JPH0456949A - Silver halide photographic sensitive material - Google Patents
Silver halide photographic sensitive materialInfo
- Publication number
- JPH0456949A JPH0456949A JP2167972A JP16797290A JPH0456949A JP H0456949 A JPH0456949 A JP H0456949A JP 2167972 A JP2167972 A JP 2167972A JP 16797290 A JP16797290 A JP 16797290A JP H0456949 A JPH0456949 A JP H0456949A
- Authority
- JP
- Japan
- Prior art keywords
- group
- silver halide
- compound
- heterocyclic
- groups
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- -1 Silver halide Chemical class 0.000 title claims abstract description 105
- 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 abstract description 31
- 125000000623 heterocyclic group Chemical group 0.000 claims abstract description 57
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 43
- 125000003118 aryl group Chemical group 0.000 claims abstract description 39
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 26
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims abstract description 16
- 125000004104 aryloxy group Chemical group 0.000 claims abstract description 10
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 8
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 claims abstract description 5
- 125000004430 oxygen atom Chemical group O* 0.000 claims abstract description 5
- 125000004434 sulfur atom Chemical group 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims description 93
- 125000000304 alkynyl group Chemical group 0.000 claims description 35
- 125000003342 alkenyl group Chemical group 0.000 claims description 32
- 239000000839 emulsion Substances 0.000 claims description 32
- 125000001424 substituent group Chemical group 0.000 claims description 21
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 17
- 125000003545 alkoxy group Chemical group 0.000 claims description 16
- 125000003302 alkenyloxy group Chemical group 0.000 claims description 8
- 125000005133 alkynyloxy group Chemical group 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 4
- 229920006395 saturated elastomer Polymers 0.000 claims description 4
- 238000012545 processing Methods 0.000 abstract description 6
- 150000003839 salts Chemical class 0.000 abstract description 6
- 150000001412 amines Chemical class 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract 2
- 125000006193 alkinyl group Chemical group 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 40
- 239000000203 mixture Substances 0.000 description 28
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 26
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- 238000000034 method Methods 0.000 description 22
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 18
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 17
- 239000013078 crystal Substances 0.000 description 15
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 14
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 14
- 238000001914 filtration Methods 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 13
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 13
- 108010010803 Gelatin Proteins 0.000 description 12
- 239000008273 gelatin Substances 0.000 description 12
- 229920000159 gelatin Polymers 0.000 description 12
- 235000019322 gelatine Nutrition 0.000 description 12
- 235000011852 gelatine desserts Nutrition 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 239000002245 particle Substances 0.000 description 11
- 229910001868 water Inorganic materials 0.000 description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 9
- 238000011161 development Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- 239000000084 colloidal system Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 239000004094 surface-active agent Substances 0.000 description 8
- 238000001308 synthesis method Methods 0.000 description 8
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 7
- 238000009472 formulation Methods 0.000 description 7
- 239000011241 protective layer Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 125000005647 linker group Chemical group 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 230000001737 promoting effect Effects 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 230000006911 nucleation Effects 0.000 description 5
- 238000010899 nucleation Methods 0.000 description 5
- 230000035945 sensitivity Effects 0.000 description 5
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 4
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 4
- 125000002252 acyl group Chemical group 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 4
- 150000002429 hydrazines Chemical class 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- SBYHFKPVCBCYGV-UHFFFAOYSA-N quinuclidine Chemical group C1CC2CCN1CC2 SBYHFKPVCBCYGV-UHFFFAOYSA-N 0.000 description 4
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 4
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 4
- MAUMSNABMVEOGP-UHFFFAOYSA-N (methyl-$l^{2}-azanyl)methane Chemical compound C[N]C MAUMSNABMVEOGP-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- 229910021612 Silver iodide Inorganic materials 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000004992 fast atom bombardment mass spectroscopy Methods 0.000 description 3
- 239000005457 ice water Substances 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 125000001624 naphthyl group Chemical group 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 125000003386 piperidinyl group Chemical group 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 229930182490 saponin Natural products 0.000 description 3
- 150000007949 saponins Chemical class 0.000 description 3
- 235000017709 saponins Nutrition 0.000 description 3
- 230000001235 sensitizing effect Effects 0.000 description 3
- 229940045105 silver iodide Drugs 0.000 description 3
- 235000010265 sodium sulphite Nutrition 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea group Chemical group NC(=S)N UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 2
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 2
- ZFIQGRISGKSVAG-UHFFFAOYSA-N 4-methylaminophenol Chemical compound CNC1=CC=C(O)C=C1 ZFIQGRISGKSVAG-UHFFFAOYSA-N 0.000 description 2
- GFFGJBXGBJISGV-UHFFFAOYSA-N Adenine Chemical compound NC1=NC=NC2=C1N=CN2 GFFGJBXGBJISGV-UHFFFAOYSA-N 0.000 description 2
- 229930024421 Adenine Natural products 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 2
- 229960000643 adenine Drugs 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000003282 alkyl amino group Chemical group 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 125000006367 bivalent amino carbonyl group Chemical group [H]N([*:1])C([*:2])=O 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 2
- 125000000480 butynyl group Chemical group [*]C#CC([H])([H])C([H])([H])[H] 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 239000013256 coordination polymer Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 description 2
- HBNYJWAFDZLWRS-UHFFFAOYSA-N ethyl isothiocyanate Chemical compound CCN=C=S HBNYJWAFDZLWRS-UHFFFAOYSA-N 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 235000019256 formaldehyde Nutrition 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229940015043 glyoxal Drugs 0.000 description 2
- UYTPUPDQBNUYGX-UHFFFAOYSA-N guanine Chemical compound O=C1NC(N)=NC2=C1N=CN2 UYTPUPDQBNUYGX-UHFFFAOYSA-N 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 239000006224 matting agent Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 125000004170 methylsulfonyl group Chemical group [H]C([H])([H])S(*)(=O)=O 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 125000005740 oxycarbonyl group Chemical group [*:1]OC([*:2])=O 0.000 description 2
- AHWALFGBDFAJAI-UHFFFAOYSA-N phenyl carbonochloridate Chemical compound ClC(=O)OC1=CC=CC=C1 AHWALFGBDFAJAI-UHFFFAOYSA-N 0.000 description 2
- 239000004848 polyfunctional curative Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000003755 preservative agent Substances 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- USPWKWBDZOARPV-UHFFFAOYSA-N pyrazolidine Chemical compound C1CNNC1 USPWKWBDZOARPV-UHFFFAOYSA-N 0.000 description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
- 239000001397 quillaja saponaria molina bark Substances 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229940124530 sulfonamide Drugs 0.000 description 2
- 150000003456 sulfonamides Chemical group 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 125000004014 thioethyl group Chemical group [H]SC([H])([H])C([H])([H])* 0.000 description 2
- 229930192474 thiophene Natural products 0.000 description 2
- 125000005147 toluenesulfonyl group Chemical group C=1(C(=CC=CC1)S(=O)(=O)*)C 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- RVXJIYJPQXRIEM-UHFFFAOYSA-N 1-$l^{1}-selanyl-n,n-dimethylmethanimidamide Chemical compound CN(C)C([Se])=N RVXJIYJPQXRIEM-UHFFFAOYSA-N 0.000 description 1
- TXJYONBSFGLSSF-UHFFFAOYSA-N 1-(diethylamino)propane-1,2-diol Chemical compound CCN(CC)C(O)C(C)O TXJYONBSFGLSSF-UHFFFAOYSA-N 0.000 description 1
- GGZHVNZHFYCSEV-UHFFFAOYSA-N 1-Phenyl-5-mercaptotetrazole Chemical compound SC1=NN=NN1C1=CC=CC=C1 GGZHVNZHFYCSEV-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- BDKLKNJTMLIAFE-UHFFFAOYSA-N 2-(3-fluorophenyl)-1,3-oxazole-4-carbaldehyde Chemical compound FC1=CC=CC(C=2OC=C(C=O)N=2)=C1 BDKLKNJTMLIAFE-UHFFFAOYSA-N 0.000 description 1
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 description 1
- QPKNFEVLZVJGBM-UHFFFAOYSA-N 2-aminonaphthalen-1-ol Chemical compound C1=CC=CC2=C(O)C(N)=CC=C21 QPKNFEVLZVJGBM-UHFFFAOYSA-N 0.000 description 1
