
- FVCHPLIQTBSXKX-UHFFFAOYSA-N azanium;2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]acetate Chemical compound N.OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O FVCHPLIQTBSXKX-UHFFFAOYSA-N 0.000 description 1
- ZFSFDELZPURLKD-UHFFFAOYSA-N azanium;hydroxide;hydrate Chemical compound N.O.O ZFSFDELZPURLKD-UHFFFAOYSA-N 0.000 description 1
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 1
- 229910001864 baryta Inorganic materials 0.000 description 1
- MXMZCLLIUQEKSN-UHFFFAOYSA-N benzimidazoline Chemical compound C1=CC=C2NCNC2=C1 MXMZCLLIUQEKSN-UHFFFAOYSA-N 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 229920002301 cellulose acetate Polymers 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
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000000460 chlorine Substances 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
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 125000000392 cycloalkenyl group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011033 desalting Methods 0.000 description 1
- FVCOIAYSJZGECG-UHFFFAOYSA-N diethylhydroxylamine Chemical compound CCN(O)CC FVCOIAYSJZGECG-UHFFFAOYSA-N 0.000 description 1
- 150000004683 dihydrates Chemical class 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
- WIYAGHSNPUBKDT-UHFFFAOYSA-N dinonyl hexanedioate Chemical compound CCCCCCCCCOC(=O)CCCCC(=O)OCCCCCCCCC WIYAGHSNPUBKDT-UHFFFAOYSA-N 0.000 description 1
- KWKXNDCHNDYVRT-UHFFFAOYSA-N dodecylbenzene Chemical compound CCCCCCCCCCCCC1=CC=CC=C1 KWKXNDCHNDYVRT-UHFFFAOYSA-N 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000007765 extrusion coating Methods 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 239000006081 fluorescent whitening agent Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910000378 hydroxylammonium sulfate Inorganic materials 0.000 description 1
- 125000005462 imide group Chemical group 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
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 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
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- 239000011259 mixed solution Substances 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
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 150000002843 nonmetals Chemical group 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 125000005499 phosphonyl group Chemical group 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 150000003021 phthalic acid derivatives Chemical class 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- MCSKRVKAXABJLX-UHFFFAOYSA-N pyrazolo[3,4-d]triazole Chemical class N1=NN=C2N=NC=C21 MCSKRVKAXABJLX-UHFFFAOYSA-N 0.000 description 1
- ZVJHJDDKYZXRJI-UHFFFAOYSA-N pyrroline Natural products C1CC=NC1 ZVJHJDDKYZXRJI-UHFFFAOYSA-N 0.000 description 1
- GZTPJDLYPMPRDF-UHFFFAOYSA-N pyrrolo[3,2-c]pyrazole Chemical compound N1=NC2=CC=NC2=C1 GZTPJDLYPMPRDF-UHFFFAOYSA-N 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 229940065287 selenium compound Drugs 0.000 description 1
- 150000003343 selenium compounds Chemical class 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 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
- 239000012321 sodium triacetoxyborohydride Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 125000000475 sulfinyl group Chemical group [*:2]S([*:1])=O 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 150000003456 sulfonamides Chemical class 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 125000006296 sulfonyl amino group Chemical group [H]N(*)S(*)(=O)=O 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical group [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 150000003536 tetrazoles Chemical class 0.000 description 1
- CBDKQYKMCICBOF-UHFFFAOYSA-N thiazoline Chemical compound C1CN=CS1 CBDKQYKMCICBOF-UHFFFAOYSA-N 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- SFENPMLASUEABX-UHFFFAOYSA-N trihexyl phosphate Chemical compound CCCCCCOP(=O)(OCCCCCC)OCCCCCC SFENPMLASUEABX-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
- 229920006163 vinyl copolymer Polymers 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、ハロゲン化銀写真感光
材料に関するもので、詳しくは赤外感光性カラー写真要
素において、仕上がり画像に色濁りがなく、かつレーザ
ープリンターで連続して画像を出力しても、安定して高
画質のカラー画像を得られるハロゲン化銀写真感光材料
に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material, and more specifically, in an infrared-sensitive color photographic element, the finished image has no color turbidity and the images are continuously output by a laser printer. Even if it is concerned, it relates to a silver halide photographic light-sensitive material capable of stably obtaining a high quality color image.
【０００２】[0002]
【発明の背景】今日、エレクトロニクスの分野では、Ｃ
ＣＤ等の撮像素子及び磁気記録媒体の著しい進歩によ
り、これまでのハロゲン化銀を使った写真と同じ手軽さ
で写真撮影を行い、直ちにテレビに写しだしてこれを楽
しむことを可能としてきた。また、印刷・製版の分野で
はスキャナーおよび画像処理機器の進歩により原画をス
キャナーで読み取った後、カラーディスプレイを見なが
ら編集、修正などの作業や、コントラスト、拡大縮小な
どを自在に、手軽に行うことが出来るようになった。BACKGROUND OF THE INVENTION In the field of electronics today, C
Due to the remarkable progress of image pickup devices such as CDs and magnetic recording media, it has become possible to take a photograph with the same ease as a photograph using silver halide up to now and immediately display it on a television to enjoy it. In the field of printing and platemaking, after reading the original image with a scanner due to the progress of scanners and image processing equipment, it is possible to easily perform editing, correction, contrast, enlargement / reduction, etc. while watching the color display. Is now possible.
【０００３】しかし、テレビ画面に画像を映し出すとい
うだけではやはり不十分であり、紙の上に記録された画
像が求められており、感熱転写方式、インクジェット方
式、電子写真方式などの種々の方式が実用化されてい
る。こうした分野でもハロゲン化銀写真感光材料のもつ
豊かな階調性は他の方式に比べ群を抜いたものであって
優れた描写力を有しているが、従来のハロゲン化銀写真
感光材料では、青、緑、赤感光性のハロゲン化銀乳剤層
を有しているためこれに記録するのに適当な光源が得難
いという問題があった。However, it is still insufficient to display an image on a television screen, and an image recorded on paper is required, and various systems such as a thermal transfer system, an inkjet system and an electrophotographic system are required. It has been put to practical use. Even in such fields, the rich gradation of silver halide photographic light-sensitive materials is outstanding compared to other methods and has excellent descriptive power, but with conventional silver halide photographic light-sensitive materials Since it has blue, green, and red-sensitive silver halide emulsion layers, there is a problem that it is difficult to obtain a light source suitable for recording on the silver halide emulsion layers.
【０００４】前記の目的でハロゲン化銀写真感光材料を
露光するのには、従来ヘリウム・ネオン、アルゴンイオ
ン、ヘリウム・カドミウム等のガスレーザーが多く用い
られてきた。しかし、これらのレーザーは、大きい、高
価である、寿命が短いなどの欠点を有していた。これに
対して半導体レーザーを用いて非線形光学素子を用いる
方法が知られているが、その変換効率は十分なものとい
えず、またハロゲン化銀写真感光材料の側から見たとき
に適切な波長の光がないなどの問題もあり実用化される
には到っていなかった。For exposing the silver halide photographic light-sensitive material for the above-mentioned purpose, gas lasers of helium / neon, argon ion, helium / cadmium and the like have been widely used. However, these lasers have drawbacks such as large size, high cost, and short life. On the other hand, a method of using a non-linear optical element using a semiconductor laser is known, but its conversion efficiency cannot be said to be sufficient, and an appropriate wavelength when viewed from the side of a silver halide photographic light-sensitive material. It was not put into practical use due to problems such as lack of light.
【０００５】しかし、赤外線に感光するハロゲン化銀乳
剤を用い、半導体レーザーを用いることにより、安価で
小型の露光装置で画像を容易に得られるようになった。However, by using a silver halide emulsion sensitive to infrared rays and using a semiconductor laser, an image can be easily obtained with an inexpensive and small exposure device.
【０００６】しかしながら、赤外光に感光性を有するハ
ロゲン化銀写真感光材料は、赤外分光増感色素による吸
収波長が短波長側で裾が広がり、そのため得られる画像
が色濁りを起こし易い欠点があった。However, in a silver halide photographic light-sensitive material having sensitivity to infrared light, the absorption wavelength of the infrared spectral sensitizing dye has a widened skirt on the short wavelength side, so that the resulting image is liable to cause color turbidity. was there.
【０００７】さらに赤外光源として発光ダイオードや半
導体レーザーを用いて連続操作すると、画像濃度が変動
するという問題があり、その要因の一つとして、該光源
が温度によって発光波長や光強度が変化することが考え
られている。Further, when a light emitting diode or a semiconductor laser is continuously operated as an infrared light source, there is a problem that the image density fluctuates. Is considered.
【０００８】これらに対して例えば特開昭61-137149号
では感光材料の層間の乳剤感度差、コントラスト、層構
成あるいはフィルター層の分光特性などを規定したり、
特開平3-138642号、同3-120535号或は同3-138638号で
は、特定の赤外増感色素を用いて分光波長領域を深く狭
くし、画像分解することにより色濁りを改良することな
どを開示している。On the other hand, for example, in JP-A-61-137149, the emulsion sensitivity difference between layers of the light-sensitive material, the contrast, the layer structure or the spectral characteristics of the filter layer are specified,
In JP-A-3-138642, JP-A-3-120535 or JP-A-3-138638, the spectral wavelength region is deeply narrowed by using a specific infrared sensitizing dye to improve color turbidity by image decomposition. Etc. are disclosed.
【０００９】しかしながらこれら従来技術では、連続し
て画像を出力した場合に於ける色濁りの改良が充分でな
く高感度で、かつ安定して高画質を得られるレーザープ
リント用ハロゲン化銀写真感光材料が強く望まれてい
た。However, in these prior arts, the silver halide photographic light-sensitive material for laser printing, which does not sufficiently improve the color turbidity when images are continuously output, has high sensitivity, and can stably obtain high image quality. Was strongly desired.
【００１０】[0010]
【発明の目的】従って本発明の目的は、レーザープリン
ターを用い連続して画像を出力しても色濁りがなく、か
つ高感度で安定して高画質のカラー画像を得られるレー
ザープリント用ハロゲン化銀写真感光材料を提供するこ
とである。その他の目的は以下の明細から明らかとな
る。SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a halogenated product for laser printing which is capable of stably producing a high quality color image without causing color turbidity even when images are continuously output using a laser printer. To provide a silver photographic light-sensitive material. Other objects will be apparent from the following specification.
【００１１】[0011]
【発明の構成】本発明の目的は、以下により達成される
ことを見い出し本発明を成すに至った。即ち、 (1)支持体上に少なくとも１層の感光性ハロゲン化銀乳
剤層を有するハロゲン化銀写真感光材料において、該ハ
ロゲン化銀乳剤層の少なくとも１層中に下記一般式
〔１〕、〔２〕及び〔３〕から選ばれる増感色素の少な
くとも一つと、ヘテロ原子を含む大環状化合物の少なく
とも一つを組み合わせて含有するハロゲン化銀写真感光
材料。SUMMARY OF THE INVENTION The object of the present invention has been accomplished by the following finding. (1) In a silver halide photographic light-sensitive material having at least one photosensitive silver halide emulsion layer on a support, at least one of the silver halide emulsion layers has the following general formula [1], A silver halide photographic light-sensitive material containing at least one sensitizing dye selected from 2] and [3] in combination with at least one macrocyclic compound containing a hetero atom.
【００１２】[0012]
【化４】 [Chemical 4]
【００１３】式中、Z1、Z2はそれぞれ複素環を形成する
に必要な原子群を表し、複素環としては窒素原子、硫黄
原子、酸素原子、セレン原子又はテルル原子を含む5〜6
員の複素環で、これらの環には置換基を有した縮合環が
結合していてもよい。In the formula, Z 1 and Z 2 each represent an atomic group necessary for forming a heterocycle, and the heterocycle includes 5 to 6 containing a nitrogen atom, a sulfur atom, an oxygen atom, a selenium atom or a tellurium atom.
Membered heterocycles, condensed rings having a substituent may be bonded to these rings.
【００１４】複素環としては例えば、チアゾール、ベン
ゾチアゾール、ナフトチアゾール、セレナゾール、ベン
ゾセレナゾール、ナフトセレナゾール、オキサゾール、
ベンゾオキサゾール、ナフトオキサゾール、イミダゾー
ル、ベンゾイミダゾール、ナフトイミダゾール、4-キノ
リン、ピロリン、ピリジン、テトラゾール、インドレニ
ン、ベンゾインドレニン、インドール、テルラゾール、
ベンゾテルラゾール、ナフトテルラゾール核などを挙げ
ることができる。Examples of the heterocycle include thiazole, benzothiazole, naphthothiazole, selenazole, benzoselenazole, naphthoselenazole, oxazole,
Benzoxazole, naphthoxazole, imidazole, benzimidazole, naphthimidazole, 4-quinoline, pyrroline, pyridine, tetrazole, indolenine, benzoindolenine, indole, tellurazole,
Examples thereof include benzoterrazole and naphthoterrazole nuclei.
