JPH04328542A - Silver halide photographic sensitive material - Google Patents
Silver halide photographic sensitive materialInfo
- Publication number
- JPH04328542A JPH04328542A JP12548791A JP12548791A JPH04328542A JP H04328542 A JPH04328542 A JP H04328542A JP 12548791 A JP12548791 A JP 12548791A JP 12548791 A JP12548791 A JP 12548791A JP H04328542 A JPH04328542 A JP H04328542A
- Authority
- JP
- Japan
- Prior art keywords
- chemical formula
- silver halide
- formula
- group
- layer
- 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 description 49
- 229910052709 silver Inorganic materials 0.000 title claims description 38
- 239000004332 silver Substances 0.000 title claims description 38
- 239000000463 material Substances 0.000 title claims description 19
- 239000000839 emulsion Substances 0.000 claims abstract description 32
- 230000001235 sensitizing effect Effects 0.000 claims abstract description 24
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 claims abstract description 6
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 3
- 150000001340 alkali metals Chemical group 0.000 claims abstract description 3
- 150000001450 anions Chemical class 0.000 claims abstract description 3
- 150000001768 cations Chemical class 0.000 claims abstract description 3
- 239000000126 substance Substances 0.000 claims description 40
- 239000000975 dye Substances 0.000 claims description 29
- 150000001875 compounds Chemical class 0.000 claims description 21
- 150000003839 salts Chemical class 0.000 claims description 8
- 125000000623 heterocyclic group Chemical group 0.000 claims description 6
- QGKMIGUHVLGJBR-UHFFFAOYSA-M (4z)-1-(3-methylbutyl)-4-[[1-(3-methylbutyl)quinolin-1-ium-4-yl]methylidene]quinoline;iodide Chemical compound [I-].C12=CC=CC=C2N(CCC(C)C)C=CC1=CC1=CC=[N+](CCC(C)C)C2=CC=CC=C12 QGKMIGUHVLGJBR-UHFFFAOYSA-M 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- RYLTXMGSVFOQKY-UHFFFAOYSA-N 1,3-thiazolidin-5-one Chemical compound O=C1CNCS1 RYLTXMGSVFOQKY-UHFFFAOYSA-N 0.000 claims description 2
- 150000008626 4-imidazolidinones Chemical class 0.000 claims description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 150000001412 amines Chemical group 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 229940006460 bromide ion Drugs 0.000 claims description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 230000035945 sensitivity Effects 0.000 abstract description 17
- 125000004429 atom Chemical group 0.000 abstract description 6
- 125000000217 alkyl group Chemical group 0.000 abstract description 3
- 125000005842 heteroatom Chemical group 0.000 abstract 3
- 239000002585 base Substances 0.000 abstract 1
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 abstract 1
- 238000000034 method Methods 0.000 description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 239000013078 crystal Substances 0.000 description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical class C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 8
- 238000011161 development Methods 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 108010010803 Gelatin Proteins 0.000 description 5
- 206010070834 Sensitisation Diseases 0.000 description 5
- 229920000159 gelatin Polymers 0.000 description 5
- 239000008273 gelatin Substances 0.000 description 5
- 235000019322 gelatine Nutrition 0.000 description 5
- 235000011852 gelatine desserts Nutrition 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 230000008313 sensitization Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 206010034960 Photophobia Diseases 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 208000013469 light sensitivity Diseases 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 230000003595 spectral effect Effects 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 229920002301 cellulose acetate Polymers 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000005070 ripening Effects 0.000 description 2
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 description 1
- AIGNCQCMONAWOL-UHFFFAOYSA-N 1,3-benzoselenazole Chemical class C1=CC=C2[se]C=NC2=C1 AIGNCQCMONAWOL-UHFFFAOYSA-N 0.000 description 1
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical class C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 description 1
- ODIRBFFBCSTPTO-UHFFFAOYSA-N 1,3-selenazole Chemical class C1=C[se]C=N1 ODIRBFFBCSTPTO-UHFFFAOYSA-N 0.000 description 1
- NOLHRFLIXVQPSZ-UHFFFAOYSA-N 1,3-thiazolidin-4-one Chemical compound O=C1CSCN1 NOLHRFLIXVQPSZ-UHFFFAOYSA-N 0.000 description 1
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-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
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 229920001817 Agar Polymers 0.000 description 1
- 102000009027 Albumins Human genes 0.000 description 1
- 108010088751 Albumins Proteins 0.000 description 1
- BMTAFVWTTFSTOG-UHFFFAOYSA-N Butylate Chemical compound CCSC(=O)N(CC(C)C)CC(C)C BMTAFVWTTFSTOG-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229920008347 Cellulose acetate propionate Polymers 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- LEVWYRKDKASIDU-IMJSIDKUSA-N L-cystine Chemical compound [O-]C(=O)[C@@H]([NH3+])CSSC[C@H]([NH3+])C([O-])=O LEVWYRKDKASIDU-IMJSIDKUSA-N 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-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
- 229920002472 Starch Polymers 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-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
- XEIPQVVAVOUIOP-UHFFFAOYSA-N [Au]=S Chemical compound [Au]=S XEIPQVVAVOUIOP-UHFFFAOYSA-N 0.000 description 1
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- 235000010419 agar Nutrition 0.000 description 1
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229920006318 anionic polymer Polymers 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000007611 bar coating method Methods 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
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 description 1
- AMTXUWGBSGZXCJ-UHFFFAOYSA-N benzo[e][1,3]benzoselenazole Chemical class C1=CC=C2C(N=C[se]3)=C3C=CC2=C1 AMTXUWGBSGZXCJ-UHFFFAOYSA-N 0.000 description 1
- KXNQKOAQSGJCQU-UHFFFAOYSA-N benzo[e][1,3]benzothiazole Chemical class C1=CC=C2C(N=CS3)=C3C=CC2=C1 KXNQKOAQSGJCQU-UHFFFAOYSA-N 0.000 description 1
- WMUIZUWOEIQJEH-UHFFFAOYSA-N benzo[e][1,3]benzoxazole Chemical class C1=CC=C2C(N=CO3)=C3C=CC2=C1 WMUIZUWOEIQJEH-UHFFFAOYSA-N 0.000 description 1
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical class C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001661 cadmium Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229960003067 cystine Drugs 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 150000002344 gold compounds Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002503 iridium Chemical class 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 235000012149 noodles Nutrition 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 150000002916 oxazoles Chemical class 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920006289 polycarbonate film Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000018102 proteins Nutrition 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- KIWUVOGUEXMXSV-UHFFFAOYSA-N rhodanine Chemical compound O=C1CSC(=S)N1 KIWUVOGUEXMXSV-UHFFFAOYSA-N 0.000 description 1
- 150000003283 rhodium Chemical class 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 239000010979 ruby Substances 0.000 description 1
- 229910001750 ruby Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- 229940045105 silver iodide Drugs 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 150000003475 thallium Chemical class 0.000 description 1
- 150000003557 thiazoles Chemical class 0.000 description 1
- 150000003549 thiazolines Chemical class 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 description 1
- 238000012549 training Methods 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は、分光増感されたハロゲ
ン化銀に関するもので、特に赤色光領域に極大分光感度
をもち、主としてＨｅ−Ｎｅレーザー光を用いて露光す
る工程を含むシステムに使用され、かつ高感度にしてカ
ブリが低く、足切れが良く、疲労液適性の優れたハロゲ
ン化銀感光材料に関するものである。[Industrial Application Field] The present invention relates to spectrally sensitized silver halide, which has maximum spectral sensitivity in the red light region, and is particularly applicable to systems that include an exposure step using mainly He-Ne laser light. The present invention relates to a silver halide photosensitive material that is used, has high sensitivity, low fog, good sharpness, and excellent suitability for fatigue liquids.