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical class NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 1
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 description 1
- MGADZUXDNSDTHW-UHFFFAOYSA-N 2H-pyran Chemical compound C1OC=CC=C1 MGADZUXDNSDTHW-UHFFFAOYSA-N 0.000 description 1
- FJWJYHHBUMICTP-UHFFFAOYSA-N 4,4-dimethylpyrazolidin-3-one Chemical compound CC1(C)CNNC1=O FJWJYHHBUMICTP-UHFFFAOYSA-N 0.000 description 1
- SVMDYSGSRGLSCG-UHFFFAOYSA-N 4-(hydroxymethyl)pyrazolidin-3-one Chemical compound OCC1CNNC1=O SVMDYSGSRGLSCG-UHFFFAOYSA-N 0.000 description 1
- XSFKCGABINPZRK-UHFFFAOYSA-N 4-aminopyrazol-3-one Chemical class NC1=CN=NC1=O XSFKCGABINPZRK-UHFFFAOYSA-N 0.000 description 1
- KMVPXBDOWDXXEN-UHFFFAOYSA-N 4-nitrophenylhydrazine Chemical compound NNC1=CC=C([N+]([O-])=O)C=C1 KMVPXBDOWDXXEN-UHFFFAOYSA-N 0.000 description 1
- RWXZXCZBMQPOBF-UHFFFAOYSA-N 5-methyl-1H-benzimidazole Chemical compound CC1=CC=C2N=CNC2=C1 RWXZXCZBMQPOBF-UHFFFAOYSA-N 0.000 description 1
- LRUDIIUSNGCQKF-UHFFFAOYSA-N 5-methyl-1H-benzotriazole Chemical compound C1=C(C)C=CC2=NNN=C21 LRUDIIUSNGCQKF-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- DHXGNDYOCQCVEF-UHFFFAOYSA-N CC1=CC2=C(NN=N2)C=C1.BrC1=CC2=C(NN=N2)C=C1 Chemical compound CC1=CC2=C(NN=N2)C=C1.BrC1=CC2=C(NN=N2)C=C1 DHXGNDYOCQCVEF-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 101150065749 Churc1 gene Proteins 0.000 description 1
- DFQVGTFDFGVTGK-KVVVOXFISA-M ClC(C(=O)[O-])CCCCCC\C=C/CCCCCCCC.[K+] Chemical compound ClC(C(=O)[O-])CCCCCC\C=C/CCCCCCCC.[K+] DFQVGTFDFGVTGK-KVVVOXFISA-M 0.000 description 1
- 102100040996 Cochlin Human genes 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 1
- 101000748988 Homo sapiens Cochlin Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- WRUZLCLJULHLEY-UHFFFAOYSA-N N-(p-hydroxyphenyl)glycine Chemical compound OC(=O)CNC1=CC=C(O)C=C1 WRUZLCLJULHLEY-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 102100038239 Protein Churchill Human genes 0.000 description 1
- 101150030723 RIR2 gene Proteins 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical class OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 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
- SJOOOZPMQAWAOP-UHFFFAOYSA-N [Ag].BrCl Chemical compound [Ag].BrCl SJOOOZPMQAWAOP-UHFFFAOYSA-N 0.000 description 1
- XCFIVNQHHFZRNR-UHFFFAOYSA-N [Ag].Cl[IH]Br Chemical group [Ag].Cl[IH]Br XCFIVNQHHFZRNR-UHFFFAOYSA-N 0.000 description 1
- TUCNEACPLKLKNU-UHFFFAOYSA-N acetyl Chemical compound C[C]=O TUCNEACPLKLKNU-UHFFFAOYSA-N 0.000 description 1
- 125000004442 acylamino group Chemical group 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- 125000004414 alkyl thio group Chemical group 0.000 description 1
- 125000005336 allyloxy group Chemical group 0.000 description 1
- HTKFORQRBXIQHD-UHFFFAOYSA-N allylthiourea Chemical compound NC(=S)NCC=C HTKFORQRBXIQHD-UHFFFAOYSA-N 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 125000004397 aminosulfonyl group Chemical group NS(=O)(=O)* 0.000 description 1
- XYXNTHIYBIDHGM-UHFFFAOYSA-N ammonium thiosulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-UHFFFAOYSA-N 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000005161 aryl oxy carbonyl group Chemical group 0.000 description 1
- 125000005110 aryl thio group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 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
- 239000002585 base Substances 0.000 description 1
- 150000001556 benzimidazoles Chemical class 0.000 description 1
- 150000001565 benzotriazoles Chemical class 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001661 cadmium Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000006297 carbonyl amino group Chemical group [H]N([*:2])C([*:1])=O 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- WBLIXGSTEMXDSM-UHFFFAOYSA-N chloromethane Chemical compound Cl[CH2] WBLIXGSTEMXDSM-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000002872 contrast media Substances 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000004802 cyanophenyl group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 238000011033 desalting Methods 0.000 description 1
- 150000004683 dihydrates Chemical class 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
- OWZFULPEVHKEKS-UHFFFAOYSA-N ethyl 2-chloro-2-oxoacetate Chemical compound CCOC(=O)C(Cl)=O OWZFULPEVHKEKS-UHFFFAOYSA-N 0.000 description 1
- OAYLNYINCPYISS-UHFFFAOYSA-N ethyl acetate;hexane Chemical compound CCCCCC.CCOC(C)=O OAYLNYINCPYISS-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 125000004005 formimidoyl group Chemical group [H]\N=C(/[H])* 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 208000015181 infectious disease Diseases 0.000 description 1
- 230000002458 infectious effect Effects 0.000 description 1
- 239000002198 insoluble material Substances 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002503 iridium Chemical class 0.000 description 1
- 159000000014 iron salts Chemical class 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 125000002757 morpholinyl group Chemical group 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 150000002891 organic anions Chemical class 0.000 description 1
- 125000003452 oxalyl group Chemical group *C(=O)C(*)=O 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 1
- 125000005981 pentynyl group Chemical group 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 125000006678 phenoxycarbonyl group Chemical group 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 125000004193 piperazinyl group Chemical group 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 description 1
- 235000019252 potassium sulphite Nutrition 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- NDGRWYRVNANFNB-UHFFFAOYSA-N pyrazolidin-3-one Chemical class O=C1CCNN1 NDGRWYRVNANFNB-UHFFFAOYSA-N 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000005554 pyridyloxy group Chemical group 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- 125000001308 pyruvoyl group Chemical group O=C([*])C(=O)C([H])([H])[H] 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003283 rhodium Chemical class 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- IYKVLICPFCEZOF-UHFFFAOYSA-N selenourea Chemical compound NC(N)=[Se] IYKVLICPFCEZOF-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229940087562 sodium acetate trihydrate Drugs 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 229960000999 sodium citrate dihydrate Drugs 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- HLWRUJAIJJEZDL-UHFFFAOYSA-M sodium;2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]acetate Chemical compound [Na+].OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC([O-])=O HLWRUJAIJJEZDL-UHFFFAOYSA-M 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 238000005556 structure-activity relationship Methods 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000003718 tetrahydrofuranyl group Chemical group 0.000 description 1
- 125000005958 tetrahydrothienyl group Chemical group 0.000 description 1
- 150000003475 thallium Chemical class 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 125000001391 thioamide group Chemical group 0.000 description 1
- 125000001425 triazolyl group Chemical group 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 125000004044 trifluoroacetyl group Chemical group FC(C(=O)*)(F)F 0.000 description 1
- 125000004205 trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
- G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
- G03C1/061—Hydrazine compounds
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
- G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
- G03C1/08—Sensitivity-increasing substances
- G03C1/10—Organic substances
- G03C2001/108—Nucleation accelerating compound
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、支持体上にハロゲン化銀感光層を有する写真
感光材料に関し、更に詳しくは高コントラストが得られ
るハロゲン化銀写真感光材料に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a photographic material having a silver halide photosensitive layer on a support, and more particularly to a silver halide photographic material capable of providing high contrast.
写真製版工程では連続調の原稿を網点画像に変換する工
程が含まれる。この工程には、超硬調の画像再現をなし
得る写真技術として伝染現像による技術が用いられてき
た。The photoengraving process includes converting a continuous tone original into a halftone image. In this process, contagious development has been used as a photographic technique capable of reproducing ultra-high contrast images.
伝染現像に用いられるリス型ハロゲン化銀写真感光材料
は、例えは平均粒子径か０．２μｍで粒子分布か狭く粒
子の形も揃っていて、かつ塩化銀の含有率の高い（少な
くとも５０モル％以上）塩臭化銀乳剤よりなる。このリ
ス型ハロゲン化銀写真感光材料を亜硫酸イオン濃度か低
いアルカリ性ハイドロキノン現像液で処理することによ
り高いコントラスト、高鮮鋭度、高解像力の画像が得ら
れる。The lithium-type silver halide photographic material used for infectious development has, for example, an average grain size of 0.2 μm, a narrow grain distribution, a uniform grain shape, and a high silver chloride content (at least 50 mol%). Above) consists of a silver chlorobromide emulsion. By processing this lithium-type silver halide photographic material with an alkaline hydroquinone developer having a low sulfite ion concentration, images with high contrast, high sharpness, and high resolution can be obtained.
しかしながら、これらのリス型現像液は空気酸化を受け
やすいことがら保恒性が極めて悪いため、連続使用の際
においても、現像品質を一定に保つことは難しい。However, these lithium-type developers are susceptible to air oxidation and have extremely poor stability, making it difficult to maintain constant development quality even during continuous use.
上記のリス型現像液を使わずに迅速に、かつ高コントラ
ストの画像を得る方法が知られている。A method of quickly obtaining a high-contrast image without using the above-mentioned Lith type developer is known.
例えば米国特許２，４１９，９７５号、特開昭５１−１
６６２３号及び特開昭５１−２０９２１号、特開昭５６
−１０６２４４号等に見られるように、ハロゲン化銀感
光材料中にヒドラジン誘導体を含有せしめるものである
。For example, U.S. Pat.