【００１５】R1、R2はそれぞれアルキル基、アルケニル
基、アルキニル基又はアラルキル基を表す。これらの基
はそれぞれ置換基を有していてもよく、例えばアルキル
基の場合は炭素数1〜8の直鎖又は分岐、環状のいずれで
もよい。R 1 and R 2 each represent an alkyl group, an alkenyl group, an alkynyl group or an aralkyl group. Each of these groups may have a substituent, and for example, in the case of an alkyl group, it may be linear, branched or cyclic having 1 to 8 carbon atoms.
【００１６】アルキル基の置換分としては、例えばハロ
ゲン原子（臭素、塩素、フッ素など）、ヒドロキシ基、
シアノ基、アルコキシ基、置換又は非置換のアミノ基、
カルボン酸、スルホン酸などが一つ又は複数個置換して
いても良い。Examples of the substituent of the alkyl group include a halogen atom (bromine, chlorine, fluorine, etc.), a hydroxy group,
A cyano group, an alkoxy group, a substituted or unsubstituted amino group,
One or more carboxylic acids, sulfonic acids, etc. may be substituted.
【００１７】アルケニル基としては例えばビニルメチル
基を、アラルキル基としては例えばベンジル基、フェネ
チル基などが挙げられる。R3、R4は水素原子、低級アル
キル基又はアラルキル基を表し、R3が水素原子の場合、
R4又はR2と連結して5〜6員環を形成してもよく、R4が水
素原子の場合、R3は他のR3と連結して炭化水素環又は複
素環を形成してもよい。Examples of the alkenyl group include a vinylmethyl group, and examples of the aralkyl group include a benzyl group and a phenethyl group. R 3 and R 4 represent a hydrogen atom, a lower alkyl group or an aralkyl group, and when R 3 is a hydrogen atom,
It may be linked to R 4 or R 2 to form a 5- to 6-membered ring, and when R 4 is a hydrogen atom, R 3 is linked to another R 3 to form a hydrocarbon ring or a heterocycle. Good.
【００１８】k、mは0又は1を表し、Lは3以上の整数を表
す。Xは酸アニオンでnは0又は1を表す。K and m represent 0 or 1, and L represents an integer of 3 or more. X is an acid anion and n is 0 or 1.
【００１９】[0019]
【化５】 [Chemical 5]
【００２０】式中、Z1、Z2はそれぞれ複素環を形成する
に必要な原子群を表し、複素環としては前述の一般式
〔１〕のZ1、Z2と同義である。R1、R2はそれぞれアルキ
ル基、アルケニル基、アルキニル基又はアラルキル基を
表し、前述の一般式〔１〕のR1、R2と同義である。 R4
はアルキル基、アルケニル基、アルキニル基又はアリー
ル基(例えば置換基を有していてもよいフェニル基など)
を表す。R3は水素原子、低級アルキル基、アリール基を
表すほか、R3と他のR3とが連結して炭化水素環又は複素
環を形成してもよい。In the formula, Z 1 and Z 2 each represent an atomic group necessary for forming a heterocycle, and the heterocycle has the same meaning as Z 1 and Z 2 in the above-mentioned general formula [1]. R 1 and R 2 each represent an alkyl group, an alkenyl group, an alkynyl group or an aralkyl group, and have the same meaning as R 1 and R 2 in the above-mentioned general formula [1]. R 4
Is an alkyl group, an alkenyl group, an alkynyl group or an aryl group (for example, a phenyl group which may have a substituent)
Represents. R 3 represents a hydrogen atom, a lower alkyl group or an aryl group, and R 3 and another R 3 may be linked to each other to form a hydrocarbon ring or a heterocycle.
【００２１】Qは硫黄原子、酸素原子、セレン原子又は=
N-R5を表しR5はR4と同義である。Lは2又は3でk、mは0又
は1を表し、Xは酸アニオンでnは0又は1を表す。Q is a sulfur atom, oxygen atom, selenium atom or =
Representing NR 5 , R 5 has the same meaning as R 4 . L is 2 or 3 and k is m or 0 or 1, X is an acid anion and n is 0 or 1.
【００２２】[0022]
【化６】 [Chemical 6]
【００２３】式中、Z1は複素環を形成するに必要な原子
群を表し、複素環としては前述の一般式〔１〕のZ1、Z2
と同義のもの他に、例えばチアゾリン、チアゾリジン、
ベンゾチアゾリン、ナフトチアゾリン、セレナゾリン、
セレナゾリジン、ベンゾセレナゾリン、ナフトセレナゾ
リン、ナフトセレナゾリン、ベンゾオキサゾリン、ナフ
トオキサゾリン、ジヒドロピリジン、ジヒドロキノリ
ン、ベンズイミダゾリン、ナフトイミダゾリンなどが挙
げられる。R1、R2はそれぞれアルキル基、アルケニル
基、アルキニル基又はアラルキル基を表す。In the formula, Z 1 represents an atomic group necessary for forming a heterocycle, and as the heterocycle, Z 1 and Z 2 in the above general formula [1] are used.
In addition to the same meaning as, for example, thiazoline, thiazolidine,
Benzothiazoline, naphthothiazoline, selenazoline,
Examples thereof include selenazolidine, benzoselenazoline, naphthoselenazoline, naphthoselenazoline, benzoxazoline, naphthoxazoline, dihydropyridine, dihydroquinoline, benzimidazoline and naphthimidazoline. R 1 and R 2 each represent an alkyl group, an alkenyl group, an alkynyl group or an aralkyl group.
【００２４】R3は水素原子、低級アルキル基、アリール
基を表すほか、R3と他のR3とが連結して炭化水素環又は
複素環を形成してもよい。Qは硫黄原子、酸素原子、セ
レン原子又は=N-R4を表し、R4ははアルキル基、アルケ
ニル基、アルキニル基又はアリール基を表す。Lは2又は
3でkは0又は1を表す。R 3 represents a hydrogen atom, a lower alkyl group or an aryl group, and R 3 and another R 3 may be linked to each other to form a hydrocarbon ring or a heterocycle. Q represents a sulfur atom, an oxygen atom, a selenium atom or = NR 4 , and R 4 represents an alkyl group, an alkenyl group, an alkynyl group or an aryl group. L is 2 or
In 3, k represents 0 or 1.
【００２５】(2)720nm以上に感光極大を有する赤感性層
を二層以上有するハロゲン化銀写真感光材料において、
より長波長の赤感性層がヘテロ原子を含む大環状化合物
の少なくとも一つを含有する上記(1)項記載のハロゲン
化銀写真感光材料により達成される。以下、本発明を詳
述する。(2) A silver halide photographic light-sensitive material having two or more red-sensitive layers having a light-sensing maximum at 720 nm or more,
This is achieved by the silver halide photographic light-sensitive material according to the above item (1), wherein the red-sensitive layer having a longer wavelength contains at least one macrocyclic compound containing a hetero atom. Hereinafter, the present invention will be described in detail.
【００２６】上記一般式〔１〕で表される分光増感色素
のうち、とくに有用な増感色素としては下記一般式
〔４〕、〔５〕及び〔６〕で表すことができる。Among the spectral sensitizing dyes represented by the above general formula [1], particularly useful sensitizing dyes can be represented by the following general formulas [4], [5] and [6].
【００２７】[0027]
【化７】 [Chemical 7]
【００２８】式中、Z1、Z2は、それぞれ置換基を有して
もよい5〜6員の複素環を形成するに必要な原子群を表
し、R1、R2はそれぞれアルキル基、アルール基で、これ
らの基は置換基を有してもよい。R3、R4、R5及びR6は水
素原子又は置換もしくは非置換のアルキル基、置換もし
くは非置換のアリール基を表す。Xはカウンターイオン
を表す。In the formula, Z 1 and Z 2 each represent an atomic group necessary for forming a 5- to 6-membered heterocyclic ring which may have a substituent, R 1 and R 2 are each an alkyl group, In the alur group, these groups may have a substituent. R 3 , R 4 , R 5 and R 6 represent a hydrogen atom or a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. X represents a counter ion.
【００２９】[0029]
【化８】 [Chemical 8]
【００３０】式中、Z1、Z2は、それぞれチアゾール、オ
キサゾール、セレナゾール、ピリジン、キノリン或はテ
ルラゾール環などを形成するに必要な原子群を表し、こ
れらの複素環は置換基を有していてもよい。Z3は5〜6員
の炭素環を形成するに必要な原子群を表し、R1、R2は置
換もしくは非置換のアルキル基、置換もしくは非置換の
アルール基で、R1はR4と、R2はR5とそれぞれ一緒になっ
て環を形成していてもよい。R3は水素原子又は置換もし
くは非置換のアルキル基、置換もしくは非置換のアリー
ル基を表す。またR3は置換基を有していてもよい複素環
を表す。Xはカウンターイオンを表す。In the formula, Z 1 and Z 2 each represent an atomic group necessary for forming a thiazole, oxazole, selenazole, pyridine, quinoline or tellurazole ring, and these heterocycles have a substituent. May be. Z 3 represents an atomic group necessary for forming a 5- to 6-membered carbocycle, R 1 and R 2 are a substituted or unsubstituted alkyl group, a substituted or unsubstituted alur group, and R 1 is R 4 and , R 2 together with R 5 may form a ring. R 3 represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. R 3 represents a heterocycle which may have a substituent. X represents a counter ion.
【００３１】[0031]
【化９】 [Chemical 9]
【００３２】式中、Z1は、ベンゾチアゾール、ベンゾオ
キサゾール、ベンゾセレナゾール、ベンゾイミダゾール
或はベンゾテルラゾール環を形成するに必要な原子群を
表し、これらの環は置換基を有していてもよい。Z2は置
換基を有していてもよい5〜6員の複素環を形成するに必
要な原子群を表す。In the formula, Z 1 represents an atomic group necessary for forming a benzothiazole, benzoxazole, benzoselenazole, benzimidazole or benzoterrazole ring, and these rings have a substituent. Good. Z 2 represents an atomic group necessary for forming a 5- to 6-membered heterocycle which may have a substituent.
【００３３】L1からL5はそれぞれ置換基を有してもよい
メチン基を表し、R1、R2は置換もしくは非置換のアルキ
ル基、置換もしくは非置換のアルール基で、R1はR4と、
R2はR5とそれぞれ一緒になって環を形成していてもよ
い。R3は水素原子又は置換もしくは非置換のアルキル
基、置換もしくは非置換のアリール基を表す。L 1 to L 5 each represent a methine group which may have a substituent, R 1 and R 2 are a substituted or unsubstituted alkyl group or a substituted or unsubstituted arule group, and R 1 is R 4 and
R 2 may form a ring together with R 5 . R 3 represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group.
【００３４】R3は置換基を有していてもよい炭素数４ま
でのアルキル基で、mは1〜2、nは0〜1を表し、Xはカウ
ンターイオンを表す。R 3 is an alkyl group having up to 4 carbon atoms which may have a substituent, m is 1 to 2, n is 0 to 1 and X is a counter ion.
【００３５】以下、本発明の前記一般式〔１〕〜〔６〕
で表される具体的化合物例を示すが、本発明はこれらに
限定されるものではない。Hereinafter, the above general formulas [1] to [6] of the present invention will be described.
Examples of specific compounds represented by are shown below, but the present invention is not limited thereto.