【０００２】0002
【従来の技術】ハロゲン化銀写真感光材料は、その目的
に応じて、それぞれ異なる特定波長に感度をもつことが
要求される。そのような感光材料の製造技術の１つとし
て、ある種の増感色素類がハロゲン化銀に添加され、特
定の波長における感度を有効に高めることは一般によく
知られている。2. Description of the Related Art Silver halide photographic materials are required to be sensitive to different specific wavelengths depending on their purpose. As one of the manufacturing techniques for such light-sensitive materials, it is generally well known that certain sensitizing dyes are added to silver halide to effectively increase sensitivity at specific wavelengths.
【０００３】さらに、近年のオプトエレクトロニクスの
急速な発展にともない、デジタル化した画像情報の出力
用光源として従来の白熱電球等に代わり、レーザー光や
ＬＥＤ光等の光源が用いられ始めている。なかでも、既
に実用域にあるＨｅ−Ｎｅレーザー光、ルビーレーザー
、赤色ＬＥＤ光は発光波長が ６００〜７００ｎｍの範
囲にあり、これらの赤色光を記録する感光材料が広く用
いられている。Furthermore, with the rapid development of optoelectronics in recent years, light sources such as laser light and LED light have begun to be used in place of conventional incandescent light bulbs and the like as light sources for outputting digitized image information. Among them, He-Ne laser light, ruby laser light, and red LED light, which are already in practical use, have emission wavelengths in the range of 600 to 700 nm, and photosensitive materials that record these red lights are widely used.
【０００４】この様な、感光材料の製造技術の１つとし
て、ある種の増感色素類がハロゲン化銀写真乳剤に添加
され、そのハロゲン化銀の固有波長域より長波長域にお
いて、特定の波長域における感度を有効に高めることは
一般によく知られている。As one of the manufacturing techniques for such light-sensitive materials, certain sensitizing dyes are added to silver halide photographic emulsions, and in a wavelength range longer than the characteristic wavelength range of the silver halide, a certain type of sensitizing dye is added. It is generally well known that sensitivity in a wavelength range can be effectively increased.
【０００５】このような増感色素としては、多くのもの
が提案されているが、特公昭４９−１３３３１号、特開
昭５０−６２４２５、英国特許第１４７１７０１号など
に示される三複素環色素（ｔｒｉｈｅｔｅｒｏｃｙｃｌ
ｉｃ ｄｙｅ）がこのような赤色光感度を高めるのに非
常に有効であることが知られている。しかしながら、こ
れらの増感色素は、ハロゲン化銀写真乳剤の赤色光感度
を高める反面、カブリの増加と写真特性曲線の足部の切
れ（足切れ）の悪化をもたらす。特にこの足切れは感光
材料の画質に大きな影響を及ぼすため、主としてＨｅ−
Ｎｅレーザー光を用いて露光する工程を含むシステムに
使用される感光材料においては重要なことである。Many such sensitizing dyes have been proposed, including triheterocyclic dyes (as shown in Japanese Patent Publication No. 49-13331, Japanese Patent Application Laid-open No. 50-62425, British Patent No. 1471701, etc.). triheterocycle
ic dye) is known to be very effective in increasing red light sensitivity. However, although these sensitizing dyes increase the red light sensitivity of silver halide photographic emulsions, they also cause an increase in fog and worsening of the toe part of the photographic characteristic curve. In particular, this shortening has a great effect on the image quality of photosensitive materials, so it is mainly
This is important in photosensitive materials used in systems that include an exposure process using Ne laser light.
【０００６】これらのカブリを抑える目的では、カブリ
防止剤の使用が一般的であるが、三複素環色素で赤色増
感したハロゲン化銀写真乳剤にメルカプト基を含んだカ
ブリ防止剤を併用すると感度の低下が大きく、また疲労
した現像液で処理した場合に写真感度が大幅に低下する
などの弊害が大きい。この疲労した現像液による処理に
関しては、感光材料の処理量に応じて適切な現像液の補
充を行っていれば問題はないが、処理液の管理は非常に
煩雑であり、疲労した処理液でも安定な特性が得られる
と言うことは重要なことである。For the purpose of suppressing these fogs, antifoggants are generally used, but when an antifoggant containing a mercapto group is used in combination with a silver halide photographic emulsion red-sensitized with a triheterocyclic dye, the sensitivity can be increased. In addition, processing with a tired developer causes significant disadvantages such as a significant decrease in photographic sensitivity. There is no problem with processing with a tired developer as long as the developer is replenished appropriately according to the amount of photosensitive material to be processed, but managing the processing solution is very complicated and even with a tired processing solution. It is important that stable characteristics can be obtained.
【０００７】しかしながら、、三複素環色素で増感を行
うことにより、これらの赤色光に十分な感度をもち、か
つカブリ濃度が低く、また足切れが良く、疲労液適性の
優れた感光材料として満足のいくものが無いのが実情で
あった。However, by sensitizing with a triheterocyclic dye, it can be used as a photosensitive material that has sufficient sensitivity to these red lights, has low fog density, has good sharpness, and has excellent suitability for fatigue liquids. The reality was that there was nothing satisfying.
【０００８】[0008]
【発明が解決しようとする課題】本発明の目的は赤色波
長域の感度が高く、かつカブリが少なく、足切れが良く
、疲労液適性の優れた感光材料を提供することにある。SUMMARY OF THE INVENTION An object of the present invention is to provide a photosensitive material that has high sensitivity in the red wavelength region, has little fog, has good foot-cutting properties, and is excellent in suitability for fatigue liquids.