No. 6623 and JP-A-51-20921, JP-A-56
As seen in No. 106244, etc., a hydrazine derivative is contained in a silver halide photosensitive material.
これらの方法によれば、現像液中に亜硫酸イオン濃度を
高く保つことができ、保恒性を高めた状態で処理するこ
とができる。According to these methods, it is possible to maintain a high sulfite ion concentration in the developer, and it is possible to process with improved preservability.
しかしながら、これらの方法では、ヒドラジン誘導体の
硬調性を充分発揮させるためにｐＨ１１以上のｐＨを有
する現像液で処理しなければならなかった。ｐＨ１１以
上の高いｐＨを有する現像液は、空気にふれると現像主
薬が酸化しやすいリス現像液よりは安定であるが、現像
主薬の酸化によって、しばしば超硬調な画像が得られな
いことがある。However, these methods require processing with a developer having a pH of 11 or higher in order to fully exhibit the high contrast properties of the hydrazine derivative. A developer having a high pH of 11 or more is more stable than a lithium developer whose developing agent is easily oxidized when exposed to air, but due to the oxidation of the developing agent, it is often impossible to obtain ultra-high contrast images.
この欠点を補うために特開昭６３〜２９７５１号及びヨ
ーロッパ特許３３３．４３５号、同３４５０２５号には
、比較的低ｐａの現像液でも硬調化する硬調化剤を含む
ハロゲン化銀写真感光材料が開示されている。In order to compensate for this drawback, Japanese Patent Application Laid-Open Nos. 63-29751 and European Patent Nos. 333.435 and 345025 disclose silver halide photographic materials containing a contrast-enhancing agent that can achieve high contrast even with a relatively low pa developer. Disclosed.
しかし、これらのような硬調化剤を含むハロゲン化銀写
真感光材料をｐＨ１１未満の現像液で処理した場合、硬
調化が不充分であり、満足な網点性能が得られないのが
現状である。However, when silver halide photographic light-sensitive materials containing high contrast agents such as these are processed with a developer having a pH of less than 11, the present situation is that the high contrast is insufficient and satisfactory halftone dot performance cannot be obtained. .
一方、ヨーロッパ特許３６４．１６６号及び特開昭６２
＝２２２２４１号、同６０−１４０３４０号、同６２−
２５０４３９号、同６２−２８０７３３号等には硬調化
を促進する為の造核促進剤が記載されており、確かにこ
れらの化合物を乳剤層に添加することにより、網点性能
は良くなるが、網点中に砂状、ビン状のカブリいわゆる
黒ピンが発生して網点画像の品質を損なうという問題点
を生ずることがわかった。On the other hand, European Patent No. 364.166 and JP-A-62
= No. 222241, No. 60-140340, No. 62-
No. 250439, No. 62-280733, etc., describe nucleation promoters for promoting high contrast, and it is true that adding these compounds to the emulsion layer improves halftone dot performance. It has been found that sand-like or bottle-like fog, so-called black pins, occur in the halftone dots, causing a problem in which the quality of the halftone dot image is impaired.
従って、上記のような諸問題を解決した、有効な硬調化
剤及び造核促進剤を用いた感光材料が望まれている。Therefore, there is a need for a photosensitive material using an effective contrast enhancer and nucleation accelerator that solves the above-mentioned problems.
本発明の目的は、ｐＨ１１未満の現像液で処理しても硬
調な写真特性を有すると共に、網点画像中に発生するカ
ブリを抑制して良好な網点性能を有するハロゲン化銀写
真感光材料を提供することにある。An object of the present invention is to provide a silver halide photographic material that has high contrast photographic properties even when processed with a developer having a pH of less than 11, and also has good halftone dot performance by suppressing fog that occurs in halftone images. It is about providing.
本発明の上記目的は、下記構成のハロゲン化銀写真感光
材料により達成された。The above objects of the present invention have been achieved by a silver halide photographic material having the following structure.
即ち、少なくとも１層の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、下記一般式〔Ａ〕及
びＣＢ）で表されるヒドラジン化合物を少なくとも１種
含有し、かつアミン化合物、ヒドラジン化合物、四級オ
ニウム塩化合物から選ばれる少なくとも１種の造核促進
化合物を含有することを特徴とするハロゲン化銀写真感
光材料によって上記目的は達成された。That is, a silver halide photographic material having at least one silver halide emulsion layer contains at least one hydrazine compound represented by the following general formulas [A] and CB), and contains an amine compound, a hydrazine compound, The above object has been achieved by a silver halide photographic material containing at least one nucleation promoting compound selected from quaternary onium salt compounds.
一般式〔Ａ〕
一般式〔Ｂ〕
Ａｒ−ＮＨＮＨ−ＣＣ−ＯＲ３
式中、Ａｒはアリール基又は硫黄原子又はは酸素原子を
少なくとも一つ含む複素環基を表し、ｎは１又は２の整
数を表す。ｎ−１の時、Ｒ１及びＲ２は各々、水素原子
、アルキル基、アルケニル基、アルキニル基、アリール
基、複素環基、ヒドロキシル基、アルコキシ基、アルケ
ニルオキシ基、アルキニルオキシ基、アリールオキシ基
又は複素環オキシ基を表し、Ｒ１とＲ２は窒素原子と共
に環を形成してもよい。ｎ＝２の時、Ｒ２及びＲ２は各
々、水素原子、アルキル基、アルケニル基、アルキニル
基、アリール基、飽和もしくは不飽和複素環基、ヒドロ
キシル基、アルコキシ基、アルケニルオキシ基、アルキ
ニルオキシ基、アリールオキシ基又は複素環オキシ基を
表す。General formula [A] General formula [B] Ar-NHNH-CC-OR3 In the formula, Ar represents an aryl group or a heterocyclic group containing at least one sulfur atom or oxygen atom, and n is an integer of 1 or 2. represent. When n-1, R1 and R2 are each a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a hydroxyl group, an alkoxy group, an alkenyloxy group, an alkynyloxy group, an aryloxy group, or a hetero It represents a ring oxy group, and R1 and R2 may form a ring together with a nitrogen atom. When n=2, R2 and R2 are each a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a saturated or unsaturated heterocyclic group, a hydroxyl group, an alkoxy group, an alkenyloxy group, an alkynyloxy group, an aryl group. Represents an oxy group or a heterocyclic oxy group.
ただし、ｎ＝２の時、Ｒ１及びＲ２のうち少なくトモ一
方はアルケニル基、アルキニル基、飽和複素環基、ヒド
ロキシル基、アルコキシ基、アルケニルオキシ基、アル
キニルオキシ基、アリールオキシ基又は複素環オキシ基
を表すものとする。However, when n=2, at least one of R1 and R2 is an alkenyl group, an alkynyl group, a saturated heterocyclic group, a hydroxyl group, an alkoxy group, an alkenyloxy group, an alkynyloxy group, an aryloxy group, or a heterocyclic group. shall represent.
Ｒ１はアルキニル基又は飽和複素環基を表す。R1 represents an alkynyl group or a saturated heterocyclic group.
一般式ＣＡ）又はＣＢ）で表される化合物には、式中の
−ＮＨＮＨ−の少なくともいずれかのＨが置換基で置換
されたものを含む。The compounds represented by the general formula CA) or CB) include compounds in which at least one H of -NHNH- in the formula is substituted with a substituent.
一般式〔Ａ〕及びＣＢ）で表される化合物を更に詳しく
説明すると、Ａｒはアリール基（例えばフェニル、ナフ
チル等）又は硫黄原子もしくは酸素原子を少なくとも一
つ含む複素環基（例えばチオフェン、フラン、ベンゾチ
オフェン、ピラン等）を表す。To explain the compounds represented by the general formulas [A] and CB) in more detail, Ar is an aryl group (e.g. phenyl, naphthyl, etc.) or a heterocyclic group containing at least one sulfur atom or oxygen atom (e.g. thiophene, furan, benzothiophene, pyran, etc.).
Ｒ８及びＲ２は各々、水素原子、アルキル基（例えばメ
チル、エチル、メトキシエチル、シアノエチル、ヒドロ
キンエチル、ベンジル、トリフルオロエチル等）、アル
ケニル基（例えばアリル、ブテニル、ペンテニル、ペン
タジェニル等）、アルキニル基（例えばプロパルギル、
ブチニル、ペンチニル等）、アリール基（例えばフェニ
ル、ナフチル、シアノフェニル、メトキシフェニル等）
、複素環基（例えばピリジン、チオフェン、７ランの様
な不飽和複素環基及びテトラヒドロ７ラン、スルホラン
の様な飽和複素環基）、ヒドロキシル基、アルコキシ基
（例えばメトキシ、エトキシ、ベンジルオキシ、シアノ
メトキシ等）、アルケニルオキシ基（例えばアリルオキ
シ、ブテニルオキシ等）、アルキニルオキシ基（例えば
グロパルギルオキシ、ブチニルオキシ等）、アリールオ
キシ基（例えばフェノキシ、ナフチルオキシ等）又は複
素環オキシ基（例えばピリジルオキシ、ピリミジルオキ
シ等）を表し、ｎ−１の時、Ｒ１とＲ１は窒素原子と共
に環（例えばピペリジン、ピペラジン、モルホリン等）
を形成してもよい。R8 and R2 each represent a hydrogen atom, an alkyl group (e.g. methyl, ethyl, methoxyethyl, cyanoethyl, hydroquinethyl, benzyl, trifluoroethyl, etc.), an alkenyl group (e.g. allyl, butenyl, pentenyl, pentagenyl, etc.), an alkynyl group (e.g. propargyl,
butynyl, pentynyl, etc.), aryl groups (e.g. phenyl, naphthyl, cyanophenyl, methoxyphenyl, etc.)