【００３６】[0036]
【化１０】 [Chemical 10]
【００３７】 No. Ｚ1 Ｚ2 Ｒ1 Ｒ2 Ｙ1 Ｙ2 Ｘ- １ Ｓ Ｏ C2H5 C2H5 Ｈ 6,7-ベンゾ Ｉ ２ Ｓ Ｏ C2H5 (CH2)3SO3 - 6,7-ベンゾ 4,5ベンゾ − ３ Ｓ Ｏ C2H5 (CH2)3SO3 - Ｈ 6-C6H5 − ４ Ｓ Ｏ C2H5 (CH2)2COO- 5,6-CH3 6-Cｌ − ５ Ｏ Ｓ C2H5 C2H5 4,5-ベンゾ 4,5-ベンゾ Br ６ Ｓ Ｓ 〃 〃 Ｈ Ｈ Ｉ ７ Ｓ Ｓ 〃 〃 5,6-SCH3 5,6-SCH3 〃 ８ Ｓ Ｓ 〃 〃 〃 4,5-ベンゾ 〃 ９ Ｓ Ｓ 〃 〃 5-SCH3 Ｈ 〃 10 Ｓ Ｓ 〃 C3H7 5-CH3 6-Cｌ 〃 11 Ｓ Ｓ 〃 CH2COOH Ｈ Ｈ 〃 12 Ｓ Ｓ C2H4OH C2H4OH Ｈ Ｈ 〃 13 Ｏ Ｓ C2H5 C2H5 Ｈ 6-CH3 〃 14 Ｓ Ｓ C2H5 (CH2)3SO3 - 6-Cl Ｈ 〃 15 Ｓ Ｓ C2H5 C2H5 5,6-SCH3 5-OCH3,6-CH3 〃 No. Ｚ1 Ｚ2 Ｒ1 Ｒ2 Ｙ1 Ｙ2 Ｘ- 16 Ｓ Ｓ CH3 CH3 4,5-ベンゾ 4,5-ベンゾ ※PTS 17 Ｓ Ｓ C2H5 C2H5 〃 Ｈ Ｉ 18 Ｓ Ｓ 〃 〃 〃 6-CH3 〃 19 Ｓ Ｓ 〃 〃 〃 5-OCH3 〃 20 Ｓ Ｓ 〃 〃 〃 5,6-CH3 〃 21 Ｓ Ｓ (CH2)4SO3K (CH2)4SO3 - 5,6-OCH3 5,6-CH3 − 22 Ｓ Ｓ (CH2)3SO3 - C4H9 6,7-ベンゾ 5-OCH3 − 23 Ｓ Ｏ C5H11 (CH2)2SO3 - 5,6-CH3 6-OCH3 − 24 Ｓ Ｓ (CH2)3OH (CH2)4SO3 5,6-CH3 5,6-CH3 − （※PTSはパラトルエンスルホン酸）[0037] No. Z 1 Z 2 R 1 R 2 Y 1 Y 2 X - 1 S O C 2 H 5 C 2 H 5 H 6,7- benzo I 2 S O C 2 H 5 (CH 2) 3 SO 3 - 6,7-benzo 4,5-benzo - 3 S O C 2 H 5 (CH 2) 3 SO 3 - H 6-C 6 H 5 - 4 S O C 2 H 5 (CH 2) 2 COO - 5 , 6-CH 3 6-Cl-5OS SC 2 H 5 C 2 H 5 4,5-benzo 4,5-benzo Br 6 SS S 〃 〃 H H I 7 S S 〃 〃 5,6-SCH 3 5,6-SCH 3 〃 8 S S 〃 〃 〃 4,5-Benzo 〃 9 S S 〃 〃 5-SCH 3 H 〃 10 S S 〃 C 3 H 7 5-CH 3 6-Cl 〃 11 S S 〃 CH 2 COOH H H 〃 12 S S C 2 H 4 OH C 2 H 4 OH H H 〃 13 OS C 2 H 5 C 2 H 5 H 6-CH 3 〃 14 S S C 2 H 5 (CH 2 ) 3 SO 3 - 6-Cl H 〃 15 S S C 2 H 5 C 2 H 5 5,6-SCH 3 5-OCH 3, 6-CH 3 〃 No. Z 1 Z 2 R 1 R 2 Y 1 Y 2 X - 16 S S CH 3 CH 3 4,5-benzo 4,5-benzo * PTS 17 S S C 2 H 5 C 2 H 5 〃 HI 18 S S 〃 〃 〃 6-CH 3 〃 19 S S 〃 undefined undefined 5-OCH 3 〃 20 S S Undefined undefined 5, 6-CH 3 〃 21 S S (CH 2) 4 SO 3 K (CH 2) 4 SO 3 - 5,6-OCH 3 5,6-CH 3 - 22 S S (CH 2) 3 SO 3 - C 4 H 9 6,7- benzo 5-OCH 3 - 23 S O C 5 H 11 (CH 2) 2 SO 3 - 5,6-CH 3 6-OCH 3 - 24 S S (CH 2) 3 OH (CH 2 ) 4 SO 3 5,6-CH 3 5,6-CH 3 − (* PTS is paratoluenesulfonic acid)
【００３８】[0038]
【化１１】 [Chemical 11]
【００３９】 No. Ｚ1 Ｚ2 Ｒ1 Ｒ2 Ｙ1 Ｙ2 Ｘ- 25 Ｓ Ｏ C2H5 CH3 Ｈ Ｈ Ｉ 26 Ｓ Ｏ 〃 C2H5 〃 4,5-ベンゾ 〃 27 Ｓ Ｏ 〃 〃 6-CH3 6-CH3 〃 28 Ｓ Ｏ 〃 〃 5-OCH3 6-CH3 〃 29 Ｏ Ｏ 〃 〃 Ｈ Ｈ 〃 30 Ｏ Ｏ 〃 〃 5,6-ベンゾ 5,6-ベンゾ 〃 31 Ｓ Ｓ CH3 CH3 5-SCH3 5-SCH3 〃No. Z 1 Z 2 R 1 R 2 Y 1 Y 2 X - 25 S OC 2 H 5 CH 3 H H I 26 S O 〃 C 2 H 5 〃 4,5-benzo 〃 27 S O 〃 〃 6-CH 3 6-CH 3 〃 28 S O 〃 〃 5-OCH 3 6-CH 3 〃 29 O O 〃 〃 H H 〃 30 O O 〃 〃 5,6-benzo 5,6-benzo 〃 31 S S CH 3 CH 3 5-SCH 3 5-SCH 3 〃
【００４０】[0040]
【化１２】 [Chemical formula 12]
【００４１】[0041]
【化１３】 [Chemical 13]
【００４２】[0042]
【表１】 [Table 1]
【００４３】[0043]
【化１４】 [Chemical 14]
【００４４】[0044]
【化１５】 [Chemical 15]
【００４５】[0045]
【化１６】 [Chemical 16]
【００４６】[0046]
【化１７】 [Chemical 17]
【００４７】[0047]
【化１８】 [Chemical 18]
【００４８】[0048]
【化１９】 [Chemical 19]
【００４９】[0049]
【化２０】 [Chemical 20]
【００５０】上記の赤外感光性増感色素は、例えばエフ
・エム・ハーマー著、（The Chemistry of Heterocylic
Compounds）第18巻、（The Cyanine Dyes and Related
Compounds）（A.Weissherger ed.Interscience社刊、N
ew York 1964年）に記載の方法によって容易に合成する
ことができる。The infrared-sensitive sensitizing dyes described above are described, for example, by F.M.Harmer, (The Chemistry of Heterocylic
Compounds) Volume 18, (The Cyanine Dyes and Related
Compounds) (A. Weissherger ed. Interscience, N
ew York 1964) and can be easily synthesized.
【００５１】次に本発明のヘテロ原子を含む大環状化合
物は、ヘテロ原子として窒素原子、酸素原子、硫黄原
子、セレン原子の少なくとも1つを含む9員環以上の大環
状化合物である。特に好ましい化合物としては、クラウ
ンエーテル化合物をあげることができる。これらの化合
物は、C.J.Pedersen,Journal of American chemical So
ciety vol.86（2495）,7017〜7036（1967）,G.W.Gokel,
S.H,Korzeniowski,“Macrocyclic polyethr synthesi
s"，Springer-Verlag.(1982)，小田、庄野、田伏編“ク
ラウンエーテルの化学"化学同人（1978），田伏等“ホ
ストーゲスト"共立出版（1979），佐々木、古賀、有機
合成化学、Vol45(6)、571〜582（1987）等に詳細に書か
れている。Next, the macrocyclic compound containing a hetero atom of the present invention is a 9-membered or larger macrocyclic compound containing at least one of a nitrogen atom, an oxygen atom, a sulfur atom and a selenium atom as a hetero atom. A crown ether compound can be mentioned as a particularly preferred compound. These compounds are available from CJPedersen, Journal of American chemical So
ciety vol.86 (2495), 7017 ~ 7036 (1967), GWGokel,
SH, Korzeniowski, “Macrocyclic polyethr synthesi
s ", Springer-Verlag. (1982), Oda, Shono, Tabushi edition" Chemistry of Crown Ether "Kagaku Dojin (1978), Tabushi et al." Host Guest "Kyoritsu Publishing (1979), Sasaki, Koga, Synthetic Organic Chemistry, Vol45 ( 6), 571-582 (1987) and so on.
【００５２】以下、本発明に用いられるヘテロ原子を含
む大環状化合物の具体例を示すが本発明はこれらに限定
されるものでない。Specific examples of the macrocyclic compound containing a hetero atom used in the present invention are shown below, but the present invention is not limited thereto.
【００５３】[0053]
【化２１】 [Chemical 21]
【００５４】[0054]
【化２２】 [Chemical formula 22]
【００５５】[0055]
【化２３】 [Chemical formula 23]
【００５６】なお、本発明に用いられるヘテロ原子を含
む大環状化合物は、上記の他に本発明者と同一の出願人
による特願平3-82798号第13頁から第18頁に記載のS-9、
S-12〜15、S-17,18、S-20、S-22〜31、S-33〜34、S-36
などを用いることができる。The macrocyclic compound containing a hetero atom used in the present invention is not limited to the above-mentioned S compounds described in Japanese Patent Application No. 3-82798, pages 13 to 18 by the same applicant as the present inventor. -9,
S-12 ~ 15, S-17, 18, S-20, S-22 ~ 31, S-33 ~ 34, S-36
Etc. can be used.
【００５７】本発明のヘテロ原子を含む大環状化合物を
ハロゲン化銀粒子を含有する親水性コロイドに添加する
には、水又はメタノール、エタノール、フッ素化アルコ
ール，N,N-ジメチルホルムアミドなどの親水性有機溶媒
に溶解したのち添加すればよい。添加時期は、乳剤の塗
布前であればいずれの時期でもよいが好ましくは化学増
感が終了する前に添加されることが好ましい。To add the macrocyclic compound containing a hetero atom of the present invention to a hydrophilic colloid containing silver halide grains, water or a hydrophilic hydrophilic substance such as methanol, ethanol, fluorinated alcohol, N, N-dimethylformamide or the like is used. It may be added after being dissolved in an organic solvent. It may be added at any time before the emulsion is coated, but it is preferably added before the completion of the chemical sensitization.
【００５８】赤外感光性増感色素と大環状化合物の添加
順序は、いずれを先に添加してもよく、同時でも又混合
溶液で添加してもよい。本発明の大環状化合物の添加量
は、化合物の種類により異なるが通常はハロゲン化銀1
モル当り1×10-6〜１×10-1モルの範囲であり、好まし
くは5×10-6〜1×10-2モルである。Regarding the order of addition of the infrared-sensitive sensitizing dye and the macrocyclic compound, any of them may be added first, at the same time or as a mixed solution. The addition amount of the macrocyclic compound of the present invention varies depending on the kind of the compound, but usually silver halide 1
It is in the range of 1 × 10 -6 to 1 × 10 -1 mole, preferably 5 × 10 -6 to 1 × 10 -2 mole per mole.
【００５９】本発明に用いられるハロゲン化銀として
は、塩化銀、臭化銀、沃化銀、塩臭化銀、沃臭化銀、塩
沃臭化銀等の任意のハロゲン化銀が包含される。本発明
に好ましく用いられるハロゲン化銀粒子は塩臭化銀であ
る。更に好ましくは、臭化銀含有率が0.01〜2モル％の
塩臭化銀であり、特に好ましくは臭化銀含有率が0.1〜2
モル％の塩臭化銀である。ハロゲン化銀粒子の組成は、
粒子内部から外部に至るまで均一なものであってもよい
し、また粒子内部と外部の組成が異なってもよい。粒子
内部と外部の組成が異なる場合、連続的に組成が変化し
てもよいし、不連続であってもよい。又、特開平1-1836
47号に記載のように局部的にハロゲン組成が異なる局在
相を有していてもよい。The silver halide used in the present invention includes any silver halide such as silver chloride, silver bromide, silver iodide, silver chlorobromide, silver iodobromide and silver chloroiodobromide. It The silver halide grain preferably used in the present invention is silver chlorobromide. More preferably, it is a silver chlorobromide having a silver bromide content of 0.01 to 2 mol%, and particularly preferably a silver bromide content of 0.1 to 2
It is mol% of silver chlorobromide. The composition of silver halide grains is
It may be uniform from the inside to the outside of the particle, or the composition inside and outside the particle may be different. When the composition inside and outside the particle is different, the composition may change continuously or may be discontinuous. Also, Japanese Patent Laid-Open No. 1-1836
As described in No. 47, it may have a localized phase having locally different halogen compositions.
【００６０】ハロゲン化銀粒子の粒子径は特に制限はな
いが、迅速処理性及び感度等、他の写真性能等考慮する
と、好ましくは0.2〜1.6μm、更に好ましくは0.25〜1.2
μmの範囲である。上記粒子径は、球状又は球に近似の
粒子の場合は粒子直径、立方体粒子の場合は稜長を粒子
径とし、投影面積に基づく平均で表す。ハロゲン化銀粒
子の粒子径の分布は、多分散であってもよいし、単分散
であってもよい。好ましくはハロゲン化銀粒子の粒径分
布において、その変動係数が0.22以下、更に好ましくは
0.15以下の単分散ハロゲン化銀粒子である。The grain size of the silver halide grain is not particularly limited, but in view of other photographic properties such as rapid processing property and sensitivity, it is preferably 0.2 to 1.6 μm, more preferably 0.25 to 1.2.