【０００９】[0009]
【課題を解決するための手段】本発明は、写真用支持体
上に感光性ハロゲン化銀乳剤層を少なくとも１層有し、
かつ支持体上の既乳剤層と同じ側に非感光性層を少なく
とも１層有するハロゲン化銀感光材料において、既乳剤
層の少なくとも１層に化１で示される増感色素を少なく
とも１つ含み、かつ化１の増感色素の含まれる層には化
２で示される化合物を実質的に含まず、かつ化１の増感
色素の含まれる層には化３で示される化合物を少なくと
も１つ含有し、既非感光性層の少なくとも１層に化２で
示される化合物を少なくとも１つ含有することによって
効果的に達成された。Means for Solving the Problems The present invention has at least one photosensitive silver halide emulsion layer on a photographic support,
and a silver halide light-sensitive material having at least one non-photosensitive layer on the same side as the emulsion layer on the support, at least one of the emulsion layers containing at least one sensitizing dye represented by formula 1; and the layer containing the sensitizing dye represented by Chemical Formula 1 does not substantially contain the compound represented by Chemical Formula 2, and the layer containing the sensitizing dye represented by Chemical Formula 1 contains at least one compound represented by Chemical Formula 3. However, this can be effectively achieved by containing at least one compound represented by Chemical Formula 2 in at least one of the non-photosensitive layers.
【００１０】化１中、Ｚ，Ｚ１はそれぞれシアニン色素
で通常用いられる５員環及び／または６員環の含窒素複
素環を形成するのに必要な原子群を表す。上記複素環核
としては例えばチアゾリン核、チアゾール核、ベンゾチ
アゾール核、ナフトチアゾール核、セレナゾール核、ベ
ンゾセレナゾール核、ナフトセレナゾール核、オキサゾ
ール核、ベンゾオキサゾール核、ナフトオキサゾール核
、２−キノリン核、４−キノリン核、２−ピリジン核、
４−ピリジン核、３，３−ジアルキルインドレニン核、
ベンゾイミダゾール核等であって、この複素環の炭素原
子にはハロゲン原子、アルキル基、アルコキシル基、ヒ
ドロキシ基、モノアリール基などの置換基がついていて
もよい。In formula 1, Z and Z1 each represent an atomic group necessary to form a 5-membered ring and/or 6-membered nitrogen-containing heterocycle commonly used in cyanine dyes. Examples of the above-mentioned heterocyclic nuclei include thiazoline nucleus, thiazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, selenazole nucleus, benzoselenazole nucleus, naphthoselenazole nucleus, oxazole nucleus, benzoxazole nucleus, naphthoxazole nucleus, 2-quinoline nucleus, 4-quinoline nucleus, 2-pyridine nucleus,
4-pyridine nucleus, 3,3-dialkylindolenine nucleus,
It is a benzimidazole nucleus, etc., and a substituent such as a halogen atom, an alkyl group, an alkoxyl group, a hydroxy group, or a monoaryl group may be attached to the carbon atom of this heterocycle.
【００１１】Ｒ，Ｒ１はそれぞれ飽和または不飽和脂肪
族基、例えば低級アルキル基（たとえばメチル基、エチ
ル基、ｎ−プロピル基、ｎ−ブチル基、など）、置換ア
ルキル基（好ましくはアルキルラジカルの炭素が５以下
のもの）たとえばヒドロキシ基、アセトキシ基、アルコ
キシ基、カルボキシ基、アルコキシカルボニル基、スル
ホ基、ビニル基、モノアリール基等の置換基を持つもの
を表す。R and R1 each represent a saturated or unsaturated aliphatic group, such as a lower alkyl group (such as a methyl group, an ethyl group, an n-propyl group, an n-butyl group, etc.), or a substituted alkyl group (preferably an alkyl radical). 5 or less carbon atoms) For example, it represents a substance having a substituent such as a hydroxy group, an acetoxy group, an alkoxy group, a carboxy group, an alkoxycarbonyl group, a sulfo group, a vinyl group, or a monoaryl group.
【００１２】ＱとＱ１（組合せ）は４−チアゾリジノン
、５−チアゾリジノン、または４−イミダゾリジノン核
を形成するのに必要な原子群を表す。Q and Q1 (combination) represent a group of atoms necessary to form a 4-thiazolidinone, 5-thiazolidinone, or 4-imidazolidinone nucleus.
【００１３】[0013]
【００１４】またＬ１とＲ、Ｌ３とＲ１はそれぞれメチ
レン鎖で結合して含窒素複素環を形成してもよい。[0014] Furthermore, L1 and R, and L3 and R1 may each be bonded through a methylene chain to form a nitrogen-containing heterocycle.
【００１５】ｍ、ｎは０または１を表す。m and n represent 0 or 1.
【００１６】Ｘはアニオンたとえばクロルイオン、ブロ
ムイオン、ヨードイオン、Ｐ−トルエンスルホン酸イオ
ン等を表す。X represents an anion such as chlorine ion, bromide ion, iodo ion, P-toluenesulfonate ion, etc.
【００１７】Ｐは０または１を表し、分子内塩の時はＰ
＝０を表す。[0017] P represents 0 or 1, and when it is an inner salt, P
= represents 0.
【００１８】化２中Ｚ２は５員環及び／または６員複素
環を形成するのに必要な非金属原子群を表す。Ｍは水素
原子、アルカリ金属原子、アンモニウム基または有機ア
ミン残基を表す。Z2 in formula 2 represents a group of nonmetallic atoms necessary to form a 5-membered ring and/or a 6-membered heterocycle. M represents a hydrogen atom, an alkali metal atom, an ammonium group, or an organic amine residue.
【００１９】化３中ＹおよびＺ３はそれぞれ独立に、メ
チン、置換メチン、または窒素原子のいずれかを表し、
Ｑ２は５ないし６員のヘテロ環を形成するのに必要な原
子群を表し、これらの環はさらに縮合されてもよい。Ｍ
１は水素原子または陽イオンを表す。In formula 3, Y and Z3 each independently represent methine, substituted methine, or a nitrogen atom,
Q2 represents an atomic group necessary to form a 5- to 6-membered heterocycle, and these rings may be further fused. M
1 represents a hydrogen atom or a cation.
【００２０】本発明に用いられる化１の増感色素の添加
量はハロゲン化銀１モルあたり５ｍｇから５００ｍｇの
広範囲にわたり、効果の得られる最適量を任意に選択す
ることが出来る。これらの増感色素は単独に用いてもよ
いが、それらを組み合わせて用いてもよい。The amount of the sensitizing dye represented by Formula 1 used in the present invention ranges over a wide range from 5 mg to 500 mg per mole of silver halide, and the optimum amount for obtaining the desired effect can be arbitrarily selected. These sensitizing dyes may be used alone or in combination.
【００２１】該増感色素をこれらのハロゲン化銀乳剤に
添加するには、メタノール、エタノール、イソプロパノ
ール、ピリジン、ジメチルホルムアミド、水等の単独ま
たは混合した溶媒の溶液として添加することが出来る。
また、超音波分散を用いて乳剤中に加えることが出来る
。さらに、米国特許第３４８２９８１号、同第３５８５
１９５号、同第３４６９９８７号、同第３６４９２８６
号、同第３４８５６３４号、同第３３４２６０５号、お
よび同第２９１２３４３号明細書に記載された方法も用
いることが出来る。The sensitizing dye can be added to these silver halide emulsions as a solution in a solvent such as methanol, ethanol, isopropanol, pyridine, dimethylformamide, water, etc. alone or in combination. It can also be added to the emulsion using ultrasonic dispersion. Additionally, U.S. Patent Nos. 3,482,981 and 3,585
No. 195, No. 3469987, No. 3649286
The methods described in Japanese Patent Application No. 3485634, Japanese Patent No. 3342605, and Japanese Patent No. 2912343 can also be used.