, heterocyclic groups (e.g. unsaturated heterocyclic groups such as pyridine, thiophene, 7-rane and saturated heterocyclic groups such as tetrahydr 7-rane, sulfolane), hydroxyl groups, alkoxy groups (e.g. methoxy, ethoxy, benzyloxy, cyano methoxy, etc.), alkenyloxy groups (e.g., allyloxy, butenyloxy, etc.), alkynyloxy groups (e.g., glopargyloxy, butynyloxy, etc.), aryloxy groups (e.g., phenoxy, naphthyloxy, etc.), or heterocyclicoxy groups (e.g., pyridyloxy, pyrimidyloxy, etc.), and when n-1, R1 and R1 represent a ring together with a nitrogen atom (e.g. piperidine, piperazine, morpholine, etc.)
may be formed.
ただしｎ＝２の時、Ｒ１及びＲ２のうち少なくとも一方
はアルケニル基、アルキニル基、飽和複素環基、ヒドロ
キシル基、アルコキシ基、アルケニルオキシ基、アルキ
ニルオキシ基、アリールオキシ基、又は複素環オキシ基
を表すものとする。However, when n=2, at least one of R1 and R2 is an alkenyl group, an alkynyl group, a saturated heterocyclic group, a hydroxyl group, an alkoxy group, an alkenyloxy group, an alkynyloxy group, an aryloxy group, or a heterocyclic group. shall be expressed.
Ｒ３で表されるアルキニル基及び飽和複素環基の具体例
としては、上述したようなものが挙げられる。Specific examples of the alkynyl group and saturated heterocyclic group represented by R3 include those mentioned above.
Ａｒで表されるアリール基又は硫黄原子もしくは酸素原
子を少なくとも一つ有する複素環基には、種々の置換基
が導入できる。導入できる置換基としては、例えばハロ
ゲン原子ならびにアルキル、アリール、アルコキシ、ア
リールオキシ、アシルオキシ、アルキルチオ、アリール
チオ、スルホニル、アルコキシカルボニル、アリールオ
キシカルボニル、カルバモイル、スルファモイル、アシ
ル、アミノ、アルキルアミノ、アルキリデンアミノ、ア
リールアミノ、アシルアミノ、スルホンアミド、アリー
ルアミノチオカルボニルアミノ、ヒドロキシル、カルボ
キシル、スルホ、ニトロ、シアノなどの基が挙げられる
。Various substituents can be introduced into the aryl group represented by Ar or the heterocyclic group having at least one sulfur atom or oxygen atom. Examples of substituents that can be introduced include halogen atoms, alkyl, aryl, alkoxy, aryloxy, acyloxy, alkylthio, arylthio, sulfonyl, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, sulfamoyl, acyl, amino, alkylamino, alkylideneamino, and aryl. Examples include groups such as amino, acylamino, sulfonamide, arylaminothiocarbonylamino, hydroxyl, carboxyl, sulfo, nitro, and cyano.
これらの置換基のうち、スルホンアミド、アルキルアミ
ノ、アルキリデンアミノ等の基が好ましい。Among these substituents, groups such as sulfonamide, alkylamino, and alkylidene amino are preferred.
又、Ａｒは耐拡散基又はハロゲン化銀吸着促進基を少な
くとも一つ含むことが好ましい。Further, it is preferable that Ar contains at least one diffusion-resistant group or silver halide adsorption-promoting group.
耐拡散基としては、カプラー等の不動性写真用添加剤に
おいて常用されているバラスト基が好ましい。The diffusion-resistant group is preferably a ballast group commonly used in immobile photographic additives such as couplers.
パラスト基は８以上の炭素数を有する写真性に対して比
較的不活性な基であり、例えばアルキル基、アルコキシ
基、フェニル基、アルキルフェニル基、フェノキシ基、
アルキルフェノキシ基などの中から選ぶことかで・きる
。The Palast group is a group having 8 or more carbon atoms and is relatively inert to photography, such as an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group,
You can choose from among alkylphenoxy groups, etc.
ハロゲン化銀吸着促進基としては、チオ尿素基、チオウ
レタン基、複素環チオアミド基、メルカプト複素環基、
トリアゾール基などの米国特許４，３８５．１０８号に
記載された基が挙げられる。Examples of silver halide adsorption promoting groups include thiourea group, thiourethane group, heterocyclic thioamide group, mercapto heterocyclic group,
Included are groups described in US Pat. No. 4,385.108, such as triazole groups.
一般式〔Ａ〕及びＣＢ）中の−ＮＨＮＨ−のＲ１即ちヒ
ドラジンの水素原子は、スルホニル基（例えばメタンス
ルホニル、トルエンスルホニル等）、アシル基（例えば
、アセチル、トリフルオロアセチル、エトキシカルボニ
ル等）、オキザリル基（例えばエトキザリル、ピルボイ
ル等）等の置換基で置換されていてもよく、一般式〔Ａ
）及び〔Ｂ〕で表される化合物はこのようなものを含む
。In the general formulas [A] and CB), R1 of -NHNH-, that is, the hydrogen atom of hydrazine, is a sulfonyl group (e.g., methanesulfonyl, toluenesulfonyl, etc.), an acyl group (e.g., acetyl, trifluoroacetyl, ethoxycarbonyl, etc.), It may be substituted with a substituent such as an oxalyl group (for example, ethoxalyl, pyruvoyl, etc.), and the general formula [A
) and [B] include such compounds.
本発明においてより好ましい化合物は、一般式ＣＡ ）
のｎ＝２の場合の化合物及び一般式〔Ｂ〕の化合物であ
る。More preferred compounds in the present invention have the general formula CA)
These are the compound when n=2 and the compound of general formula [B].
一般式〔Ａ〕のｎ＝２の化合物において、Ｒ１及びＲ２
が水素原子、アルキル基、アルケニル基、アルキニル基
、アリール基、飽和もしくは不飽和複素環基、ヒドロキ
シル基又はアルコキシ基であり、かつＲ１及びＲ２のう
ち少なくとも一方はアルケニル基、アルキニル基、飽和
複素環基、ヒドロキシル基又はアルコキシ基を表す化合
物が更に好ましい。In the compound of general formula [A] where n=2, R1 and R2
is a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a saturated or unsaturated heterocyclic group, a hydroxyl group, or an alkoxy group, and at least one of R1 and R2 is an alkenyl group, an alkynyl group, or a saturated heterocyclic group. More preferred are compounds representing a group, a hydroxyl group or an alkoxy group.
上記一般式ＣＡ、 ）及び〔Ｂ〕で表される化合物の代
表的具体例を以下に示すが、本発明はこれらネーＮＨＮ
ＨＣＯＣＯＮ（ＣＨ２ＣミＣ）Ｉ）２（ｌＯ）
ＣＨ。Typical specific examples of the compounds represented by the above general formulas CA, ) and [B] are shown below, and the present invention
HCOCON(CH2CmiC)I)2(lO) CH.
＊ −ＮＨＮＨＣＯＣＯＮＨＣＨ２ＣＨ＝ ＣＨ２υ２ ２Ｈ５ しｒＩ３ しＩ′＋３ Ｃ，Ｈ。*-NHNHCOCONHCH2CH=CH2υ2 2H5 ShirI3 I'+3 C,H.
しｆ１１ しｉコ しｆ１３ し１′１３ ＣＨ。Shif11 Shiiko Shif13 1'13 CH.
し１′１３ しＩ′Ｉｓ しｆｌ。1'13 I'Is Shi fl.
ＣＨ，ＣＨ，Ｓ）！ ＣＢ 、ＣＨ２ＣＨ２ＳＨ ＣＨ，Ｃ１（２５Ｈ しｌ ｍＮ３１ し１１３ し１′１３ しｉコ しｆ１３ しｎ３ 響 ＣＨ３ＣＯ，５）Ｉ ＣＨ２ＣＨ、ＳＨ 次に本発明に係る化合物の合成法の例について述べる。CH, CH, S)! CB, CH2CH2SH CH, C1 (25H Shil mN31 113 1'13 Shiiko Shif13 Shinn3 sound CH3CO,5)I CH2CH, SH Next, an example of the method for synthesizing the compound according to the present invention will be described.
例えば化合物 は次の合成法に従って合成 できる°。For example, compounds is synthesized according to the following synthesis method Can be done.
あるいは次の方法でも合成できる。Alternatively, it can be synthesized by the following method.
これらの合成法は、
例えば特開昭５５−５２０５０号、
米国特許４，６８６．１６７号等に記載の合成法も参考
にできる。For these synthesis methods, the synthesis methods described in, for example, JP-A-55-52050 and US Pat. No. 4,686.167 can also be referred to.