It is in the range of μm. The above-mentioned particle diameter is expressed as an average based on the projected area, with the particle diameter being the particle diameter in the case of spherical or spherical particles, and the ridge length being the particle diameter in the case of cubic particles. The grain size distribution of the silver halide grains may be polydisperse or monodisperse. Preferably in the grain size distribution of the silver halide grains, the coefficient of variation is 0.22 or less, more preferably
It is a monodisperse silver halide grain of 0.15 or less.
【００６１】本発明において、乳剤に用いられるハロゲ
ン化銀粒子は酸性法、中性法、アンモニア法のいずれで
得られたものでもよい。該粒子は一時に成長させてもよ
いし、種粒子をつくった後、成長させてもよい。本発明
に用いられるハロゲン化銀粒子の形状は任意のものを用
いることができる。好ましい1つの例は、｛100｝面を結
晶表面として有する立方体である。8面体、14面体、12
面体等の形状を有する粒子を用いることもできる。又、
球状、棒状、板状等の粒子でもよい。更に、双晶面を有
する粒子を用いてもよい。In the present invention, the silver halide grains used in the emulsion may be those obtained by any of the acid method, neutral method and ammonia method. The particles may be grown at one time, or may be grown after forming seed particles. The silver halide grains used in the present invention may have any shape. One preferable example is a cube having a {100} plane as a crystal surface. Octahedron, 14-sided, 12
Particles having a shape such as a face piece can also be used. or,
It may be spherical, rod-shaped or plate-shaped particles. Further, grains having twin planes may be used.
【００６２】本発明に用いられるハロゲン化銀乳剤、本
発明に係るハロゲン化銀写真感光材料は、イエローカプ
ラー、マゼンタカプラー、シアンカプラーに組み合わせ
て、400〜900nmの波長域に分光増感されたハロゲン化銀
乳剤を含む層を有する。該ハロゲン化銀乳剤は一種また
は、二種以上の増感色素を組み合わせて含有する。The silver halide emulsion used in the present invention and the silver halide photographic light-sensitive material according to the present invention are combined with a yellow coupler, a magenta coupler and a cyan coupler and are spectrally sensitized in the wavelength range of 400 to 900 nm. It has a layer containing a silver halide emulsion. The silver halide emulsion contains one kind or a combination of two or more kinds of sensitizing dyes.
【００６３】増感色素と共にそれ自身分光増感作用を持
たない色素、或いは可視光を実質的に吸収しない化合物
であって、増感色素の増感作用を強める強色増感剤を乳
剤中に含有させてもよい。A dye having no spectral sensitizing action by itself together with the sensitizing dye, or a compound which does not substantially absorb visible light and enhances the sensitizing action of the sensitizing dye is added to the emulsion. It may be contained.
【００６４】本発明において、イエローカプラーとして
は、アシルアセトアニリド系カプラーを好ましく用いる
ことができる。これらのうち、ベンゾイルアセトアニリ
ド系及びピバロイルアセトアニリド系化合物は有利であ
り、特に特開昭63-85631号に記載されている例示化合物
Y-１〜Y-146、特開昭63-97951号に記載されている例示
化合物Y-１〜Y-98及び特開平1-156748号（67〜78頁）に
記載されている例示化合物Y-１〜Y-24等が好ましく用い
られる。In the present invention, as the yellow coupler, an acylacetanilide type coupler can be preferably used. Among these, benzoylacetanilide compounds and pivaloylacetanilide compounds are advantageous, and the exemplified compounds described in JP-A-63-85631 are particularly advantageous.
Y-1 to Y-146, exemplary compounds Y-1 to Y-98 described in JP-A-63-97951, and exemplary compound Y described in JP-A-1-56748 (pages 67 to 78) -1 to Y-24 are preferably used.
【００６５】本発明に用いうるマゼンタカプラーとして
は、オイルプロテクト型のインダゾロン系もしくはシア
ノアセチル系、好ましくは5-ピラゾロン系及びピラゾロ
トリアゾール類などのピラゾロアゾール系のカプラーが
挙げられる。本発明に好ましく用いられるマゼンタカプ
ラーとしては、下記一般式〔M-I〕及び〔M-XI〕で表さ
れるマゼンタカプラーが挙げられる。Examples of the magenta coupler which can be used in the present invention include oil-protection type indazolone type or cyanoacetyl type, preferably 5-pyrazolone type and pyrazoloazole type couplers such as pyrazolotriazoles. Examples of the magenta coupler preferably used in the present invention include magenta couplers represented by the following general formulas [MI] and [M-XI].
【００６６】[0066]
【化２４】 [Chemical formula 24]
【００６７】式中、Zは含窒素複素環を形成するに必要
な非金属原子群を表し、該Zにより形成される環は置換
基を有してもよい。Xは水素原子又は発色現像主薬の酸
化体との反応により離脱しうる基を表す。In the formula, Z represents a non-metal atom group necessary for forming a nitrogen-containing heterocycle, and the ring formed by Z may have a substituent. X represents a hydrogen atom or a group capable of splitting off upon reaction with an oxidized product of a color developing agent.
【００６８】又、Rは水素原子又は置換基を表す。Rの表
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
ロアルキル等の各基が挙げられるが、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
ホニル、スルフィニル、ホスホニル、アシル、カルバモ
イル、スルファモイル、シアノ、アルコキシなどが挙げ
られる。R represents a hydrogen atom or a substituent. The substituent represented by R is not particularly limited, but typically includes each group such as alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl, cycloalkyl, and the like. Atoms and cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, alkoxy and the like.
【００６９】一般式〔M-I〕で表される化合物の具体例
としては特開昭63-167360号の第5頁右下欄〜第9頁左下
欄に記載のM-１〜M-61ならびに特開昭62-166339号の第1
8頁右上欄〜第32頁右上欄に記載されている化合物の中
で、No.1〜4，6，8〜17，19〜24，26〜43，45〜59，61
〜104，106〜121，123〜162，164〜223で示される化合
物等を挙げることができる。Specific examples of the compound represented by the general formula [MI] include M-1 to M-61 described in JP-A-63-167360, lower right column, page 5 to lower left column, page 9; No. 1 of Kaisho 62-166339
Among the compounds described in the upper right column on page 8 to the upper right column on page 32, No. 1 to 4, 6, 8 to 17, 19 to 24, 26 to 43, 45 to 59, 61
~ 104, 106 ~ 121, 123 ~ 162, 164-223 and the like.
【００７０】[0070]
【化２５】 [Chemical 25]
【００７１】式中、Arはアリール基、Xはハロゲン原
子、アルコキシ基又はアルキル基、Rはベンゼン環に置
換可能な基を表す。nは1又は2を表す。nが2の時はRは同
じ基であっても異なった基でもよい。Yは芳香族第１級
アミン系発色現像主薬の酸化体とのカップリング反応に
より離脱しうる基を表す。In the formula, Ar represents an aryl group, X represents a halogen atom, an alkoxy group or an alkyl group, and R represents a group capable of substituting on the benzene ring. n represents 1 or 2. When n is 2, R may be the same group or different groups. Y represents a group capable of splitting off by a coupling reaction with an oxidation product of an aromatic primary amine type color developing agent.
【００７２】一般式〔M-XI〕において、Yは芳香族第1級
アミン系発色現像主薬の酸化体とのカップリング反応に
より離脱し得る基で、例えばハロゲン原子、アルコキシ
基、アリールオキシ基、アシルオキシ基、アリールチオ
基、アルキルチオ基、5〜6員のヘテロ環基等が挙げられ
る。ここでYは水素原子を表すことはない。In the general formula [M-XI], Y is a group capable of splitting off by a coupling reaction with an oxidation product of an aromatic primary amine type color developing agent, for example, a halogen atom, an alkoxy group, an aryloxy group, Examples thereof include an acyloxy group, an arylthio group, an alkylthio group, and a 5- to 6-membered heterocyclic group. Here, Y does not represent a hydrogen atom.
【００７３】一般式〔M-XI〕で表されるカプラーとして
は、例えば特開昭63-52138号に記載の例示化合物No.218
〜No.244等を挙げることができ、更に米国特許2,600,78
8号、同3,061,432号、同3,062,653号、同3,127,269号、
同3,311,476号、同3,152,896号、同3,419,391号、同3,5
19,429号、同3,555,318号、同3,684,514号、同3,888,68
0号、同3,907,571号、同3,928,044号、同3,930,861号、
同3,930,866号、同3,933,500号、特開昭49-29639号、同
49-111631号、同49-129538号、同50-13041号、同52-589
22号、同55-62454号、同55-118034号、同56-38043号、
同57-35858号、同60-2953号、同60-23855号、同60-6064
4号、英国特許1,247,493号、ベルギー特許789,116号、
同792,525号、西独特許2,156,111号、特公昭46-60479
号、同57-36577号等に記載されている。Examples of the coupler represented by the general formula [M-XI] include Exemplified Compound No. 218 described in JP-A-63-52138.
~ No. 244 and the like, further U.S. Patent 2,600,78
No. 8, No. 3,061,432, No. 3,062,653, No. 3,127,269,
3,311,476, 3,152,896, 3,419,391, 3,5
19,429, 3,555,318, 3,684,514, 3,888,68
0, 3,907,571, 3,928,044, 3,930,861,
3,930,866, 3,933,500, JP-A-49-29639,
49-111631, 49-129538, 50-13041, 52-589
No. 22, No. 55-62454, No. 55-118034, No. 56-38043,
57-35858, 60-2953, 60-23855, 60-6064
4, British patent 1,247,493, Belgian patent 789,116,
No. 792,525, West German Patent No. 2,156,111, Japanese Patent Publication No. 46-60479
No. 57-36577, etc.
【００７４】シアンカプラーとしては、フェノール系シ
アンカプラーとナフトール系シアンカプラーを用いう
る。本発明に好ましく用いられるシアンカプラーとして
は、下記一般式〔C-I〕及び〔C-II〕で表されるシアン
カプラーが挙げられる。As the cyan coupler, a phenol type cyan coupler and a naphthol type cyan coupler can be used. Examples of cyan couplers preferably used in the present invention include cyan couplers represented by the following general formulas [CI] and [C-II].
【００７５】[0075]
【化２６】 [Chemical formula 26]
【００７６】式中、R1は炭素原子数2〜6のアルキル基を
表す。R2はバラスト基を表す。Zは水素原子又は発色現
像主薬の酸化体との反応により離脱可能な原子もしくは
基を表す。R1で表されるアルキル基は直鎖でも分岐でも
よく、置換基を有するものも包含する。In the formula, R 1 represents an alkyl group having 2 to 6 carbon atoms. R 2 represents a ballast group. Z represents a hydrogen atom or an atom or group capable of splitting off upon reaction with an oxidized product of a color developing agent. The alkyl group represented by R 1 may be linear or branched and includes those having a substituent.
【００７７】R2で表されるバラスト基は、カプラーが適
用される層からカプラーを実質的に他層へ拡散できない
ようにするのに十分な嵩ばりをカプラー分子に与えると
ころの大きさと形状を有する有機基である。The ballast group represented by R 2 is of a size and shape that provides the coupler molecule with sufficient bulk to prevent the coupler from substantially diffusing the coupler from the layer to which it is applied. It is an organic group having.
【００７８】該バラスト基として好ましいものは下記一
般式で表されるものである。The preferred ballast group is represented by the following general formula.
【００７９】[0079]
【化２７】 [Chemical 27]
【００８０】R3は炭素原子数1〜12のアルキル基を表
し、Arは、フェニル基等のアリール基を表し、このアリ
ール基は置換基を有するものを包含する。一般式〔C-
I〕で表されるシアンカプラーの具体例としては、特開
平1-156748号第116頁〜119頁に記載されている例示化合
物PC-１〜PC-19、特開昭62-249151号に記載されている
例示化合物C-１〜C-28の他、特公昭49-11572号、特開昭
61-3142号、同61-9652号、同61-9653号、同61-39045
号、同61-50136号、同61-99141号、同61-105545号など
に記載されているシアンカプラーを挙げることができ
る。R 3 represents an alkyl group having 1 to 12 carbon atoms, Ar represents an aryl group such as a phenyl group, and the aryl group includes those having a substituent. General formula (C-
Specific examples of the cyan coupler represented by the formula I) include the exemplified compounds PC-1 to PC-19 described in JP-A 1-156748, pages 116 to 119, and JP-A-62-249151. In addition to the exemplified compounds C-1 to C-28 described in JP-B-49-11572,
61-3142, 61-9652, 61-9653, 61-39045
No. 61-50136, No. 61-99141, No. 61-105545 and the like.
【００８１】[0081]
【化２８】 [Chemical 28]
【００８２】式中、R1はアルキル基又はアリール基を表
す。R2はアルキル基、シクロアルキル基、アリール基又
は複素環基を表す。In the formula, R 1 represents an alkyl group or an aryl group. R 2 represents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group.