【００２２】また、これらの増感色素をハロゲン化銀写
真乳剤に添加する時期は乳剤製造工程中いかなる時期で
もよい。Further, these sensitizing dyes may be added to the silver halide photographic emulsion at any time during the emulsion manufacturing process.
【００２３】次に、本発明に使用される増感色素の具体
例を列挙するが、これにより本発明に使用する増感色素
が、限定されるものではない。Next, specific examples of the sensitizing dyes used in the present invention will be listed, but the sensitizing dyes used in the present invention are not limited by these.
【００２４】[0024]
【化４】[C4]
【００２５】[0025]
【化５】[C5]
【００２６】[0026]
【化６】[C6]
【００２７】[0027]
【化７】[C7]
【００２８】[0028]
【化８】[Chemical formula 8]
【００２９】[0029]
【化９】[Chemical formula 9]
【００３０】[0030]
【化１０】[Chemical formula 10]
【００３１】[0031]
【化１１】[Chemical formula 11]
【００３２】[0032]
【化１２】[Chemical formula 12]
【００３３】[0033]
【化１３】[Chemical formula 13]
【００３４】[0034]
【化１４】[Chemical formula 14]
【００３５】[0035]
【化１５】[Chemical formula 15]
【００３６】[0036]
【化１６】[Chemical formula 16]
【００３７】[0037]
【化１７】[Chemical formula 17]
【００３８】[0038]
【化１８】[Chemical formula 18]
【００３９】[0039]
【化１９】[Chemical formula 19]
【００４０】[0040]
【化２０】[C20]
【００４１】[0041]
【化２１】[C21]
【００４２】[0042]
【化２２】[C22]
【００４３】[0043]
【化２３】[C23]
【００４４】[0044]
【化２４】[C24]
【００４５】[0045]
【化２５】[C25]
【００４６】[0046]
【化２６】[C26]
【００４７】[0047]
【化２７】[C27]
【００４８】[0048]
【化２８】[C28]
【００４９】[0049]
【化２９】[C29]
【００５０】[0050]
【化３０】[C30]
【００５１】[0051]
【化３１】[Chemical formula 31]
【００５２】[0052]
【化３２】[C32]
【００５３】[0053]
【化３３】[Chemical formula 33]
【００５４】[0054]
【化３４】[C34]
【００５５】[0055]
【化３５】[C35]
【００５６】[0056]
【化３６】[C36]
【００５７】[0057]
【化３７】[C37]
【００５８】[0058]
【化３８】[C38]
【００５９】[0059]
【化３９】[C39]
【００６０】[0060]
【化４０】[C40]
【００６１】[0061]
【化４１】[C41]
【００６２】本発明に使用される増感色素は、フランシ
ス．エム．ハーマー（Ｆｒａｎｃｅｓ．Ｍ．Ｈａｍｅｒ
）著 ザ シアニン ダイズ アンドリレ
イテッド コンパウンズ（Ｔｈｅｃｙａｎｉｎｅ ｄ
ｙｅｓ ａｎｄ ｒｅｌａｔｅｄ ｃｏｍｐｏｕｎｄｓ
）、ジョンウィリー アンド サンズリミテッド（
Ｊｏｈｎ Ｗｉｌｅｙ ａｎｄ Ｓｏｎｓ Ｌｔｄ）刊
（１９６４）、ドイツ特許第９７１９４１号、同第１０
１３１６７号や米国特許第２９４７６号明細書などを参
考にすれば関係技術者には容易に合成できる。The sensitizing dye used in the present invention is Francis. M. Frances.M.Hamer
) by The Cyanine Soybeans and Related Compounds
yes and related compounds
), John Wiley & Sons Limited (
John Wiley and Sons Ltd) (1964), German Patent No. 971941, German Patent No. 10
13167, US Pat. No. 29476, etc., it can be easily synthesized by those skilled in the art.
【００６３】次に化２で示される本発明に用いられる化
合物の具体例を列挙するが、これにより本発明に使用す
る化合物が、限定されるものではない。[0063] Specific examples of the compound shown by formula 2 used in the present invention will be listed below, but the compounds used in the present invention are not limited thereby.
【００６４】[0064]
【化４２】[C42]
【００６５】[0065]
【化４３】[C43]
【００６６】[0066]
【化４４】[C44]
【００６７】[0067]
【化４５】[C45]
【００６８】[0068]
【化４６】[C46]
【００６９】[0069]
【化４７】[C47]
【００７０】[0070]
【化４８】[C48]
【００７１】[0071]
【化４９】[C49]
【００７２】[0072]
【化５０】[C50]
【００７３】[0073]
【化５１】[C51]
【００７４】[0074]
【化５２】[C52]
【００７５】[0075]
【化５３】[C53]
【００７６】[0076]
【化５４】[C54]
【００７７】[0077]
【化５５】[C55]
【００７８】[0078]
【化５６】[C56]
【００７９】[0079]
【化５７】[C57]
【００８０】[0080]
【化５８】[C58]
【００８１】[0081]
【化５９】[C59]
【００８２】[0082]
【化６０】[C60]
【００８３】[0083]
【化６１】[C61]
【００８４】[0084]
【化６２】[C62]
【００８５】[0085]
【化６３】[C63]
【００８６】[0086]
【化６４】[C64]
【００８７】[0087]
【化６５】[C65]
【００８８】[0088]
【化６６】[C66]
【００８９】[0089]
【化６７】[C67]
【００９０】[0090]
【化６８】[C68]
【００９１】[0091]
【化６９】[C69]
【００９２】[0092]
【化７０】[C70]
【００９３】[0093]
【化７１】[C71]
【００９４】[0094]
【化７２】[C72]
【００９５】本発明に用いられる化２の化合物は、塗布
までの任意の時期に添加すればよい。The compound of formula 2 used in the present invention may be added at any time before coating.
【００９６】また、既非感光層については０．１〜３０
ｍｇ／ｍ２、好ましくは０．５〜１０ｍｇ／ｍ２である
。[0096] For the non-photosensitive layer, 0.1 to 30
mg/m2, preferably 0.5 to 10 mg/m2.
【００９７】添加に際しては、適当な溶媒、例えばメタ
ノール、エタノール、イソプロパノール、ピリジン、ジ
メチルホルムアミド、水等の単独または混合した溶媒の
溶液として添加する。When added, it is added as a solution in a suitable solvent such as methanol, ethanol, isopropanol, pyridine, dimethylformamide, water, etc. alone or in combination.
【００９８】次に化３で示される本発明に用いられる化
合物の具体例を列挙するが、これにより本発明に使用す
る化合物が、限定されるものではない。[0098] Specific examples of the compound shown by formula 3 used in the present invention are listed below, but the compounds used in the present invention are not limited thereby.