化合物（３） は次の合成法に従って合成できる。Compound (3) can be synthesized according to the following synthesis method.
あるいは次の方法でも合成できる。Alternatively, it can be synthesized by the following method.
本ＮＨＮ）ＩＣＯＣＯＮＩ（Ｃ）１２ｃＨ＝ＣＨ。This NHN) ICOCONI (C) 12cH=CH.
化合物（５） は次の合成法に従って合成できる。Compound (5) can be synthesized according to the following synthesis method.
化合物（３５）は次の合成法に従って合成できる。Compound (35) can be synthesized according to the following synthesis method.
又、化合物（１）、（５）の別の合成法及び化合物（５
７）の合成法の、それぞれの例を以下に記す。In addition, another method for synthesizing compounds (1) and (5) and compound (5)
Examples of the synthesis method 7) are described below.
化合物（４９）は次の合成法に従って合成できる。Compound (49) can be synthesized according to the following synthesis method.
化合物（１）
ｐ−ニトロフェニルヒドラジン１５ｇ及びアセトニトリ
ル１５０ｍｆｆの懸濁液に氷水冷下、エトキシオキザリ
ルクロライド１９ｇ、次いでトリエチルアミン１４ｇを
滴下する。滴下終了後、室温で１時間撹拌する。次いで
不溶物を濾過除去後、濾液を濃縮して残渣をクロロホル
ム４００ｍ（２に溶解する。希アルカリ水で洗浄後、分
液し、クロロホルム層を濃縮して組成物２９．７ｇを得
た。これをインプロパツール１２０ｍ１２中撹拌洗浄に
て精製し、化合物（Ｉ）１６−９ ｇを得た。酢酸１６
０ｍ４中に化合物（Ｉ）１６．ｇ及びｐｄ／Ｃ触媒５ｇ
を加え、水素気流下、常圧常温にて撹拌し、反応終了後
、触媒残渣を除去し濾液を濃縮して組成物を得た。これ
をカラムクロマトグラフィーによって精製し化合物（Ｉ
Ｉ）５．６ｇを得た。Compound (1) 19 g of ethoxyoxalyl chloride and then 14 g of triethylamine are added dropwise to a suspension of 15 g of p-nitrophenylhydrazine and 150 mff of acetonitrile under cooling with ice water. After the dropwise addition was completed, the mixture was stirred at room temperature for 1 hour. Next, after removing insoluble materials by filtration, the filtrate was concentrated and the residue was dissolved in 400 m of chloroform (2). After washing with dilute alkaline water, the layers were separated, and the chloroform layer was concentrated to obtain 29.7 g of a composition. was purified by stirring and washing in 120 ml of Improper Tools to obtain 16-9 g of Compound (I). Acetic acid 16
Compound (I) 16. g and pd/C catalyst 5g
was added and stirred under a hydrogen stream at normal pressure and room temperature. After the reaction was completed, the catalyst residue was removed and the filtrate was concentrated to obtain a composition. This was purified by column chromatography to obtain the compound (I
I) 5.6 g was obtained.
化合物（ＩＩ）８．１ｇ及びアセトニトリル８０ｍ１２
の懸濁液に還流加熱下、エチルイソチオシアナート９．
５ｇを滴下する。更に２時間加熱還流後、濃縮して組成
物１１ｇを得た。これをアセトニトリルによる再結晶に
よって精製し、化合物（ＩＩＩ）４．５ｇを得た。Compound (II) 8.1g and acetonitrile 80ml
Ethylisothiocyanate 9.
Add 5g dropwise. After further heating under reflux for 2 hours, the mixture was concentrated to obtain 11 g of a composition. This was purified by recrystallization with acetonitrile to obtain 4.5 g of compound (III).
アリルアミン４０■ａに化合物（Ｉ［［）５．０ｇを溶
解し、２時間加熱還流する。終了後濃縮して組成物４．
９ｇを得た。これをクロロホルム２５ｔＱ中撹拌洗浄に
て精製し、化合物（１） ４．３ｇを得た。5.0 g of compound (I) was dissolved in allylamine 40■a and heated under reflux for 2 hours. After finishing, concentrate and prepare composition 4.
9g was obtained. This was purified by stirring and washing in 25 tQ of chloroform to obtain 4.3 g of compound (1).
融点２０６．９℃。Melting point: 206.9°C.
ＦＡＢ−ＭＳでＭ”＋１−３２２を検出した。M''+1-322 was detected by FAB-MS.
化合物（５）
米国特許４，６８６，１６７号記載の方法に従って化合
物（１）を合成した。化合物（Ｉ ） ３１．１ｇとエ
タノール３００ｏ１２とアリルアミン１０．６ ｇを加
熱し還流温度で一晩反応した。反応液を濃縮し、残音に
ベンゼンを６００ｍ１２加え、５℃に冷却して析出結晶
を濾取し、化合物（Ｉ［）３０ｇを得た。Compound (5) Compound (1) was synthesized according to the method described in US Pat. No. 4,686,167. 31.1 g of compound (I), 300 ml of ethanol, and 10.6 g of allylamine were heated and reacted at reflux temperature overnight. The reaction solution was concentrated, 600ml of benzene was added to the residual sound, and the mixture was cooled to 5°C and the precipitated crystals were collected by filtration to obtain 30g of compound (I[).
化合物（ｎ）３０ｇをＴＨＦ （テトラヒドロフラン）
５４０ａ＋Ｑに溶解し、濃塩酸１５０ｍ１２を添加する
。次いで塩化第一錫１５０．８ｇのＴＨＦ ５４０＋ｎ
Ｑ溶液を室温で添加し４０〜５０℃にて一晩反応した。30g of compound (n) in THF (tetrahydrofuran)
540a+Q and add 150ml of concentrated hydrochloric acid. Then 150.8 g of stannous chloride THF 540+n
Q solution was added at room temperature and reacted overnight at 40-50°C.
反応後、析出結晶を濾取し、メタノールＩＱに懸濁させ
撹拌下アンモニア水にてｐＨ７，５〜８とし１時間撹拌
した。After the reaction, the precipitated crystals were collected by filtration, suspended in methanol IQ, and adjusted to pH 7.5-8 with aqueous ammonia under stirring for 1 hour.
その後メタノールを半分濃縮し、０℃に冷却後結晶を濾
取し、化合物（ＤＩ） １９．８ｇを得た。Thereafter, methanol was half concentrated, and after cooling to 0° C., the crystals were collected by filtration to obtain 19.8 g of compound (DI).
化合物（ＩＩ）１５ｇをピリジン６００＋ｎＱに溶解し
た後、外部より冷却しながらクロル蟻酸フェニル１１ｇ
を内５１１５℃以下で滴下した。滴下後、室温にて一晩
反応した。反応後、ピリジンを濃縮し、残音をアセトン
２００ｍｆｆで撹拌洗浄し濾取し、化合物（■）１７ｇ
を得た。After dissolving 15 g of compound (II) in pyridine 600+nQ, 11 g of phenyl chloroformate was added while cooling from the outside.
was added dropwise at a temperature below 5115°C. After the dropwise addition, the mixture was reacted overnight at room temperature. After the reaction, the pyridine was concentrated, the residual sound was washed with 200 mff of acetone, and the mixture was filtered to obtain 17 g of compound (■).
I got it.
化合物（ｒＶ ） １６．２ｇをピリジン１６０＋ｎＱ
に溶解し、化合物（Ｖ ） １６．８ｇのピリジン１６
０ｍ１２溶液を加え加熱し還流温度で３時間反応した。Compound (rV) 16.2g to pyridine 160+nQ
Compound (V) 16.8 g of pyridine 16
A 0ml2 solution was added, heated, and reacted at reflux temperature for 3 hours.
反応後、ピリジンを留去し、残音にｎ−ヘキサン３００
ｍ＜２を加え撹拌洗浄し、結晶を濾取した。この粗結晶
をＤＭＦ（ジメチルホルムアミド） ６０ｍＱに加熱溶
解しアセトン１８０ｎ１２を加え、０℃に冷却して析出
した結晶を取り出し、化合物（５） １３．８ｇを得た
。After the reaction, pyridine was distilled off, and the residual sound was mixed with 300% n-hexane.
m<2 was added, stirred and washed, and the crystals were collected by filtration. The crude crystals were heated and dissolved in 60 mQ of DMF (dimethylformamide), 180 n12 of acetone was added, and the mixture was cooled to 0°C and the precipitated crystals were taken out to obtain 13.8 g of compound (5).
融点１９８．５〜１９９．５°Ｃ０ ＦＡＢ−ＭＳでＭ ” −５６５を検出した。Melting point 198.5-199.5°C0 M''-565 was detected by FAB-MS.
（Ｉ） （Ｉｔ）
（ＩＩＩ）
化合物（Ｉ ） ２７ｇとエタノール２５ｏＩＩ＋２ト
化合物（ＩＩ）２５ｇを加熱し還流温度で一晩反応した
。反応後、反応液を０℃に冷却し析出結晶を濾取しエタ
ノールで洗浄した。得られた粗結晶３１ｇをメタノール
３Ｑより再結晶し、化合物（ｍ） ２０．８ｇを得た。(I) (It) (III) 27 g of Compound (I) and 25 g of Compound (II) were heated and reacted at reflux temperature overnight. After the reaction, the reaction solution was cooled to 0° C., and the precipitated crystals were collected by filtration and washed with ethanol. 31 g of the obtained crude crystals were recrystallized from methanol 3Q to obtain 20.8 g of compound (m).