【００８３】R3は水素原子、ハロゲン原子、アルキル基
又はアルコキシ基を表す。R 3 represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group.
【００８４】又、R3はR1と共同して環を形成してもよ
い。Zは水素原子又は芳香族第１級アミン系発色現像主
薬の酸化体との反応により離脱可能な基を表す。R 3 may form a ring together with R 1 . Z represents a hydrogen atom or a group capable of splitting off upon reaction with an oxidized product of an aromatic primary amine type color developing agent.
【００８５】前記一般式で〔C-II〕で表されるシアンカ
プラーにおいて、R1で表されるアルキル基としては、炭
素数1〜32のものが好ましく、これらは直鎖でも分岐で
もよく、置換基を有するものも含む。R1で表されるアリ
ール基としてはフェニル基が好ましく、置換基を有する
ものも含む。R2で表されるアルキル基としては炭素数1
〜32のものが好ましく、これらのアルキル基は直鎖でも
分岐でもよく、又置換基を有するものも含む。R2で表さ
れるシクロアルキル基としては炭素数３〜12のものが好
ましく、これらのシクロアルキル基は置換基を有するも
のも含む。R2で表されるアリール基としてはフェニル基
が好ましく、置換基を有するものも含む。R2で表される
複素環基としては5〜7員のものが好ましく、置換基を有
するものを含み、又縮合していてもよい。In the cyan coupler represented by [C-II] in the above general formula, the alkyl group represented by R 1 is preferably one having 1 to 32 carbon atoms, which may be linear or branched. It also includes those having a substituent. The aryl group represented by R 1 is preferably a phenyl group and includes those having a substituent. The alkyl group represented by R 2 has 1 carbon atom
To 32 are preferable, and these alkyl groups may be linear or branched and include those having a substituent. The cycloalkyl group represented by R 2 is preferably one having 3 to 12 carbon atoms, and these cycloalkyl groups include those having a substituent. The aryl group represented by R 2 is preferably a phenyl group, and includes those having a substituent. The heterocyclic group represented by R 2 is preferably a 5- to 7-membered heterocyclic group, which may have a substituent and may be condensed.
【００８６】R3は水素原子、ハロゲン原子、アルキル基
又はアルコキシ基を表し、該アルキル基及び該アルコキ
シ基は置換基を有するものを含むが、Ｒ3は好ましくは
水素原子である。R 3 represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group, and the alkyl group and the alkoxy group include those having a substituent, but R 3 is preferably a hydrogen atom.
【００８７】又、R1とR3が共同して形成する環としては
5〜6員環が好ましく、その例としては、The ring formed by R 1 and R 3 in cooperation is
A 5- to 6-membered ring is preferable, and examples thereof include:
【００８８】[0088]
【化２９】 [Chemical 29]
【００８９】一般式〔C-II〕においてZで表される発色
現像主薬の酸化体との反応により離脱可能な基として
は、ハロゲン原子、アルコキシ基、アリールオキシ基、
アシルオキシ基、スルホニルオキシ基、アシルアミノ
基、スルホニルアミノ基、アルコキシカルボニルオキシ
基、アリールオキシカルボニルオキシ基及びイミド基な
ど（それぞれ置換基を有するものを含む）が挙げられる
が、好ましくは、ハロゲン原子、アリールオキシ基、ア
ルコキシ基である。As the group capable of splitting off upon reaction with the oxidized product of the color developing agent represented by Z in the general formula [C-II], a halogen atom, an alkoxy group, an aryloxy group,
Examples thereof include an acyloxy group, a sulfonyloxy group, an acylamino group, a sulfonylamino group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group and an imide group (including those each having a substituent), but preferably a halogen atom or aryl An oxy group and an alkoxy group.
【００９０】上述のシアンカプラーのうち特に好ましい
ものは、下記一般式〔C-II-A〕で示されるものである。Of the above-mentioned cyan couplers, particularly preferable ones are those represented by the following general formula [C-II-A].
【００９１】[0091]
【化３０】 [Chemical 30]
【００９２】式中、RA1は少なくとも１個のハロゲン原
子で置換されたフェニル基を表し、これらのフェニル基
は更にハロゲン原子以外の置換基を有するものを含む。In the formula, R A1 represents a phenyl group substituted with at least one halogen atom, and these phenyl groups further include those having a substituent other than a halogen atom.
【００９３】ＲA2は前記一般式〔C-II〕のR1と同義であ
る。XAはハロゲン原子、アリールオキシ基又はアルコキ
シ基を表し、置換基を有するものを含む。R A2 has the same meaning as R 1 in the above general formula [C-II]. X A represents a halogen atom, an aryloxy group or an alkoxy group, and includes those having a substituent.
【００９４】一般式〔C-II〕で表されるシアンカプラー
の代表的具体例としては、特開昭63-96656号に記載され
ている例示化合物C-１〜C-25、特開平1-156748号第124
頁〜127頁に記載されている例示化合物PC-II-1〜PC-II-
31の他、特開昭62-178962号第7頁右下の欄〜9頁左下の
欄、特開昭60-225155号第7頁左下の欄〜10頁右下の欄、
特開昭60-222853号第6頁左上の欄〜8頁右下の欄及び特
開昭59-185335号第6頁左下の欄〜9頁左上の欄の記載さ
れた 2,5−ジアシルアミノ系シアンカプラー等が挙げら
れる。Typical examples of the cyan coupler represented by the general formula [C-II] are exemplified compounds C-1 to C-25 described in JP-A-63-96656 and JP-A-1- No. 156748 No. 124
Exemplified Compounds PC-II-1 to PC-II-
In addition to 31, JP-A-62-178962, page 7, lower right column to page 9, lower left column, JP-A-60-225155, page 7, lower left column to page 10, lower right column,
2,5-diacylamino described in JP-A-60-222853, page 6, upper left column to page 8, lower right column, and JP-A 59-185335, page 6, lower left column to page 9, upper left column Examples include cyan couplers.
【００９５】上記カプラー等をハロゲン化銀乳剤に添加
するのに水中油滴型乳化分散法を用いる場合には、通
常、沸点約150℃以上の水不溶性高沸点有機溶媒に、必
要に応じて低沸点及び／又は水溶性有機溶媒を併用して
溶解し、ゼラチン水溶液などの親水性バインダー中に界
面活性剤を用いて撹拌器として、ホモジナイザー、コロ
イドミル、フロージェットミキサー、超音波装置等の分
散手段を用いて、乳化分散した後、目的とする写真構成
層（親水性コロイド層）中に添加すればよい。When the oil-in-water type emulsion dispersion method is used to add the above couplers to the silver halide emulsion, it is usually added to a water-insoluble high boiling organic solvent having a boiling point of about 150 ° C. Dispersing means such as a homogenizer, a colloid mill, a flow jet mixer, an ultrasonic device, etc., which is dissolved in combination with a boiling point and / or a water-soluble organic solvent, and a surfactant is used in a hydrophilic binder such as an aqueous gelatin solution as a stirrer. After being emulsified and dispersed by using, it may be added to a desired photographic constituent layer (hydrophilic colloid layer).
【００９６】分散後、又は分散と同時に低沸点有機溶媒
を除去する工程を入れてもよい。A step of removing the low boiling point organic solvent may be added after or at the same time as the dispersion.
【００９７】このような目的に用いられる高沸点有機溶
媒としては、ジブチルフタレート、ジ-（２-エチルヘキ
シル）フタレート、ジノニルフタレート、ジシクロヘキ
シルフタレート等のフタル酸エステル類、トリクレンジ
ルホスフェート、トリ（2-エチルヘキシル）ホスフェー
ト、ジ-フェニル-クレジルホスフェート、トリヘキシル
ホスフェート等の隣酸エステル類、ジエチルラウラミ
ド、ジブチルラウラミド等の有機酸アミド類、ジノニル
フェノール、p-ドデシルフェノール等のフェノール類、
デカリン、ドデシルベンゼン等の炭化水素類、1,4-ビス
（2-エチルヘキシルカルボニルオキシメチル）シクロヘ
キサン、アジピン酸ジノニル等のエステル類が好ましく
用いられる。中でもフタル酸、隣酸、その他の有機酸エ
ステル類がより好ましく用いられる。これらの高沸点有
機溶媒は1種でも2種以上を併用して用いてもよい。Examples of the high-boiling point organic solvent used for such purpose include phthalic acid esters such as dibutyl phthalate, di- (2-ethylhexyl) phthalate, dinonyl phthalate, dicyclohexyl phthalate, triclenzel phosphate and tri (2- Ethylhexyl) phosphate, di-phenyl-cresyl phosphate, phosphoric acid esters such as trihexyl phosphate, organic acid amides such as diethyllauramide and dibutyllauramide, phenols such as dinonylphenol and p-dodecylphenol,
Hydrocarbons such as decalin and dodecylbenzene, and esters such as 1,4-bis (2-ethylhexylcarbonyloxymethyl) cyclohexane and dinonyl adipate are preferably used. Among them, phthalic acid, phosphoric acid, and other organic acid esters are more preferably used. These high boiling point organic solvents may be used alone or in combination of two or more.
【００９８】カプラー等の分散に用いられる水不溶性で
有機溶媒可溶性のポリマーとしては、 （１）ビニル重合体及び共重合体 （２）多価アルコールと多塩基酸との縮重合体 （３）開還重合法により得られるポリエステル （４）その他ポリカーボネート樹脂、ポリウレタン樹
脂、ポリアミド樹脂 等がある。Water-insoluble and organic solvent-soluble polymers used for dispersing couplers and the like include (1) vinyl polymers and copolymers (2) polycondensed polymers of polyhydric alcohols and polybasic acids (3) opening Polyester obtained by the return polymerization method (4) Other examples include polycarbonate resin, polyurethane resin, polyamide resin and the like.
【００９９】これら重合体の数平均分子量は特に限定さ
れないが、好ましくは20万以下であり、更に好ましくは
5,000〜10万である。重合体のカプラーに対する割合
（重合比）は、１：20〜20：１が好ましく、より好まし
くは１：10〜10：１である。The number average molecular weight of these polymers is not particularly limited, but is preferably 200,000 or less, and more preferably
It is 5,000 to 100,000. The ratio of the polymer to the coupler (polymerization ratio) is preferably 1:20 to 20: 1, more preferably 1:10 to 10: 1.
【０１００】本発明に係る感光材料には、画像色素の耐
久性を高めるため種々の化合物を用いることができる。Various compounds can be used in the light-sensitive material according to the present invention in order to enhance the durability of the image dye.
【０１０１】又本発明においては、カプラーと共に溶
解、分散し、本発明の感光材料に添加することにより、
形成される色素の分光吸収を変化させる種々の化合物を
用いることが出来る。Further, in the present invention, by dissolving and dispersing together with the coupler and adding to the light-sensitive material of the present invention,
Various compounds that change the spectral absorption of the dye formed can be used.
【０１０２】また、これ以外にも米国特許4,774,187号
に記載の蛍光色素放出化合物を用いることも出来る。Besides, the fluorescent dye-releasing compounds described in US Pat. No. 4,774,187 can also be used.
【０１０３】本発明のハロゲン化銀写真感光材料には、
イラジェーション防止、ハレーション防止の目的や感度
調整の目的のために種々の波長域に吸収を有する染料を
用いることが出来る。The silver halide photographic light-sensitive material of the present invention comprises
Dyes having absorption in various wavelength regions can be used for the purpose of preventing irradiation, halation and adjusting sensitivity.
【０１０４】本発明に係るハロゲン化銀写真感光材料に
は、色カブリ防止剤、硬膜剤、可塑剤、ポリマーラテッ
クス、紫外線吸収剤、ホルマリンスカベンジャー、現像
促進剤、現像遅延剤、蛍光増白剤、マット剤、滑剤、帯
電防止剤、界面活性剤等を任意に用いることができる。The silver halide photographic light-sensitive material according to the present invention includes a color antifoggant, a hardener, a plasticizer, a polymer latex, an ultraviolet absorber, a formalin scavenger, a development accelerator, a development retarder and a fluorescent whitening agent. , A matting agent, a lubricant, an antistatic agent, a surfactant and the like can be optionally used.
【０１０５】本発明の乳剤は、常法により化学増感され
る。即ち、銀イオンと反応できる硫黄を含む化合物や、
活性ゼラチンを用いる硫黄増感法、セレン化合物を用い
るセレン増感法、還元性物質を用いる還元増感法などを
単独又は組み合わせて用いることができる。The emulsion of the present invention is chemically sensitized by a conventional method. That is, a compound containing sulfur that can react with silver ions,
The sulfur sensitization method using active gelatin, the selenium sensitization method using a selenium compound, the reduction sensitization method using a reducing substance and the like can be used alone or in combination.