【００９９】0099
【化７３】[C73]
【０１００】[0100]
【化７４】[C74]
【０１０１】[0101]
【化７５】[C75]
【０１０２】[0102]
【化７６】[C76]
【０１０３】[0103]
【化７７】[C77]
【０１０４】[0104]
【化７８】[C78]
【０１０５】[0105]
【化７９】[C79]
【０１０６】[0106]
【化８０】[C80]
【０１０７】[0107]
【化８１】[Chemical formula 81]
【０１０８】[0108]
【化８２】[C82]
【０１０９】[0109]
【化８３】[Chemical formula 83]
【０１１０】[0110]
【化８４】[Chemical formula 84]
【０１１１】[0111]
【化８５】[Chemical formula 85]
【０１１２】[0112]
【化８６】[C86]
【０１１３】[0113]
【化８７】[Chemical formula 87]
【０１１４】[0114]
【化８８】[Chemical formula 88]
【０１１５】本発明に用いられる化３の化合物は、塗布
までの任意の時期に添加すればよい。The compound of formula 3 used in the present invention may be added at any time before coating.
【０１１６】また、添加量については、０．１〜５０ｍ
ｇ／ｍ２、好ましくは０．５〜３０ｍｇ／ｍ２である。[0116] Also, regarding the amount added, 0.1 to 50 m
g/m2, preferably 0.5 to 30 mg/m2.
【０１１７】添加に際しては、適当な溶媒、例えばメタ
ノール、エタノール、イソプロパノール、ピリジン、ジ
メチルホルムアミド、水等の単独または混合した溶媒の
溶液として添加する。When added, it is added as a solution in a suitable solvent such as methanol, ethanol, isopropanol, pyridine, dimethylformamide, water, etc. alone or in combination.
【０１１８】本発明に用いられるハロゲン化銀写真乳剤
は公知の種々の方法によって調製することが出来る。The silver halide photographic emulsion used in the present invention can be prepared by various known methods.
【０１１９】写真乳剤中のハロゲン化銀粒子は、立方体
、八面体、１４面体、斜方１２面体のような規則的な結
晶体を有するものでもよく、また、球状、板状等の変則
的な結晶系を持つもの、あるいはこれらの結晶形の複合
形を持つものでも良い。また、種々の結晶形の粒子の混
合からなっていても良い。The silver halide grains in the photographic emulsion may have a regular crystal structure such as a cube, an octahedron, a tetradecahedron, or a rhombic dodecahedron, or may have an irregular crystal structure such as a spherical shape or a plate shape. It may have a crystalline system or a composite of these crystalline forms. Further, it may be composed of a mixture of particles of various crystal forms.
【０１２０】ハロゲン化銀粒子は、内部と表層が異なる
相を持っていても、また均一な相からなっていてもよい
。The silver halide grains may have different phases inside and on the surface, or may consist of a uniform phase.
【０１２１】また、例えば、ＰｂＯの様な酸化物結晶と
塩化銀のようなハロゲン化銀結晶を結合させた、複合型
ハロゲン化銀結晶、エピタキシャアル成長をさせたハロ
ゲン化銀結晶（例えば、臭化銀上に塩化銀、ヨウ臭化銀
、ヨウ化銀等をエピタキシャルに成長させる。）等でも
良い。[0121] Also, for example, composite silver halide crystals in which oxide crystals such as PbO and silver halide crystals such as silver chloride are combined, epitaxially grown silver halide crystals (for example, Alternatively, silver chloride, silver iodobromide, silver iodide, etc. may be grown epitaxially on silver bromide.
【０１２２】また、アスペクト比３以上、好ましくは５
〜２０の平板状ハロゲン化銀粒子を用いることもできる
。より詳しくは、米国特許４４３４２２６号、同４４３
９５２０号、特開昭５９−９９４３３号、「リサーチデ
スクロージャー」第２２５巻、Ｎｏ．２２５３４（１９
８３年１月）等に記載されている。[0122] Also, the aspect ratio is 3 or more, preferably 5
-20 tabular silver halide grains can also be used. For more details, see U.S. Pat. Nos. 4,434,226 and 443
No. 9520, JP-A No. 59-99433, "Research Disclosure" Vol. 225, No. 22534 (19
(January 1983), etc.
【０１２３】また、本発で用いられるハロゲン化銀粒子
の粒子サイズ分布は、任意であるが、単分散であっても
よい。ここで、単分散とは９５％の粒子が数平均粒子サ
イズの±６０％以内、好ましくは４０％以内のサイズに
はいる分散系である。ここで、数平均粒子サイズとは、
ハロゲン化銀粒子の投影面積径の数平均直径である。Further, the grain size distribution of the silver halide grains used in the present invention is arbitrary, and may be monodisperse. Here, monodisperse means a dispersion system in which 95% of the particles are within ±60%, preferably within 40%, of the number average particle size. Here, the number average particle size is
It is the number average diameter of the projected area diameter of silver halide grains.
【０１２４】本発明に用いられる写真乳剤は、ジー・エ
フ・デュフィン（Ｇ．Ｆ．Ｄｕｆｆｉｎ）著フォトグラ
フィック エマルジョン ケミストリー（Ｐｈｏｔ
ｏｇｒａｐｈｉｃ ＥｍｕｌｓｉｏｎＣｈｅｍｉｓｔｒ
ｙ）、ザ フォーカル プレス（Ｔｈｅ Ｆｏｃａ
ｌ Ｐｒｅｓｓ）刊（１９６６年）、ヴイ エル
ツエリクマン他著（Ｖ．Ｌ．Ｚｅｌｉｋｍａｎ ｅｔ
ａｌ）メーキング アンド コーティング フォ
トグラフィック エマルジョン（Ｍａｋｉｎｇ ａｎ
ｄ Ｃｏａｔｉｎｇ Ｐｈｏｔｏ−ｇｒａｐｈｉｃ Ｅ
ｍｕｌｓｉｏｎ）、ザ フォーカル プレス（Ｔｈ
ｅ Ｆｏｃａｌ Ｐｒｅｓｓ）刊（１９６４年）等に記
載された方法を用いて調整することが出来る。即ち、酸
性法、中性法、アンモニア法等のいずれでもよく、また
可溶性銀塩と可溶性ハロゲン塩を反応させる形式として
は、片側混合法、同時混合法、それらの組合せ等のいず
れを用いてもよい。[0124] The photographic emulsion used in the present invention is based on the book "Photographic Emulsion Chemistry" by G.F. Duffin.
graphic Emulsion Chemistry
y), The Focal Press (The Foca
Press) (1966), V.L.
V.L. Zelikman et al.
al) Making and Coating Photographic Emulsion
dCoating Photo-graphic E
mulsion), The Focal Press (Th
It can be adjusted using the method described in e.g. Focal Press (1964). That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt with the soluble halogen salt may be any one-sided mixing method, simultaneous mixing method, or a combination thereof. good.