化合物（ＤＩ）１９ｇをＴＨＦ ４００ｍＱに懸濁し、
濃塩酸１１５ｍＱを添加した。次いで塩化第一錫６９．
４ｇのＴＨＦ ３００ｍ１２溶液を室温で添加し４０〜
５０℃で一晩反応した。反応後、析出結晶を濾取し、メ
タノール４２０ｍＱに溶解後、ＴＨＦ １６８０ｍＱを
加え懸濁させ撹拌下アンモニア水にてｐＨ８，５とし１
５分間撹拌した。19 g of compound (DI) was suspended in 400 mQ of THF,
115 mQ of concentrated hydrochloric acid was added. Then stannous chloride69.
Add 4g of THF 300ml solution at room temperature
The reaction was carried out at 50°C overnight. After the reaction, the precipitated crystals were collected by filtration, dissolved in 420 mQ of methanol, suspended in 1680 mQ of THF, and adjusted to pH 8.5 with aqueous ammonia under stirring.
Stir for 5 minutes.
その後析出結晶を濾取し、化合物（ＩＶ ） １１．５
ｇを得た。Thereafter, the precipitated crystals were collected by filtration, and compound (IV) 11.5
I got g.
化合物（■）１０ｇをピリジンｌｆ２に溶解した後、外
部より冷却しながらクロル蟻酸フェニル５．２ｇを内温
１５°Ｃ以下で滴下した。滴下後室温にて一晩反応した
。After dissolving 10 g of compound (■) in pyridine lf2, 5.2 g of phenyl chloroformate was added dropwise to the solution while cooling from the outside at an internal temperature of 15°C or less. After the dropwise addition, the mixture was reacted overnight at room temperature.
反応後ピリジンを７００〜８００＋ｎ１２に濃縮し、残
音にアセトン４００ｍＱを加え撹拌し析出結晶を濾取し
た。After the reaction, pyridine was concentrated to 700-800+n12, 400 mQ of acetone was added to the residual sound, and the mixture was stirred and the precipitated crystals were collected by filtration.
この粗結晶をアセトン２００ｍＱに懸濁し還流させ、次
いでＤＭＦ ２６０＋ｎ＋２を滴下し溶解させ不溶分を
除き０℃に冷却した。析出結晶を濾取し化合物（Ｖ）８
．５ｇを得た。This crude crystal was suspended in 200 mQ of acetone and refluxed, and then DMF 260+n+2 was added dropwise to dissolve it, and insoluble matter was removed, and the mixture was cooled to 0°C. The precipitated crystals were collected by filtration and compound (V) 8
．． 5g was obtained.
化合物（Ｖ’）１０ｇをピリジン２００ｍ１２に懸濁し
、化合物（Ｖｌ）８．１ｇのピリジンｌｏｏｍＱ溶液を
加え還流温度で３時間反応した。反応後、反応液にアセ
トン２Ｑを加え結晶化させ濾取した。この粗結晶をアセ
トン８５ｍ＋２に懸濁し還流させメタノール８５ｍＱを
滴下溶解後、直ちに０°Ｃに冷却し、析出した結晶を濾
取し、化合物（５７） ６ｇを得た。10 g of Compound (V') was suspended in 200 ml of pyridine, a solution of 8.1 g of Compound (Vl) in pyridine roomQ was added, and the mixture was reacted at reflux temperature for 3 hours. After the reaction, acetone 2Q was added to the reaction solution to crystallize it, which was collected by filtration. The crude crystals were suspended in 85 m+2 of acetone and refluxed, and 85 mQ of methanol was added dropwise to dissolve therein, immediately cooled to 0°C, and the precipitated crystals were collected by filtration to obtain 6 g of compound (57).
融点２３０〜２３１°Ｃ０ ＦＡＢ−ＭＳにてＭ”＋ １ ＝６６５を検出した。Melting point 230-231°C0 M''+1=665 was detected by FAB-MS.
化合物（Ｉ）１０ｇのピッ９フ５０
トロベンゼンスルホニルクロライド６．６ｇを外部より
氷水浴冷却しながら添加した。室温で１０時間反応させ
た後、溶媒を溜去し水を加え固体を濾取した。これをカ
ラムクロマト（クロロホルム／メタノール＝ ３／２）
にて精製を行い、化合物（］Ｉ）を５、９ｇ得た。10 g of Compound (I) and 6.6 g of trobenzenesulfonyl chloride were added externally while cooling in an ice water bath. After reacting at room temperature for 10 hours, the solvent was distilled off, water was added, and the solid was collected by filtration. This was subjected to column chromatography (chloroform/methanol = 3/2)
Purification was performed to obtain 5.9 g of compound (]I).
化合物（ ＩＦ ） ５．５ｇ 、 ｗｅｔ５％Ｐｄ／
Ｃ １．Ｏｇ 、メタノール１５０ｍ１２の混合液を常
圧で水添還元を行った。Compound (IF) 5.5g, wet5%Pd/
C1. A mixed solution of Og and 150 ml of methanol was hydrogenated and reduced at normal pressure.
反応後、Ｐｄ／Ｃを濾別し、溶媒を溜去して化合物（Ｉ
［［）を得た。これをピリジン５０＋ｎ１２に溶かし、
外部より氷水浴冷却しながら化合物（ＩＶ）４．０ｇの
ピリジン１０ｍ１２溶液を滴下した。室温で５時間撹拌
後、溶媒を溜去して水を加え固体を濾取した。こカラム
クロマト（メチレンクロライド／メタノール− ！Ｍｌ
）で精製した後、酢酸エチル−ｎ−ヘキサンで再結晶を
行い化合物（６１）１．Ｏｇを得た。融点１６５〜１７
２℃。化合物の構造ＭＳ及びＮＭＲにて確認した。After the reaction, Pd/C was filtered off, the solvent was distilled off, and the compound (I
I got [[). Dissolve this in pyridine 50+n12,
A solution of 4.0 g of compound (IV) in 10 ml of pyridine was added dropwise while cooling from the outside in an ice-water bath. After stirring at room temperature for 5 hours, the solvent was distilled off, water was added, and the solid was collected by filtration. This column chromatography (methylene chloride/methanol-!Ml
), and then recrystallized from ethyl acetate-n-hexane to obtain compound (61) 1. Obtained Og. Melting point 165-17
2℃. The structure of the compound was confirmed by MS and NMR.
化合物（６２）は次の方法で合成できる。Compound (62) can be synthesized by the following method.
化合物（ １３３）は次の方法で合成できる。Compound (133) can be synthesized by the following method.
化合物（１１６）は次の方法で合成できる。Compound (116) can be synthesized by the following method.
化合物（１３３） 化合物（１４０）は次の方法で合成できる。Compound (133) Compound (140) can be synthesized by the following method.
化合物（１４９）は次の方法で合成できる。Compound (149) can be synthesized by the following method.
化合物（１４０） 化合物（７１）は次の方法で合成できる。Compound (140) Compound (71) can be synthesized by the following method.
化合物（７１）
本発明において一般式〔Ａ〕及び〔Ｂ〕で表される化合
物と併用される造核促進化合物のアミン化合物、ヒドラ
ジン化合物、四級オニウム塩化合物としては、下記の一
般式（１）〜（ＶＩ）の化合物が挙げられる。Compound (71) In the present invention, the amine compound, hydrazine compound, and quaternary onium salt compound of the nucleation promoting compound to be used in combination with the compounds represented by the general formulas [A] and [B] include the following general formula (1). ) to (VI).
この中で好ましい化合物としては、（Ｖ〕−ａ。Among these, preferred compounds include (V]-a.
［Ｖ） ｂ、 Ｉ：Ｖ）−ｃ、 ｌ：ＶＩ）−ａ、
（ＶＩ）−ｂ、 Ｃ■）Ｃの化合物が挙げられる。[V) b, I:V)-c, l:VI)-a,
(VI)-b, C■)C compounds are mentioned.
一般式〔■〕
Ｒ、、Ｒ２，Ｒ３は水素原子又は置換基表す。ＲｌＲ２
，Ｒ、は互いに連結して環を形成してもよい。General formula [■] R, , R2 and R3 represent a hydrogen atom or a substituent. RlR2
, R, may be connected to each other to form a ring.
Ｒ、、Ｒ２，Ｒ３が表す置換基としては、例えばアルキ
ル基（例えばメチル、エチル、プロピル、ブチル、ヘキ
シル、シクロヘキシル等の基）、アルケニル基（例スば
アリル、ブテニル等の基）、アルキニル基（例えばプロ
パルギル、ブチニル等の基）、アリール基（例えばフェ
ニル、ナフチル等の基）、ヘテロ環基（例えばピペリジ
ニル、ピペラジニル、モルホリニル、ピリジル、フリル
、チエニル、テトラヒドロフリル、テトラヒドロチエニ
ル、スルホラニル等の基）が挙げられる。Examples of the substituents represented by R, R2, and R3 include alkyl groups (e.g., methyl, ethyl, propyl, butyl, hexyl, cyclohexyl, etc.), alkenyl groups (e.g., allyl, butenyl, etc.), and alkynyl groups. (e.g., propargyl, butynyl, etc.), aryl groups (e.g., phenyl, naphthyl, etc.), heterocyclic groups (e.g., piperidinyl, piperazinyl, morpholinyl, pyridyl, furyl, thienyl, tetrahydrofuryl, tetrahydrothienyl, sulfolanyl, etc.) can be mentioned.