【０１０６】本発明のハロゲン化銀乳剤には、感光材料
の製造工程、保存中、或いは写真処理中のカブリの防
止、又は写真性能を安定に保つことを目的として化学熟
成中、化学熟成の終了時、及び／又は化学熟成の終了後
ハロゲン化銀乳剤を塗布するまでに、カブリ防止剤又は
安定剤を加えることができる。The silver halide emulsion of the present invention is chemically ripened for the purpose of preventing fog during the manufacturing process of the light-sensitive material, during storage, or during photographic processing, or for maintaining stable photographic performance. An antifoggant or stabilizer can be added at any time and / or before the silver halide emulsion is coated after the completion of chemical ripening.
【０１０７】本発明に用いられるハロゲン化銀写真感光
材料のバインダーとしては、ゼラチンを用いることが有
利であるが、必要に応じて他のゼラチン、ゼラチン誘導
体、ゼラチンと他の高分子のグラフトポリマー、それ以
外の蛋白質、糖誘導体、セルロース誘導体、単一或いは
共重合体の如き合成親水性高分子物質等の親水性コロイ
ドも用いることができる。As the binder of the silver halide photographic light-sensitive material used in the present invention, it is advantageous to use gelatin, but if necessary, other gelatin, gelatin derivatives, graft polymers of gelatin and other polymers, Other hydrophilic colloids such as proteins, sugar derivatives, cellulose derivatives, and synthetic hydrophilic polymer substances such as single or copolymers can also be used.
【０１０８】本発明に係るハロゲン化銀写真感光材料の
写真構成層はバライタ紙又はα-オレフィンポリマー等
をラミネートした紙、及び、紙支持体とα-オレフィン
層が容易に剥離できる紙支持体、合成紙等の可撓性反射
支持体、酢酸セルロース、硝酸セルロース、ポリスチレ
ン、ポリ塩化ビニル、ポリエチレンテフタレート、ポリ
カーボネート、ポリアミド等の半合成又は合成高分子か
らなるフィルムに白色顔料を含有あるいは塗布した反射
支持体や金属、陶器などの剛体等に塗布できる。又、12
0〜160μmの薄手型反射支持体を用いることもできる。The photographic constituent layers of the silver halide photographic light-sensitive material according to the present invention are baryta paper or paper laminated with α-olefin polymer, and a paper support from which the paper support and the α-olefin layer can be easily peeled off, Flexible reflective support such as synthetic paper, reflection made by containing or coating white pigment on a film made of semi-synthetic or synthetic polymer such as cellulose acetate, cellulose nitrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, polyamide. It can be applied to a support, metal, rigid body such as pottery. Also, 12
It is also possible to use a thin reflective support having a thickness of 0 to 160 μm.
【０１０９】白色顔料としては、無色及び／又は有機の
白色顔料を用いることができ、好ましくは無機の白色顔
料であり、例えば、硫酸バリウム等のアルカリ土類金属
の硫酸塩、炭酸カルシウム等のアルカリ土類金属の炭酸
塩、微粉珪酸、合成珪酸塩のシリカ類、珪酸カルシウ
ム、アルミナ、アルミナ水和物、酸化チタン、酸化亜
鉛、タルク、クレイ等が挙げられる。白色顔料として好
ましくは硫酸バリウム、酸化チタンである。As the white pigment, colorless and / or organic white pigments can be used, and inorganic white pigments are preferable, and examples thereof include alkaline earth metal sulfates such as barium sulfate and alkali salts such as calcium carbonate. Examples thereof include carbonates of earth metals, finely divided silicic acid, silicas of synthetic silicates, calcium silicate, alumina, hydrated alumina, titanium oxide, zinc oxide, talc and clay. The white pigment is preferably barium sulfate or titanium oxide.
【０１１０】本発明に係るハロゲン化銀感光材料は、必
要に応じて支持体表面にコロナ放電、紫外線照射、火焔
処理等に施した後、直接又は下塗層（支持体表面の接着
性、帯電防止性、寸度安定性、耐摩擦性硬さ、ハレーシ
ョン防止性、摩擦特性及び／又はその他の特性を向上す
るための1又は2以上の下塗層）を介して塗布されてもよ
い。The silver halide light-sensitive material according to the present invention is, if necessary, subjected to corona discharge, ultraviolet ray irradiation, flame treatment or the like on the surface of the support and then directly or undercoat layer (adhesiveness of the surface of the support, charging of the support). It may be applied via one or more subbing layers) for improving anti-prevention properties, dimensional stability, abrasion resistance hardness, anti-halation properties, friction properties and / or other properties.
【０１１１】本発明に係るハロゲン化銀乳剤を用いた写
真感光材料の塗布に際して、塗布性を向上させる為に増
粘剤を用いてもよい。塗布法としては2種以上の層を同
時に塗布することのできるエクストルージョンコーティ
ング及びカーテンコーティングが特に有用である。When coating a photographic light-sensitive material using the silver halide emulsion according to the present invention, a thickener may be used in order to improve coatability. As a coating method, extrusion coating and curtain coating, which can simultaneously coat two or more layers, are particularly useful.
【０１１２】本発明のハロゲン化銀写真感光材料は、当
業界公知の発色現像処理を行うことにより画像を形成す
ることができる。The silver halide photographic light-sensitive material of the present invention can form an image by being subjected to color development processing known in the art.
【０１１３】本発明のハロゲン化銀写真感光材料の現像
処理において発色現像液に使用される発色現像主薬は、
種々のカラー写真プロセスにおいて広範囲に使用されて
いるアミノフェノール系及びp-フェニレンジアミン系誘
導体を包含する。The color developing agent used in the color developing solution in the development processing of the silver halide photographic light-sensitive material of the present invention is
It includes aminophenol-based and p-phenylenediamine-based derivatives that are widely used in various color photographic processes.
【０１１４】本発明のハロゲン化銀写真感光材料の現像
処理に適用される発色現像液には、前記の芳香族第1級
アミン系発色現像主薬に加えて、既知の現像液成分化合
物を添加することができる。To the color developing solution applied to the development processing of the silver halide photographic light-sensitive material of the present invention, a known developing solution component compound is added in addition to the above aromatic primary amine type color developing agent. be able to.
【０１１５】本発明のハロゲン化銀写真感光材料は、発
色現像後、漂白処理及び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。定着処理の後は、通
常は水洗処理が行われる。又、水洗処理の代替として、
安定化処理を行ってもよい。The silver halide photographic light-sensitive material of the present invention is subjected to bleaching treatment and fixing treatment after color development. The bleaching process may be performed at the same time as the fixing process. After the fixing process, a washing process is usually performed. Also, as an alternative to the washing process,
You may perform a stabilization process.
【０１１６】本発明に係る画像形成方法においてハロゲ
ン化銀写真感光材料の現像処理に用いる現像処理装置と
しては、処理槽に配置されたローラーに感光材料を挟ん
で搬送するローラートランスポートタイプであっても、
ベルトに感光材料を固定して搬送するエンドレスベルト
方式であっても、処理槽をスリット状に形成して、この
処理槽に処理液を供給すると共に感光材料を搬送する方
式であってもよい。In the image forming method according to the present invention, the development processing apparatus used for the development processing of the silver halide photographic light-sensitive material is a roller transport type in which the light-sensitive material is nipped and conveyed by the rollers arranged in the processing tank. Also,
An endless belt method in which the photosensitive material is fixed to a belt and conveyed, or a method in which a processing tank is formed in a slit shape and a processing solution is supplied to the processing tank and the photosensitive material is conveyed may be used.
【０１１７】[0117]
【実施例】以下実施例により、本発明を説明するが、本
発明の実施態様はこれらに限定されない。EXAMPLES The present invention will be described below with reference to examples, but the embodiments of the present invention are not limited to these.
【０１１８】実施例１ マゼンタカプラーM-１と色素画像安定剤（ST-１、ST-
２、ST-３）に、高沸点有機溶媒（DNP）と酢酸エチル60
mlを加え溶解し、この溶液を20％界面活性剤（SU-1）7m
lを含有する10％ゼラチン水溶液220mlに超音波ホモジナ
イザーを用いて乳化分散させて、マゼンタカプラー分散
液を作製した。この分散液を下記の構成で塗布した赤外
感光性ハロゲン化銀乳剤と混合し、塗布液を調整し、試
料101〜118を作製した。Example 1 Magenta coupler M-1 and dye image stabilizer (ST-1, ST-
2, ST-3), high boiling organic solvent (DNP) and ethyl acetate 60
Add 20 ml of this solution and dissolve, and add this solution to 20% surfactant (SU-1) 7m.
A magenta coupler dispersion was prepared by emulsifying and dispersing in 220 ml of 10% gelatin aqueous solution containing l using an ultrasonic homogenizer. This dispersion was mixed with an infrared-sensitive silver halide emulsion coated in the following constitution to prepare a coating liquid, to prepare samples 101 to 118.
【０１１９】硬膜剤として、H-1、H-2を添加した。塗布
助剤としては、界面活性剤（SU-2）、（SU-3）を添加
し、表面張力を調整した。H-1 and H-2 were added as hardeners. Surfactants (SU-2) and (SU-3) were added as coating aids to adjust the surface tension.
【０１２０】 保護層 添加量(g/m2) ゼラチン 1.00 防バイ剤（F-1） 0.002 赤外感光層 ゼラチン 1.40 赤外感光性塩臭化銀乳剤（Em-IR1） 0.170 マゼンタカプラー（M-1） 0.35 色素画像安定化剤（ST-1） 0.15 色素画像安定化剤（ST-2） 0.15 色素画像安定化剤（ST-3） 0.15 DNP 0.20 イラジェーション防止染料（AI-1) 0.01 支持体 ポリエチレンラミネート紙 （赤外感光性ハロゲン化銀乳剤の調製方法）40℃に保温
した２％ゼラチン水溶液1000ml中に下記（Ａ液）及び
（Ｂ液）をpAg＝6.5、pH＝3.0に制御しつつ30分かけて
同時添加し、更に下記（Ｃ液）及び（Ｄ液）をpAg＝7.
3、pH＝5.5に制御しつつ180分かけて同時添加した。こ
の時、pAgの制御は特開昭59-45437号記載の方法により
行い、pHの制御は硫酸又は水酸化ナトリウムの水溶液を
用いて行った。Protective layer Addition amount (g / m 2 ) Gelatin 1.00 Antifungal agent (F-1) 0.002 Infrared photosensitive layer Gelatin 1.40 Infrared photosensitive silver chlorobromide emulsion (Em-IR1) 0.170 Magenta coupler (M- 1) 0.35 Dye image stabilizer (ST-1) 0.15 Dye image stabilizer (ST-2) 0.15 Dye image stabilizer (ST-3) 0.15 DNP 0.20 Anti-irradiation dye (AI-1) 0.01 Support Body Polyethylene laminated paper (Method for preparing infrared-sensitive silver halide emulsion) The following (solution A) and (solution B) were controlled to pAg = 6.5 and pH = 3.0 in 1000 ml of 2% gelatin aqueous solution kept at 40 ° C. While simultaneously adding over 30 minutes, the following (C solution) and (D solution) were added to pAg = 7.
3. Simultaneously added over 180 minutes while controlling pH = 5.5. At this time, the pAg was controlled by the method described in JP-A-59-45437, and the pH was controlled by using an aqueous solution of sulfuric acid or sodium hydroxide.
【０１２１】 （Ａ液） 塩化ナトリウム 3.42g 臭化カリウム 0.03g 水を加えて 200ml （Ｂ液） 硝酸銀 10g 水を加えて
２００ｍｌ （Ｃ液） 塩化ナトリウム
１０２．７ｇ 臭化カリウム 1.0g 水を加えて 600ml （Ｄ液） 硝酸銀 300g 水を加えて 600ml 添加終了後、花王アトラス社製デモールＮの5％水溶液
と硫酸マグネシウムの20％水溶液を用いて脱塩を行った
後、ゼラチン水溶液と混合して平均粒径0.43μm、変動
係数＝0.08、塩化銀含有率99.5モル％の単分散立方体乳
剤EMP-1を得た。(Solution A) Sodium chloride 3.42 g Potassium bromide 0.03 g Water was added to 200 ml (Solution B) Silver nitrate 10 g Water was added
200 ml (liquid C) sodium chloride
102.7 g Potassium bromide 1.0 g Water was added to 600 ml (D liquid) Silver nitrate 300 g Water was added to 600 ml After the addition was completed, desalting was performed using a 5% aqueous solution of Kao Atlas Demol N and a 20% aqueous solution of magnesium sulfate. After that, it was mixed with an aqueous gelatin solution to obtain a monodisperse cubic emulsion EMP-1 having an average particle size of 0.43 μm, a coefficient of variation of 0.08 and a silver chloride content of 99.5 mol%.
【０１２２】上記乳剤EMP-1に対し、下記化合物を用
い、50℃にて90分化学熟成を行い、赤外感光性ハロゲン
化銀乳剤（Em-IR1）を得た。The emulsion EMP-1 was chemically ripened at 50 ° C. for 90 minutes using the following compound to obtain an infrared-sensitive silver halide emulsion (Em-IR1).