【０１２５】同時混合法の一つの形式として、ハロゲン
化銀の生成される液相中のｐＡｇを一定に保つ方法、即
ちコントロールド・ダブルジェット法を用いることもで
きる。この方法によると、結晶形が規則的で粒子サイズ
が均一に近いハロゲン化銀乳剤が得られる。As one type of simultaneous mixing method, a method in which the pAg in the liquid phase in which silver halide is produced can be kept constant, that is, a controlled double jet method can also be used. According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained.
【０１２６】また、別々に形成した２種以上のハロゲン
化銀乳剤を混合してもよい。Furthermore, two or more silver halide emulsions formed separately may be mixed.
【０１２７】ハロゲン化銀粒子形成または物理熟成の過
程に於て、カドミウム塩、亜鉛塩、鉛塩、タリウム塩、
イリジウム塩またはその錯塩、ロジウム塩またはその錯
塩等を共存させてもよい。In the process of silver halide grain formation or physical ripening, cadmium salt, zinc salt, lead salt, thallium salt,
Iridium salts or complex salts thereof, rhodium salts or complex salts thereof, etc. may also be present.
【０１２８】沈澱形成後あるいは物理塾成後の乳剤から
可溶性塩類を除去する方法としては、ゼラチンをゲル化
させるヌードル法や、無機塩類、アニオン性界面活性剤
、アニオン性ポリマーあるいは変性ゼラチン等を利用し
た沈澱法（フロッキュレーション法）等が用いられる。[0128] Methods for removing soluble salts from the emulsion after precipitation or physics training include the noodle method of gelatin gelling, inorganic salts, anionic surfactants, anionic polymers, modified gelatin, etc. A precipitation method (flocculation method), etc., is used.
【０１２９】ハロゲン化銀乳剤は、公知の方法で化学増
感を施すことが出来る。硫黄増感剤としては、例えばチ
オ硫酸塩、チオ尿素、アリルイソチアシアネート、シス
チン、ローダニンや、米国特許１５７４９４４号、同２
２７８９４７号、同２４１０６８９号、同２４４０２０
６号、同３１８７４５８号、同３４１５６４９号、同３
５０１３１３号等に記載されているような含硫黄化合物
を用いることが出来る。また、米国特許２５９７８５６
号、同２５９７９１５号、同２３９９０８３号等に記載
されている金化合物による金増感を施すことが出来る。
また、米国特許２４４８０６０号、同２５４００３６号
、同２５５６２４５号、同２５６６２６３号に記載され
ている白金パラジウム、イリジウム、ロジウム、ルテニ
ウムのような貴金属の塩を用いる増感法を組み合わせて
用いることが出来る。そしてこれらの増感法は単一でな
く組み合わせて使うこともできる。The silver halide emulsion can be chemically sensitized by a known method. Examples of the sulfur sensitizer include thiosulfate, thiourea, allyl isothiacyanate, cystine, rhodanine, and US Pat.
No. 278947, No. 2410689, No. 244020
No. 6, No. 3187458, No. 3415649, No. 3
Sulfur-containing compounds such as those described in No. 501313 can be used. Also, US Patent No. 2,597,856
Gold sensitization using gold compounds described in Japanese Patent No. 2,597,915, No. 2,399,083, etc. can be performed. Further, sensitization methods using salts of noble metals such as platinum palladium, iridium, rhodium, and ruthenium described in U.S. Pat. No. 2,448,060, U.S. Pat. No. 2,540,036, U.S. Pat. These sensitization methods can be used not only singly but also in combination.
【０１３０】本発明では、ポリアルキレンオキサイド、
チオエーテル化合物、四級アンモニウム塩化合物等の各
種の現像促進剤を用いることが出来る。[0130] In the present invention, polyalkylene oxide,
Various development accelerators such as thioether compounds and quaternary ammonium salt compounds can be used.
【０１３１】本発明のに用いられるハロゲン化銀写真乳
剤は必要に応じて、他の増感色素、例えば、シアニン、
メロシアニン類を併用して分光増感してもよく、さらに
公知の方法により安定剤、界面活性剤、硬膜剤のような
添加を含有することができる。The silver halide photographic emulsion used in the present invention may contain other sensitizing dyes, such as cyanine,
Spectral sensitization may be carried out by using merocyanines in combination, and additions such as stabilizers, surfactants, and hardening agents can be added by known methods.
【０１３２】本発明に用いられる親水性コロイドとして
は、ゼラチン、コロイド状アルブミン、カゼイン等のタ
ンパク質、カルボキシメチルセルローズ等のセルロース
誘導体、寒天、アルギン酸ナトリウム、澱粉等の糖誘導
体、ポリビニールアルコール、ポリアクリルアミド等の
合成ポリマー等を単独あるいは適当な比率で混合して用
いることが出来る。Hydrophilic colloids used in the present invention include proteins such as gelatin, colloidal albumin, and casein, cellulose derivatives such as carboxymethyl cellulose, agar, sodium alginate, sugar derivatives such as starch, polyvinyl alcohol, and polyacrylamide. These synthetic polymers can be used alone or in a mixture at an appropriate ratio.
【０１３３】本発明の感光材料においては、通常写真感
光材料の支持体として用いられるものがすべて用いられ
る。例えばセルロースナイトレートフィルム、セルロー
スアセテートフィルム、セルロースアセテートプチレー
トフィルム、セルロースアセテートプロピオネートフィ
ルム、ポリスチレンフィルム、ポリエチレンテレフタレ
ートフィルム、ポリカーボネートフィルムその他これら
の積層物、紙などがある。バライタまたはα−オレフィ
ンポリマー、特にポリエチレン、ポリプロピレンなどの
炭素原子１〜１０のα−オレフィンのポリマーを塗布ま
たはラミネートした紙などの支持体も好適である。[0133] In the light-sensitive material of the present invention, any support that is normally used as a support for photographic light-sensitive materials can be used. Examples include cellulose nitrate film, cellulose acetate film, cellulose acetate butylate film, cellulose acetate propionate film, polystyrene film, polyethylene terephthalate film, polycarbonate film, laminates thereof, and paper. Also suitable are supports such as paper coated or laminated with baryta or alpha-olefin polymers, especially polymers of alpha-olefins having from 1 to 10 carbon atoms, such as polyethylene or polypropylene.
【０１３４】[0134]
【実施例】以下に、実施例により本発明を具体的に説明
するが、むろんこの記述により本発明が制限されるもの
ではない。EXAMPLES The present invention will be specifically explained below with reference to Examples, but the present invention is of course not limited to these descriptions.