Ｒｌ、Ｒ２，Ｒｓが互いに連結して形成してもよい環と
しては、例えばピペリジン、モルホリン、ピペラジン、
キヌクリジン、ピリジン等の環が挙げられる。Examples of the ring that R1, R2, and Rs may be linked to each other to form include piperidine, morpholine, piperazine,
Examples include rings such as quinuclidine and pyridine.
Ｒ、、Ｒ２，Ｒ、で表される基には更に置換基（例えば
ヒドロキシル、アルコキシ、アリールオキシ、カルボキ
シル
基）が置換していてもよい。Ｒ 、、Ｒ 、、Ｒ 、と
しては水素原子及びアルキル基が好ましい。The groups represented by R, , R2, and R may be further substituted with a substituent (eg, hydroxyl, alkoxy, aryloxy, carboxyl group). As R , , R , , R , hydrogen atoms and alkyl groups are preferred.
以下に代表的具体例を示す。Typical specific examples are shown below.
１−Ｉ Ｉ−２
（ＣｚＨｓ）ｚＮＣＨｚＣＨｚＣＩｈＯ）Ｉ ＣＨ
ｘＮ）ＩＣＨｚＣＨ２０Ｈ（ＣＪｓ）ｚＮｃＨｘｃＨｚ
ＯＨ （ＣＪｓ）ｚＮｃＨ２ｃＨｃＨｔＯ
ＨＨ
（＋−Ｃ３Ｈ７）２ＮＨ
■ −１０
Ｃ４ＨｓＮ（ＣＪＣＨｚＯ）Ｉ）ｚ
■ −１２
（ＣＪＪｚＮＣ）ｌｚｃ）ｂＯＨ
（Ｃ４Ｈｓ）ＪＣＨｚＣＨＣＨｚＯＨ
Ｈ
一般式ＣＩり
（Ｐｈ Ｃ［（ｚ）ＪＣＨ２Ｃｆ（２０Ｈ（Ｃ＋ａＨ
ｓｉ）ｚＮｃＨｚｃＨ２０）１（ＣａＨ＋ ｔ）ｘＮｃ
Ｈ＊ｃ１ｈＯＨＱはＮ又はＰ原子を表し、Ｒ，、Ｒ２，
Ｒ，、Ｒ。1-I I-2 (CzHs)zNCHzCHzCIhO)I CH
xN) ICHzCH20H(CJs)zNcHxcHz
OH (CJs)zNcH2cHcHtO
HH (+-C3H7)2NH ■ -10 C4HsN(CJCHzO)I)z ■ -12 (CJJzNC)lzc)bOH (C4Hs)JCHzCHCHzOH H General formula CI (Ph
si)zNcHzcH20)1(CaH+ t)xNc
H*c1hOHQ represents N or P atom, R,, R2,
R,,R.
は各々、水素原子又は置換可能な基を表す。Ｘｏはアニ
オンを表す。Ｒ，、Ｒ，、Ｒ，、Ｒ４は互いに連結して
環を形成してもよい。each represents a hydrogen atom or a substitutable group. Xo represents an anion. R,, R,, R,, R4 may be connected to each other to form a ring.
Ｒ，、Ｒ，、Ｒ，、Ｒ，で表される置換可能な基として
は、例えばアルキル、アルケニル、アルキニル、アリー
ル、ヘテＯ環、アミノ等の多基が挙げられ、具体的には
一般式ＣＩ）のＲ，、Ｒ，、Ｒ３゜で説明したものが挙
げられる。Examples of substitutable groups represented by R,, R,, R,, R, include multiple groups such as alkyl, alkenyl, alkynyl, aryl, hetero-O ring, and amino. Examples include those explained in relation to R, , R, , R3° of CI).
Ｒ１＋ Ｒ２，Ｒ３，Ｒ４が形成し得る環としては、一
般式〔Ｉ〕のＲ，、Ｒ，、Ｒ，で形成し得る環として説
明したものと同様のものが挙げられる。Examples of the ring that can be formed by R1+ R2, R3, and R4 include the same rings as those described as the ring that can be formed by R, , R, and R in general formula [I].
ｘｏが表すアニオンとしては、ハロゲン化物イオン、硫
酸イオン、硝酸イオン、酢酸イオン、パラトルエンスル
ホン酸イオン等の無機及び有機のアニオンが挙げられる
。Examples of the anion represented by xo include inorganic and organic anions such as halide ions, sulfate ions, nitrate ions, acetate ions, and paratoluenesulfonate ions.
以下に代表的具体例を示す。Typical specific examples are shown below.
トｌト２
Ｐｈ ＣＨｚＮ（ＣＨａ）ｓ ＣＱｅＣｌｍＨｓｓＮＣ
ＣＨｓ）ｘ（Ｃ４ＨＩ）４Ｎ
（ＣＨａ）ｓＮｃＨｚｃＨｚＯＨ
Ｐｈ ＣＨｚＮ（ＣＨａ）ｚ
ｌ４Ｈ２９
ＣＨｚＣＯＯＣＨａ
（ＣＪｓ）ｉＮｃＨ２ＧＨｚＮ（Ｃ＊Ｈ＊）ｓＳ０４′
ｅ
（ＣＪＪｚＮ（ＣＨｚ）ｓＮ（ＣＪｓ）ｓＣｆｆｅ
ごＨ２ＣＪＯＯＣ（ＣＨ２）４ＣＯＯＣＨｚＣＨ２ｎ−
１７
■ −１８
１［−１９
Ｆ−２７
■ −２０
２Ｃ（２θ
Ｂｒｅ
■ −２８
（ＣａＨ＊）ｓＰ＠ＣＩ＠Ｈ３３
ｒ０
しｉ３
しＲ３
一般式ＣＩ［ｌ）
Ｒ、、Ｒ、はアルキル基を表し、Ｒ１とＲ２は連結して
環を形成してもよい。Ｒ３はアルキル基、アリール基、
ヘテロ環基を表し、Ａはアルキレン基を表す。Tolt2 Ph CHzN(CHa)s CQeClmHssNC
CHs)
e (CJJzN(CHz)sN(CJs)sCffe H2CJOOC(CH2)4COOCHzCH2n-
17 ■ -18 1[-19 F-27 ■ -20 2C(2θ Bre ■ -28 (CaH*)sP@CI@H33 r0 shi3 shiR3 General formula CI[l) R,,R,represents an alkyl group and R1 and R2 may be connected to form a ring. R3 is an alkyl group, an aryl group,
It represents a heterocyclic group, and A represents an alkylene group.
Ｙは−ＣＯＮＲ，−、−０ＣＯＮＲ４−，−ＮＲ，Ｃ０
ＮＲ，−、−ＮＲ，Ｃｏｏ−。Y is -CONR,-,-0CONR4-,-NR,C0
NR,-, -NR,Coo-.
−Ｃｏｏ−、−０ＣＯ−、−ＣＯ−、−０ＣＯＯ−、−
ＮＲ，ＣＯ−、−５Ｏ２ＮＲ，−。-Coo-, -0CO-, -CO-, -0COO-, -
NR,CO-, -5O2NR,-.
ＮＲ４５Ｏ＊ 、 ＮＲ１５ＯＪＲａ 、−ｓｏ、−
、−Ｓ−、−０−、−ＮＲ，−。NR45O*, NR15OJRa, -so, -
, -S-, -0-, -NR,-.
−Ｎ−基を表し、Ｒ４は水素原子又はアルキル基を表す
。-N- group, and R4 represents a hydrogen atom or an alkyl group.
Ｒ、、Ｒ、で表されるアルキル基としては、一般式ＣＩ
）で説明したＲ ｌ＋Ｒｘ、Ｒｓのアルキル基と同様の
ものが挙げられ、Ｒ１とＲ２で形成し得る環も同様のも
のが挙げられる。The alkyl group represented by R, ,R, has the general formula CI
) The same alkyl groups as R l+Rx and Rs explained in ) can be mentioned, and the same rings that can be formed by R1 and R2 can also be mentioned.
Ｒ１で表されるアルキル基、アリール基、ヘテロ環基も
一般式（１）のＲＩＲ２，Ｒｓの表すアルキル基、アリ
ール基、ヘテロ環基と同様のものが挙げられる。Examples of the alkyl group, aryl group, and heterocyclic group represented by R1 include those similar to the alkyl group, aryl group, and heterocyclic group represented by RIR2 and Rs in general formula (1).