【０１２３】 チオ硫酸ナトリウム 1.5mg／モルAgX 塩化金酸 1.0mg／モルAgX 安定剤 STAB-1 6×10-4モル／モルAgX 最適なセンシトメトリー性能が得られる時間でSTAB-1を
添加し、温度を低下させて化学熟成を停止させたがSTAB
-1の添加の3分前に本発明に係る増感色素（例示化合
物）を1×10-4モル／モルAgXとヘテロ原子を含む大環状
化合物（例示化合物）を0.7g／モルAgXを添加し、次の
表２に示す内訳の塗布液を調製した。Sodium thiosulfate 1.5 mg / mol AgX Chloroauric acid 1.0 mg / mol AgX Stabilizer STAB-1 6 × 10 −4 mol / mol AgX Add STAB-1 at a time to obtain optimum sensitometric performance , Lowered the temperature and stopped chemical ripening, but STAB
-3 minutes before the addition of -1, 1 × 10 −4 mol / mol AgX of the sensitizing dye according to the present invention (exemplary compound) and 0.7 g / mol AgX of a macrocyclic compound containing a hetero atom (exemplary compound) were added. Then, a coating liquid having the breakdown shown in Table 2 below was prepared.
【０１２４】[0124]
【表２】 [Table 2]
【０１２５】[0125]
【化３１】 [Chemical 31]
【０１２６】[0126]
【化３２】 [Chemical 32]
【０１２７】[0127]
【化３３】 [Chemical 33]
【０１２８】このようにして得られた試料をレーザープ
リンタ（約830nmガリウム・アルミニウム・ヒ素半導体
レーザー）を用い100μmピッチでビーム径80μmのレー
ザー光束により、1.6m／秒の走査速度で走査を行い画像
出力後連続して画像を出し最初の試料と１hr後の試料を
下記の処理工程に従って処理した。The sample thus obtained was scanned at a scanning speed of 1.6 m / sec with a laser beam having a beam diameter of 80 μm at a pitch of 100 μm using a laser printer (gallium-aluminum-arsenic semiconductor laser of 830 nm) and imaged. Images were continuously output after output, and the first sample and the sample after 1 hr were processed according to the following processing steps.
【０１２９】処理工程 温 度 時 間 発色現像 35.0±0.3℃ 45秒 漂白定着 35.0±0.5℃ 45秒 安 定 化 30〜34℃ 90秒 乾 燥 60〜80℃ 60秒 （発色現像液） 純水 800ml トリエタノールアミン 10g N,N‐ジエチルヒドロキシルアミン 5g 臭化カリウム 0.02g 塩化カリウム 2g 亜硫酸カリウム 0.3g 1‐ヒドロキシエチリデン1,1‐ジホスホン酸 1.0g エチレンジアミン四酢酸 1.0g カテコール‐3,5‐ジスルホン酸二ナトリウム塩 1.0g N‐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 4.5g 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 炭酸カリウム 27g 水を加えて全量を100mlとし、pH＝10.10に調整する。 Processing process Temperature Time Color development 35.0 ± 0.3 ℃ 45 seconds Bleach fixing 35.0 ± 0.5 ℃ 45 seconds Stabilization 30-34 ℃ 90 seconds Dry 60-80 ℃ 60 seconds (Color developer) Pure water 800ml Triethanolamine 10g N, N-diethylhydroxylamine 5g Potassium bromide 0.02g Potassium chloride 2g Potassium sulfite 0.3g 1-Hydroxyethylidene 1,1-diphosphonic acid 1.0g Ethylenediaminetetraacetic acid 1.0g Catechol-3,5-disulfonic acid diester Sodium salt 1.0g N-ethyl-N-β-methanesulfonamide Ethyl-3-methyl-4-aminoaniline sulfate 4.5g Optical brightener (4,4'-diaminostilbenedisulfonic acid derivative) 1.0g Potassium carbonate 27g Add water to bring the total volume to 100 ml, and adjust the pH to 10.10.
【０１３０】 （漂白定着液） エチレンジアミン四酢酸第二鉄アンモニウム2水塩 60g エチレンジアミン四酢酸 3g チオ硫酸アンモニウム (70％水溶液) 100ml 亜硫酸アンモニウム (40％水溶液) 27.5ml 水を加えて全量を100mlとし、炭酸カリウム又は氷酢酸でpH＝5.7に調整する。(Bleach-fixing solution) Ethylenediaminetetraacetic acid ammonium ferric dihydrate 60 g Ethylenediaminetetraacetic acid 3 g Ammonium thiosulfate (70% aqueous solution) 100 ml Ammonium sulfite (40% aqueous solution) 27.5 ml Add water to bring the total volume to 100 ml, and add carbonic acid. Adjust to pH = 5.7 with potassium or glacial acetic acid.
【０１３１】 （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 1.0g 1-ヒドロキシエチリデン-1,1-ジホスホン酸 2.0g エチレンジアミン四酢酸 1.0g 水酸化アンモニウム（20％水溶液） 3.0g 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） 1.5g 水を加えて全量を100mlとし、硫酸又は水酸化カリウムでpH＝7.0に調整する。(Stabilizing Solution) 5-Chloro-2-methyl-4-isothiazolin-3-one 1.0 g Ethylene glycol 1.0 g 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0 g Ethylenediaminetetraacetic acid 1.0 g Ammonium hydroxide (20% aqueous solution) 3.0 g Optical brightener (4,4'-diaminostilbenedisulfonic acid derivative) 1.5 g Water is added to bring the total volume to 100 ml, and the pH is adjusted to 7.0 with sulfuric acid or potassium hydroxide.
【０１３２】得られた試料の濃度を求め最初に出力した
試料と1hr後の試料の濃度差（ΔＤ）を求め評価した。The concentration of the obtained sample was determined, and the difference in concentration (ΔD) between the sample initially output and the sample after 1 hour was determined and evaluated.
【０１３３】また、別途780nmのガリウム・アルミニウ
ム・ヒ素半導体レーザーで露光し、下記処理工程にて処
理を行なった。Separately, a 780 nm gallium-aluminum-arsenic semiconductor laser was used for exposure, and the following processing steps were carried out.
【０１３４】露光時の波長が830nmの時の各試料間での
感度比較を行ない感度を求め、試料No.101の感度を100
として表した相対感度で示した。The sensitivity of each sample when the exposure wavelength was 830 nm was compared to find the sensitivity, and the sensitivity of sample No. 101 was set to 100.
The relative sensitivity is expressed as
【０１３５】得られた結果を次の表３に示す。The results obtained are shown in Table 3 below.
【０１３６】[0136]
【表３】 [Table 3]
【０１３７】表から明らかな如く、試料101〜104はΔＤ
が大きく、露光装置を連続して稼動した場合の濃度変動
が大きい。試料105は色素の併用により、連続して走査
露光を行なった時の画像の安定性は良くなっているが、
波長の違いによる感度差が小さい。As is apparent from the table, samples 101 to 104 have ΔD
Is large, and the fluctuation in density is large when the exposure apparatus is continuously operated. Sample 105 has improved image stability when continuously subjected to scanning exposure due to the combined use of a dye,
The difference in sensitivity due to the difference in wavelength is small.
【０１３８】本発明の赤外増感色素と含ヘテロ大環状化
合物の併用によりΔＤが小さく、安定した画像が得られ
ることが分かる。又、ΔＳが大きく分光感度の短波側の
切れがよいことが分かる。このことから、色濁りの要因
が著しく改良されることが分かる。It can be seen that the combined use of the infrared sensitizing dye of the present invention and the hetero-macrocyclic compound containing a heterogeneous compound gives a small ΔD and a stable image can be obtained. Further, it can be seen that the ΔS is large and the spectral sensitivity on the short-wave side is good. From this, it is understood that the factor of color turbidity is remarkably improved.
【０１３９】更に試料106、117、112と試料114、115、1
16を比べて分かるように、一般式の〔4〕、〔5〕、
〔6〕を使用することにより、ΔＤ、ΔＳが小さくより
効果が発揮されていることが分かる。Further, samples 106, 117 and 112 and samples 114, 115 and 1
As can be seen by comparing 16, the general formulas [4], [5],
It can be seen that by using [6], ΔD and ΔS are small and more effective.
【０１４０】又、本発明の含ヘテロ大環状化合物で強色
増感した場合、試料106、109、118と試料119、120、121
を比べて分かるように、クラウンエーテルを用いること
により、より効果が大きいこととが分かる。When supersensitized with the hetero macrocyclic compound of the present invention, Samples 106, 109 and 118 and Samples 119, 120 and 121 were used.
As can be seen by comparing, the use of crown ether is more effective.
【０１４１】実施例２ 実施例１同様に塗布液を調製し、下記の表４，５に示す
構成層で多層ハロゲン化銀写真感光材料201〜205を作製
した。Example 2 A coating solution was prepared in the same manner as in Example 1, and multilayer silver halide photographic light-sensitive materials 201 to 205 having the constituent layers shown in Tables 4 and 5 below were prepared.
【０１４２】（青感性ハロゲン化銀乳剤層の調製）（Ａ
液）と（Ｂ液）の添加時間及び（Ｃ液）と（Ｄ液）の添
加時間を変更する以外はEMP-1と同様にして、平均粒径
0.85μm、変動係数＝0.07、塩化銀含有率99.5％の単分
散立方体乳剤EMP-2を得た。(Preparation of Blue-Sensitive Silver Halide Emulsion Layer) (A
The average particle size is the same as for EMP-1 except that the addition time of (solution) and (solution B) and the addition time of (solution C) and (solution D) are changed.
A monodisperse cubic emulsion EMP-2 having a coefficient of variation of 0.05 and a silver chloride content of 99.5% was obtained.
【０１４３】EMP-2に対し、下記化合物を用いて、50℃
で90分化学熟成を行い、青感性ハロゲン化銀乳剤（Em-
Ｂ）を得た。The following compounds were used for EMP-2 at 50 ° C.
Chemical ripening for 90 minutes with a blue-sensitive silver halide emulsion (Em-
B) was obtained.
【０１４４】 チオ硫酸ナトリウム 0.8mg／モルAgX 塩化金酸 0.5mg／モルAgX 安定剤 STAB-1 6×10-4モル／モルAgX 増感色素 BS-1 4×10-4モル／モルAgX 増感色素 BS-2 1×10-4モル／モルAgX （赤感光性ハロゲン化銀乳剤の調製）（Ａ液）と（Ｂ
液）の添加時間及び（Ｃ液）と（Ｄ液）の添加時間を変
更する以外は実施例１のEMP-1と同様にして、平均粒径
0.50μm、変動係数＝0.08、塩化銀含有率99.5モル％の
単分散立方体乳剤を得た。Sodium thiosulfate 0.8 mg / mol AgX chloroauric acid 0.5 mg / mol AgX stabilizer STAB-1 6 × 10 -4 mol / mol AgX sensitizing dye BS-1 4 × 10 -4 mol / mol AgX sensitization Dye BS-2 1 × 10 -4 mol / mol AgX (preparation of red-sensitive silver halide emulsion) (solution A) and (B
The average particle size was the same as that of EMP-1 of Example 1 except that the addition time of (solution) and the addition time of (solution C) and (solution D) were changed.
A monodispersed cubic emulsion having a coefficient of variation of 0.08 and a silver chloride content of 99.5 mol% was obtained.
【０１４５】この乳剤に、下記化合物を用いて60℃で90
分化学熟成を行い、赤感光性ハロゲン化銀乳剤（Em-R）
を得た。The following compounds were added to this emulsion at 90 ° C. to 90 ° C.
Red-sensitive silver halide emulsion (Em-R)
Got
【０１４６】 チオ硫酸ナトリウム 1.8mg／モルAgX 塩化金酸 2.0mg／モルAgX 安定剤 STAB-1 ６×10-4モル／モルAgX 増感色素 RS-1 １×10-4モル／モルＡｇＸSodium thiosulfate 1.8 mg / mol AgX Chloroauric acid 2.0 mg / mol AgX Stabilizer STAB-1 6 × 10 −4 mol / mol AgX Sensitizing dye RS-1 1 × 10 −4 mol / mol AgX
【０１４７】[0147]
【表４】 [Table 4]
【０１４８】[0148]
【表５】 [Table 5]
【０１４９】[0149]
【化３４】 [Chemical 34]
【０１５０】[0150]
【化３５】 [Chemical 35]
【０１５１】[0151]
【化３６】 [Chemical 36]
【０１５２】[0152]
【化３７】 [Chemical 37]
【０１５３】[0153]
【化３８】 [Chemical 38]
【０１５４】得られた試料をレーザープリンタ（約７８
０ｎｍガリウム・アルミニウム・ヒ素半導体レーザー）
で適宜露光量を変え、実施例１に示した処理工程にて処
理を行ない、イエローのカラーパッチを作成した。得ら
れた試料を光学濃度計（コニカ［株］製PDA-65型）を用
いて、濃度測定し、Ｂ濃度1.8のところのＧ濃度（Ｇ
Ｄ）を求め色濁りの評価を行なった。得られた結果を表
６に示す。The obtained sample was applied to a laser printer (about 78
0nm gallium / aluminum / arsenic semiconductor laser)
Then, the exposure amount was appropriately changed, and the processing was performed in the processing steps shown in Example 1 to prepare a yellow color patch. The concentration of the obtained sample was measured using an optical densitometer (PDA-65 type manufactured by Konica Corporation), and the G concentration at the B concentration of 1.8 (G
D) was obtained and the color turbidity was evaluated. The obtained results are shown in Table 6.