【０１３５】実施例１
慣用のハロゲン化銀写真乳剤の製法により作られたハロ
ゲン化銀結晶粒子の平均粒子径が０．３μのヨウ臭化銀
乳剤を硫黄−金増感法による第２熟成を施した後、化４
０の増感色素をハロゲン化銀１モル当り２５ｍｇ添加し
、化２及び化３の化合物を表１に示すように添加した後
、安定剤、塗布助剤、硬膜剤を添加して塗布乳剤とした
。Example 1 A silver iodobromide emulsion with silver halide crystal grains having an average grain size of 0.3 μm prepared by a conventional method for producing a silver halide photographic emulsion was subjected to second ripening by a sulfur-gold sensitization method. After applying, chemical 4
After adding 25 mg of the sensitizing dye No. 0 per mole of silver halide, and adding the compounds of Chemicals 2 and 3 as shown in Table 1, stabilizers, coating aids, and hardeners were added to form a coated emulsion. And so.
【０１３６】また、５％ゼラチン水溶液に表１に示すよ
うに化２の化合物を添加した後、塗布助剤、硬膜剤を添
加して 塗布オーバー液とした。[0136] Further, after adding the compound of formula 2 as shown in Table 1 to a 5% gelatin aqueous solution, a coating aid and a hardening agent were added to prepare a coating over solution.
【０１３７】これらの塗布乳剤と塗布オーバー液を、厚
さ１００μの写真用ポリエチレン被覆紙に塗布乳剤層が
塗布銀量１．８ｇ／ｍ２、オーバー層の乾燥後のゼラチ
ン塗布量が１．５ｇ／ｍ２になるようにワイヤーバー塗
布法により塗布し、乾燥して試料を得た。These coated emulsions and overcoat liquid were coated on photographic polyethylene coated paper with a thickness of 100 μm, so that the emulsion layer had a coated silver amount of 1.8 g/m 2 and the gelatin coated amount of the over layer after drying was 1.5 g/m2. It was coated using a wire bar coating method so as to have a coating thickness of m2, and dried to obtain a sample.
【０１３８】この試料を色温度５４００゜Ｋの光源を持
つ感光計を用いて、光源に６３３ｎｍの光を透過する干
渉フィルターをつけて露光した。引き続き各々の試料を
三菱製紙（株）製現像液ＭＲＡ−ＣＤ２３１を用いて３
８℃２０秒現像し、停止、三菱製紙（株）製定着液ＭＲ
Ａ−ＣＦ６０１を用いて定着さらに水洗を行ない所定の
黒白像を持つストリップスを得た。[0138] This sample was exposed to light using a sensitometer having a light source with a color temperature of 5400°K and an interference filter that transmits light of 633 nm attached to the light source. Subsequently, each sample was processed using developer MRA-CD231 manufactured by Mitsubishi Paper Mills Co., Ltd.
Develop at 8℃ for 20 seconds, stop, and use fixer MR manufactured by Mitsubishi Paper Mills Co., Ltd.
The strips were fixed using A-CF601 and washed with water to obtain strips having a predetermined black and white image.
【０１３９】その試料を米国マクベスコーポレーション
製ＭＡＣＢＥＴＨ ＴＤ−５０４濃度計を用いて濃度
測定し、赤色光感度を得た。感度を決定した光学濃度の
基準点は、いずれも濃度０．７５の点であった。また未
露光の試料を３８℃６０秒現像した後、同様の方法で処
理し、カブリ濃度測定を行った。さらに、現像進行性を
見るために現像時間を３２℃２０秒にし同様の処理を行
い、３８℃２０秒現像処理した場合との感度差△Ｓを求
める。The density of the sample was measured using a MACBETH TD-504 densitometer manufactured by Macbeth Corporation, USA, to obtain the red light sensitivity. The optical density reference point at which sensitivity was determined was a point with a density of 0.75. Further, an unexposed sample was developed at 38° C. for 60 seconds and then treated in the same manner, and the fog density was measured. Further, in order to check the progress of development, the same process was performed with the development time changed to 32°C for 20 seconds, and the sensitivity difference ΔS was determined compared to when the development process was performed at 38°C for 20 seconds.
【０１４０】この結果を表１に示す。感度は３８℃２０
秒現像処理した場合の値で、試料１を１００とした相対
感度で示している。化２、化３の添加量は１ｍ２当りの
添加量（ｍｇ）である。また足切れについては、３８℃
２０秒現像処理した場合の写真特性曲線の足部の切れを
５段階評価した。１が最も良く５が最も悪く３以上は画
質にはっきりとした悪影響があり実用上問題となるレベ
ルである。[0140] The results are shown in Table 1. Sensitivity is 38℃20
The value is when the second development process is performed, and the relative sensitivity is shown with sample 1 set as 100. The amount of chemical compounds 2 and 3 added is the amount (mg) added per 1 m2. Also, regarding leg cuts, 38℃
The breakage at the toe of the photographic characteristic curve when developed for 20 seconds was evaluated in five grades. 1 is the best, 5 is the worst, and 3 or more has a clear negative effect on image quality and is at a level that poses a practical problem.
【０１４１】[0141]
【０１４２】表１から明らかなように、本発明は感度が
高く、かつカブリが少なく、足切れがよく、現像進行性
がいいことがわかる。[0142] As is clear from Table 1, the present invention has high sensitivity, little fog, good toe-cutting, and good development progress.
【０１４３】実施例２
増感色素及び化２、化３の化合物を表２に示したように
する以外は、実施例１に従って同様の試料を作製した。
比較色素として化８９を用いた。増感色素の添加量はハ
ロゲン化銀１モル当りの量（ｍｇ）であり、化２の添加
量は１ｍ２当りの添加量（ｍｇ）である。Example 2 A similar sample was prepared according to Example 1, except that the sensitizing dye and the compounds of Chemical Formulas 2 and 3 were changed as shown in Table 2. Chemical compound 89 was used as a comparison dye. The amount of the sensitizing dye added is the amount (mg) per mole of silver halide, and the amount of chemical compound 2 added is the amount (mg) added per 1 m2.
【０１４４】この試料を実施例１と同様に、色温度５４
００゜Ｋの光源を持つ感光計を用いて、光源に６３３ｎ
ｍの光を透過する干渉フィルターをつけて露光し、引き
続き各々の試料を三菱製紙（株）製現像液ＭＲＡ−ＣＤ
２３１を用いて３８℃２０秒現像し、停止、三菱製紙（
株）製定着液ＭＲＡ−ＣＦ６０１を用いて定着さらに水
洗を行ない所定の黒白像を持つストリップスを得るが、
疲労した液での特性を調べるために、現像液については
、新液での現像と、試料１を現像液１Ｌ当り５ｍ２現像
を行い疲労させた現像液で同様の処理を行った。[0144] This sample was prepared at a color temperature of 54 in the same manner as in Example 1.
Using a sensitometer with a 00°K light source, set the light source to 633n.
After exposing each sample to light using an interference filter that transmits light of
231 at 38°C for 20 seconds, stop, and develop with Mitsubishi Paper Mills (
The strips are fixed using fixer MRA-CF601 manufactured by Co., Ltd., and then washed with water to obtain strips with a predetermined black and white image.