【０１５５】[0155]
【表６】 [Table 6]
【０１５６】表６から本発明の化合物を用いることによ
り色濁りが少なく本発明の効果が得られていることが判
る。From Table 6, it can be seen that by using the compound of the present invention, the color turbidity is small and the effect of the present invention is obtained.
【０１５７】実施例３ 実施例−１で試料102、105、106、107の作成において臭
化銀含有率10モル％の塩臭化銀乳剤を用いた以外、実施
例１同様に試料301〜304を作製した。Example 3 Samples 301 to 304 were prepared in the same manner as in Example 1 except that a silver chlorobromide emulsion having a silver bromide content of 10 mol% was used in the preparation of Samples 102, 105, 106 and 107 in Example-1. Was produced.
【０１５８】また、上記同様に臭化銀含有率70モル％の
塩臭化銀乳剤を用い、試料305〜308及び塩化銀含有率10
0モル％の塩化銀乳剤を用い試料309〜312を作製した。Also, as in the above, using a silver chlorobromide emulsion having a silver bromide content of 70 mol%, samples 305 to 308 and a silver chloride content of 10 mol% were used.
Samples 309-312 were prepared using 0 mol% silver chloride emulsion.
【０１５９】このようにして作製した試料を実施例１同
様に評価した。The sample thus produced was evaluated in the same manner as in Example 1.
【０１６０】試料305〜318については、最適な画像を得
るため、下記処理工程に従って処理した。Samples 305 to 318 were processed according to the following processing steps in order to obtain an optimum image.
【０１６１】 （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−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 ポリ燐酸（TPPS） 2.5g N-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 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100mlとし、水酸化カリウム又は硫酸でpH10.20に調整する。漂白定着液 エチレンジアミン四酢酸第2鉄 アンモニウム2水塩 60g エチレンジアミン四酢酸 3g チオ硫酸アンモニウム（70％溶液） 100ml 亜硫酸アンモニウム（40％溶液） 27.5ml 水を加え全量100mlとし、炭酸カリウム又は氷酢酸でpH7.1に調整する。 得られた結果を次の表７に示す。[0161] (Processing 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 N-ethyl- N- (β-methanesulfonamido ethyl) -3-methyl-4-aminoaniline sulfate 5.5g Optical brightener (4,4'-diaminostilbenedisulfonic acid derivative) 1.0g Potassium hydroxide 2.0g Add water Adjust the total volume to 100 ml and adjust to pH 10.20 with potassium hydroxide or sulfuric acid. Bleach-fixing solution Ethylenediaminetetraacetic acid ferric ammonium dihydrate 60 g Ethylenediaminetetraacetic acid 3 g Ammonium thiosulfate (70% solution) 100 ml Ammonium sulfite (40% solution) 27.5 ml Add water to bring the total volume to 100 ml, and add pH 7 with potassium carbonate or glacial acetic acid. Adjust to 1. The results obtained are shown in Table 7 below.
【０１６２】[0162]
【表７】 [Table 7]
【０１６３】表７で明らかなように塩化銀乳剤又は臭化
銀含有量の高い塩臭化銀乳剤においても、色濁りが小さ
く、連続して画像を出力した時の濃度差も小さく本発明
の効果が得られた。更に臭化銀含有率0.05モル％ではよ
り効果が発揮されることが分かった。As is clear from Table 7, even in a silver chloride emulsion or a silver chlorobromide emulsion having a high silver bromide content, the color turbidity is small and the difference in density when images are continuously output is small, and the density difference of the present invention is small. The effect was obtained. Further, it was found that the effect is more exhibited when the silver bromide content is 0.05 mol%.
【０１６４】[0164]
【発明の効果】本発明により、色濁りがなく、レーザー
プリンターで連続して画像を出力した場合にも安定して
高画質を有するハロゲン化銀写真感光材料を得ることが
できた。According to the present invention, it is possible to obtain a silver halide photographic light-sensitive material having no color turbidity and having a stable high image quality even when images are continuously output by a laser printer.
Claims (2)
ゲン化銀乳剤層を有するハロゲン化銀写真感光材料にお
いて、該ハロゲン化銀乳剤層の少なくとも１層中に下記
一般式〔１〕、〔２〕及び〔３〕から選ばれる増感色素
の少なくとも一つと、ヘテロ原子を含む大環状化合物の
少なくとも一つを組み合わせて含有することを特徴とす
るハロゲン化銀写真感光材料。 【化１】 式中、Z1、Z2はそれぞれ複素環を形成するに必要な原子
群を表し、R1、R2はそれぞれアルキル基、アルケニル
基、アルキニル基又はアラルキル基を表す。R3、R4は水
素原子、低級アルキル基又はアラルキル基を表し、R3が
水素原子の場合、R4又はR2と連結して5〜6員環を形成し
てもよく、R4が水素原子の場合、R3は他のR3と連結して
炭化水素環又は複素環を形成してもよい。k、mは0又は1
を表し、Lは3以上の整数を表す。Xは酸アニオンでnは0
又は1を表す。 【化２】 式中、Z1、Z2はそれぞれ複素環を形成するに必要な原子
群を表し、R1、R2はそれぞれアルキル基、アルケニル
基、アルキニル基又はアラルキル基を表す。R4はアルキ
ル基、アルケニル基、アルキニル基又はアリール基を表
し、R3は水素原子、低級アルキル基、アリール基を表す
ほか、R3と他のR3とが連結して炭化水素環又は複素環を
形成してもよい。Qは硫黄原子、酸素原子、セレン原子
又は=N-R5を表しR5はR4と同義である。Lは2又は3でk、m
は0又は1を表し、Xは酸アニオンでnは0又は1を表す。 【化３】 式中、Z1は複素環を形成するに必要な原子群を表し、
R1、R2はそれぞれアルキル基、アルケニル基、アルキニ
ル基又はアラルキル基を表す。R3は水素原子、低級アル
キル基、アリール基を表すほか、R3と他のR3とが連結し
て炭化水素環又は複素環を形成してもよい。Qは硫黄原
子、酸素原子、セレン原子又は=N-R4を表し、R4ははア
ルキル基、アルケニル基、アルキニル基又はアリール基
を表す。Lは2又は3でkは0又は1を表す。1. A silver halide photographic light-sensitive material having at least one photosensitive silver halide emulsion layer on a support, wherein at least one of the silver halide emulsion layers has the following general formula [1], A silver halide photographic light-sensitive material comprising at least one sensitizing dye selected from 2] and [3] and at least one macrocyclic compound containing a hetero atom in combination. [Chemical 1] In the formula, Z 1 and Z 2 each represent an atomic group necessary for forming a heterocycle, and R 1 and R 2 each represent an alkyl group, an alkenyl group, an alkynyl group or an aralkyl group. R 3 and R 4 represent a hydrogen atom, a lower alkyl group or an aralkyl group, and when R 3 is a hydrogen atom, it may be bonded to R 4 or R 2 to form a 5- to 6-membered ring, and R 4 is In the case of a hydrogen atom, R 3 may combine with another R 3 to form a hydrocarbon ring or a heterocycle. k or m is 0 or 1
And L represents an integer of 3 or more. X is an acid anion and n is 0
Or represents 1. [Chemical 2] In the formula, Z 1 and Z 2 each represent an atomic group necessary for forming a heterocycle, and R 1 and R 2 each represent an alkyl group, an alkenyl group, an alkynyl group or an aralkyl group. R 4 represents an alkyl group, an alkenyl group, an alkynyl group or an aryl group, R 3 represents a hydrogen atom, a lower alkyl group or an aryl group, and R 3 and another R 3 are linked to each other to form a hydrocarbon ring or a heterocycle. You may form a ring. Q represents a sulfur atom, an oxygen atom, a selenium atom or = NR 5, and R 5 has the same meaning as R 4 . L is 2 or 3 and k, m
Represents 0 or 1, X represents an acid anion, and n represents 0 or 1. [Chemical 3] In the formula, Z 1 represents an atomic group necessary for forming a heterocycle,
R 1 and R 2 each represent an alkyl group, an alkenyl group, an alkynyl group or an aralkyl group. R 3 represents a hydrogen atom, a lower alkyl group or an aryl group, and R 3 and another R 3 may be linked to each other to form a hydrocarbon ring or a heterocycle. Q represents a sulfur atom, an oxygen atom, a selenium atom or = NR 4 , and R 4 represents an alkyl group, an alkenyl group, an alkynyl group or an aryl group. L represents 2 or 3, and k represents 0 or 1.
を、二層以上有するハロゲン化銀写真感光材料におい
て、より長波長の赤感性層がヘテロ原子を含む大環状化
合物の少なくとも一つを含有することを特徴とする請求
項１記載のハロゲン化銀写真感光材料。2. A silver halide photographic light-sensitive material having two or more red-sensitive layers having a light-sensitive maximum at 720 nm or more, wherein the longer wavelength red-sensitive layer contains at least one macrocyclic compound containing a hetero atom. The silver halide photographic light-sensitive material according to claim 1, wherein
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3226022A JP2990315B2 (en) | 1991-09-05 | 1991-09-05 | Silver halide photographic material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3226022A JP2990315B2 (en) | 1991-09-05 | 1991-09-05 | Silver halide photographic material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0566515A true JPH0566515A (en) | 1993-03-19 |
| JP2990315B2 JP2990315B2 (en) | 1999-12-13 |
Family
ID=16838562
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3226022A Expired - Lifetime JP2990315B2 (en) | 1991-09-05 | 1991-09-05 | Silver halide photographic material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2990315B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0768570A1 (en) | 1995-10-09 | 1997-04-16 | Konica Corporation | Image forming method |
| EP0779545A1 (en) | 1995-12-15 | 1997-06-18 | Konica Corporation | Image forming method of silver halide color photographic light-sensitive material |
| US7556797B2 (en) * | 2000-10-16 | 2009-07-07 | Mallinckrodt Inc. | Minimally invasive physiological function monitoring agents |
-
1991
- 1991-09-05 JP JP3226022A patent/JP2990315B2/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0768570A1 (en) | 1995-10-09 | 1997-04-16 | Konica Corporation | Image forming method |
| EP0779545A1 (en) | 1995-12-15 | 1997-06-18 | Konica Corporation | Image forming method of silver halide color photographic light-sensitive material |
| US7556797B2 (en) * | 2000-10-16 | 2009-07-07 | Mallinckrodt Inc. | Minimally invasive physiological function monitoring agents |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2990315B2 (en) | 1999-12-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2990315B2 (en) | Silver halide photographic material | |
| EP0915370B1 (en) | Silver halide light-sensitive photographic material | |
| JPH09222707A (en) | Silver halide color photographic sensitive material | |
| JPH05188546A (en) | Silver halide photographic sensitive material | |
| JP3038422B2 (en) | Silver halide photographic emulsion and silver halide photographic light-sensitive material | |
| US6265144B1 (en) | Silver halide emulsion and photographic material by use thereof | |
| JP2847557B2 (en) | Image forming method | |
| JPH0862764A (en) | Silver halide photographic sensitive material | |
| US7163785B2 (en) | Silver halide photosensitive material and image forming method therefor | |
| JP2898115B2 (en) | Silver halide photographic material | |
| JPH11295853A (en) | Silver halide photographic sensitive material | |
| JPH0545776A (en) | Silver halide photographic sensitive material | |
| JPH10186558A (en) | Silver halide emulsion and silver halide photographic sensitive material | |
| JPH086201A (en) | Silver halide photographic sensitive material | |
| JP2001022018A (en) | Silver halide photographic sensitive material and its manufacture | |
| JP2001356453A (en) | Silver halide color photographic sensitive material and method for producing the same | |
| JP2000338631A (en) | Silver halide photographic sensitive material and image forming method | |
| JPH03294849A (en) | Color image forming method | |
| JP2001318444A (en) | Color image forming method | |
| JPH03223749A (en) | Image forming method | |
| JP2004205573A (en) | Silver halide color photosensitive material and developing processing method | |
| JPH0450835A (en) | Silver halide photographic sensitive material | |
| JPH0869067A (en) | Silver halide photographic sensitive material and color image forming method | |
| JP2002006429A (en) | Silver halide photosensitive material and area gradation image forming method | |
| JP2006258879A (en) | Silver halide color photosensitive material and area coverage modulation image forming method |