In order to investigate the characteristics with a tired solution, the same processing was performed with a new developer and with a developer that had been fatigued by developing Sample 1 with 5 m2 per liter of developer.
【０１４５】この結果を表２に示した。[0145] The results are shown in Table 2.
【０１４６】[0146]
【化８９】[Chemical formula 89]
【０１４７】[0147]
【０１４８】このように、本発明品は感度が高く、疲労
液、新液とも足切れが良く、カブリも少ないことがわか
る。[0148] Thus, it can be seen that the product of the present invention has high sensitivity, good cutting performance in both fatigue liquid and fresh liquid, and less fog.
【０１４９】[0149]
【発明の効果】本発明によって、赤色光領域に極大分光
感度をもち、主としてＨｅ−Ｎｅレーザー光を用いて露
光する工程を含むシステムに使用されるハロゲン化銀感
光材料において、赤色波長域の感度が高く、かつカブリ
が少なく、現像進行性の優れた感光材料が得られる。Effects of the Invention According to the present invention, in a silver halide photosensitive material which has maximum spectral sensitivity in the red light region and is used in a system that includes an exposure step mainly using He-Ne laser light, the sensitivity in the red wavelength region can be improved. It is possible to obtain a photosensitive material which has a high color balance, low fog, and excellent development progress.
Claims (1)
乳剤層を少なくとも１層有し、かつ支持体上の既乳剤層
と同じ側に非感光性層を少なくとも１層有するハロゲン
化銀感光材料において、既乳剤層の少なくとも１層に化
１で示される増感色素を少なくとも１つ含み、かつ化１
の増感色素の含まれる層には化２で示される化合物を実
質的に含まず、かつ化１の増感色素の含まれる層には化
３で示される化合物を少なくとも１つ含有し、既非感光
性層の少なくとも１層に化２で示される化合物を少なく
とも１つ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】 化１中、Ｚ，Ｚ１はそれぞれシアニン色素で通常用いら
れる５員環及び／または６員環の含窒素複素環を形成す
るのに必要な原子群を表す。Ｒ，Ｒ１はそれぞれ飽和ま
たは不飽和脂肪族基を表す。ＱとＱ１（組合せ）は４−
チアゾリジノン、５−チアゾリジノン、または４−イミ
ダゾリジノン核を形成するのに必要な原子群を表す。 またＬ１とＲ、Ｌ３とＲ１はそれぞれメチレン鎖で
結合して含窒素複素環を形成してもよい。ｍ、ｎは０ま
たは１を表す。Ｘはアニオンたとえばクロルイオン、ブ
ロムイオン、ヨードイオン、Ｐ−トルエンスルホン酸イ
オン等を表す。Ｐは０または１を表し、分子内塩の時は
Ｐ＝０を表す。 【化２】 化２中Ｚ２は５員環及び／または６員複素環を形成する
のに必要な非金属原子群を表す。Ｍは水素原子、アルカ
リ金属原子、アンモニウム基または有機アミン残基を表
す。 【化３】 化３中ＹおよびＺ３はそれぞれ独立に、メチン、置換メ
チン、または窒素原子のいずれかを表し、Ｑ２は５ない
し６員のヘテロ環を形成するのに必要な原子群を表し、
これらの環はさらに縮合されてもよい。Ｍ１は水素原子
または陽イオンを表す。Claim 1: A silver halide photosensitive material having at least one photosensitive silver halide emulsion layer on a photographic support and at least one non-photosensitive layer on the same side of the support as the emulsion layer. In the material, at least one of the emulsion layers contains at least one sensitizing dye represented by chemical formula 1, and
The layer containing the sensitizing dye of Chemical Formula 1 does not substantially contain the compound represented by Chemical Formula 2, and the layer containing the sensitizing dye of Chemical Formula 1 contains at least one compound represented by Chemical Formula 3. A silver halide photographic material, characterized in that at least one of the non-photosensitive layers contains at least one compound represented by Chemical Formula 2. embedded image In Chemical Formula 1, Z and Z1 each represent an atomic group necessary to form a 5-membered ring and/or 6-membered nitrogen-containing heterocycle commonly used in cyanine dyes. R and R1 each represent a saturated or unsaturated aliphatic group. Q and Q1 (combination) is 4-
Represents an atomic group necessary to form a thiazolidinone, 5-thiazolidinone, or 4-imidazolidinone nucleus. Further, L1 and R, and L3 and R1 may be bonded to each other via a methylene chain to form a nitrogen-containing heterocycle. m and n represent 0 or 1. X represents an anion such as chlorine ion, bromide ion, iodo ion, P-toluenesulfonate ion, etc. P represents 0 or 1, and when it is an inner salt, P=0. embedded image Z2 in Chemical Formula 2 represents a nonmetallic atomic group necessary to form a 5-membered ring and/or a 6-membered heterocycle. M represents a hydrogen atom, an alkali metal atom, an ammonium group, or an organic amine residue. [Chemical Formula 3] In Chemical Formula 3, Y and Z3 each independently represent either methine, substituted methine, or a nitrogen atom, Q2 represents an atomic group necessary to form a 5- to 6-membered heterocycle,
These rings may be further fused. M1 represents a hydrogen atom or a cation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3125487A JP2597432B2 (en) | 1991-04-26 | 1991-04-26 | Silver halide photographic material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3125487A JP2597432B2 (en) | 1991-04-26 | 1991-04-26 | Silver halide photographic material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04328542A true JPH04328542A (en) | 1992-11-17 |
| JP2597432B2 JP2597432B2 (en) | 1997-04-09 |
Family
ID=14911310
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3125487A Expired - Lifetime JP2597432B2 (en) | 1991-04-26 | 1991-04-26 | Silver halide photographic material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2597432B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4454133B2 (en) * | 2000-10-02 | 2010-04-21 | ヤンマー株式会社 | Vegetable transplanter |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62215272A (en) * | 1986-02-17 | 1987-09-21 | Fuji Photo Film Co Ltd | Color image forming method |
| JPS6413539A (en) * | 1987-07-07 | 1989-01-18 | Mitsubishi Paper Mills Ltd | Silver halide photographic sensitive material |
| JPH01144041A (en) * | 1987-11-30 | 1989-06-06 | Mitsubishi Paper Mills Ltd | Photographic silver halide emulsion |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4910129A (en) | 1987-04-17 | 1990-03-20 | Mitsubishi Paper Mills, Ltd. | Silver halide photographic light sensitive material |
-
1991
- 1991-04-26 JP JP3125487A patent/JP2597432B2/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62215272A (en) * | 1986-02-17 | 1987-09-21 | Fuji Photo Film Co Ltd | Color image forming method |
| JPS6413539A (en) * | 1987-07-07 | 1989-01-18 | Mitsubishi Paper Mills Ltd | Silver halide photographic sensitive material |
| JPH01144041A (en) * | 1987-11-30 | 1989-06-06 | Mitsubishi Paper Mills Ltd | Photographic silver halide emulsion |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2597432B2 (en) | 1997-04-09 |
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