Ａで表されるアルキレン基としては、例えばメチレン、
エチレン、トリメチレン、テトラメチレン等が挙げられ
、Ａの置換基としてはアリール基、アルコキシ基、ヒド
ロキシル基、ハロゲン原子などを挙げることができる。Examples of the alkylene group represented by A include methylene,
Examples include ethylene, trimethylene, tetramethylene, etc., and examples of substituents for A include aryl groups, alkoxy groups, hydroxyl groups, and halogen atoms.
Ｒ４で表されるアルキル基は、炭素数ｌ〜５の低級アル
キル基又はアラルキル基（例えばベンジル基など）が好
ましい。The alkyl group represented by R4 is preferably a lower alkyl group having 1 to 5 carbon atoms or an aralkyl group (for example, a benzyl group).
以下に代表的具体例を示す。Typical specific examples are shown below.
Ｉ［［−２
（Ｃ２）１ｓ）ｘＮ（ＣＨｚ’ｈＮＦＩＣＯＮＨＣ＋
２Ｈｚｓ１ｌ−５
（ＣＪｓ）ｚＮ（ＣＨｚ）ｚＯｃＯＮＨｃａＨ＋ ｔＣ
ＣｚＨｓ）ｚＮＣＣＨｚ）ｘＮＨＣＯＣＩｓＨｚｒｍ−
３
（ＣＨ３）２Ｎ（ＣＨ２）２ＣＯＮＨＣ，、Ｒ２゜ｌ−
２０
（Ｃ−１（ｓ）ｚＮ（ＣＨ，）＊ＮＨ３０□Ｎ（ＣＨ。I[[-2 (C2)1s)xN(CHz'hNFICONHC+
2Hzs1l-5 (CJs)zN(CHz)zOcONHcaH+ tC
CzHs)zNCCHz)xNHCOCIsHzrm-
3 (CH3)2N(CH2)2CONHC,, R2゜l-
20 (C-1(s)zN(CH,)*NH30□N(CH.
ｐｈ）２
（Ｐｈ ＣＨ２）ｚＮ（ＣＨｚ）２ＮＨｓＯ２Ｎ（Ｃ
Ｈ３）２■
（Ｐｈ Ｃｔ（ｚ）２Ｎ（ＣＨｚ）３０ｃ＊Ｈｓ■
−１９
一般式ＣＩＶ）
Ｒ＋、Ｒｘは水素原子、アルキル基、アルケニル基、ア
ルキニル基、アリール基、ヘテロ環基を表し、Ｒｌ＋Ｒ
２＋Ｅで環を形成してもよい。ph)2 (Ph CH2)zN(CHz)2NHsO2N(C
H3)2■ (Ph Ct(z)2N(CHz)30c*Hs■
-19 General formula CIV) R+ and Rx represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, and Rl+R
2+E may form a ring.
Ｅは１１（ｚｃＨ，６ｉ で表される基を少なくとも一
つ含む基であり、ｎは２以上の整数を表す。E is a group containing at least one group represented by 11(zcH,6i), and n represents an integer of 2 or more.
Ｒ＋ 、 Ｒ！で表されるアルキル基、アルケニル基、
アルキニル基、アリール基、ヘテロ環基及びＲ，。R+, R! Alkyl group, alkenyl group represented by
Alkynyl group, aryl group, heterocyclic group and R.
Ｒ２，Ｅで形成し得る環としては、一般式〔■〕のＲｌ
＋Ｒｘ、Ｒｓで説明したものと同様のものが挙げられる
。As a ring that can be formed by R2 and E, Rl of the general formula [■]
+Rx and the same ones as explained for Rs can be mentioned.
以下に代表的具体例を示す。Typical specific examples are shown below.
Ｖ−１
（ｉ −Ｃ３）１７）２Ｎ（ＣＨ２ＣＨ２０）〜、ＨＶ
−２
（ＣｓＨｒ）ｔＮ（ＣＨ，ＣＩｈＯ）ｚＨ■
■ −
（Ｃ４ＨＩ）２Ｎ（ＣＨ２ＣＨ２０）３Ｈ■ −
（Ｃ２Ｈｓ）２Ｎ（ＣＨ２ＣＨｚＯ）〜１ａｃＴｏｃＨ
ｚＮ（ＣＪｓ）２Ｖ−７
（ｉ ＣＪｔ）２Ｎ（ＣＨ２ＣＨ２０）ｓｃＨｚｃＨ
ｚＮ（ＣＪ７−〇ｚＶ−１０
■−１１
（ＣＪｓ）ｚＮ（ＣＨ２ＣＨ２０）〜３ｚｃＨｚｃＨｚ
Ｎ（ＣＪｓ）２（ＣｓＨｙ）ｚＮ（ＣＨ２ＣＨ２Ｏ）〜
５ＣＨ２ＣＨ２Ｎ（Ｃ３Ｈ７）２■
ＣＩ、 −Ｃ１（ＣＨ２ＮＨ（ＣＨ，ＣＨ２０）〜、、
ＣＨ２ＣＨ２ＮＨＣＨ２Ｃ）ｌ＝ｃＨ２■
Ｃ）Ｉ＝ＣＣＨ２ＮＨ（ＣＨ２ＣＨ２０）〜、 、ＣＨ
ｘＣＨＪＨＣＦＩ２ＣミＣＨ■−２８
（ＣＪｓ）２Ｎ（ＣＨｚＣ）ＩｚＯ）Ｊ■−２９
（ＣａＨ＋ｙ）２Ｎ（ＣＨ２ＣＨ２０）ｚＨＶ−３０
（Ｃ＋Ｊｚｉ）ｚＮ（ＣＨ２ＣＨ２０）ＪＶ−３１
（Ｐｈ Ｃ）（ｚ）２Ｎ（ＣＨｚＣＨｚＯ）Ｊ■−３
２
（Ｃ４Ｈｓ）ｉＮ（ＣＨ２ＣＨｚＯ）ｚｃＨｚｃＨｘＮ
（ＣＪｓ）ｉＩＶ−３３−
（ＣａＨ＋ ｙ）２Ｎ（ＣＨ２ＣＨｚＯ）ｔｃＨｚｃＨ
ｔＮ（ＣｓＨ＋ Ｊ＊■−３４
（ＦｌｏＣ）１．ＣＨ２）、Ｎ（ＣＨ，ＣＨ２Ｏ）２Ｃ
Ｈ，ＣＨ，Ｎ（ＣＨ，ＣＯ２０Ｈ）！（Ｃ３Ｈ，）、Ｎ
（ＣＨ２Ｃｌ（２０）〜、 、ＣＨ，ＣＨ２Ｎ（Ｃ３Ｈ
ｒ）２ＩＶ −１５
（ＣＪｒ）ｚＮ（ＣＨ２ＣＨｚＯ）〜３２ＣＨ２ＣＨ２
Ｎ（ＣＪｙ）ｚＮ−１６
（ＣＪＪｚＮ（ＣＨｚＣＨｚＯ）〜５ｃｎ２ｃｕｚＮ（
ｃ４ｎｓ）２■−１８
（Ｃ，ＨＩ）２Ｎ（ＣＨ２ＣＨ２Ｏ）〜＋＋ＣＨｚＣＨ
ｚＮ（ＣＪｅ）ｚＮ−２１
Ｃ８Ｈ□、ＮＨ（ＣＨ，Ｃ）１２０）〜＋ ４ＣＨｚＣ
ＨｚＮＨＣＪｘ ｔ■−２２
Ｃ，Ｈ，、ＮＨ（ＣＨ，ＣＨ２０）〜＋ ４ ＣＨ２Ｃ
Ｈｘ ＮＨＣｔ Ｈ１＊■−２３
（ＨＯＣＨｚＣＨｚ）ｚＮ（ＣＨ，ＣＨｚＯ）〜＋ ＊
ＣＨｚＣＨｚＮ（ＣＨ２ＣＨ２０Ｈ）ｚＮ−３５
（ＣＨｚ−ＣＨｚＣＨｚ）ｚＮ（ＣＨｚＣＨｚＯ）２Ｈ
■−３６
（ＣＨ２寓ＣＨＣ）１．）２Ｎ（ＣＨ，ＣＨ，○）ｚｃ
ＨｘｃＨ２Ｎ（ＣＨｚＣＨ−ＣＨｚ）ｚＮ−３７
Ｃ＠Ｈ＋ｓＣＪ＋３
■−３８
ＣＨ，−Ｐｈ
ＣＨ，−Ｐｈ
一般式（Ｖ） −ａ
Ｖ−ａ−１
（ＣＨ３）２Ｎ（ＣＨ２）３ＮＨＣＯＮＨ（ＣＨ２）８
ＣＨ−ＣＨＣｓＨｌ ７−ａ−２
Ｒｌ＋Ｒｚ、Ｒｓはアルキル基、アルケニル基、アルキ
ニル基、アリール基、ヘテロ環基を示す。V-1 (i -C3)17)2N(CH2CH20) ~, HV
-2 (CsHr)tN(CH,CIhO)zH■ ■ - (C4HI)2N(CH2CH20)3H■ - (C2Hs)2N(CH2CHzO) ~ 1acTocH
zN(CJs)2V-7 (i CJt)2N(CH2CH20)scHzcH
zN(CJ7-〇zV-10 ■-11 (CJs)zN(CH2CH20)~3zcHzcHz
N(CJs)2(CsHy)zN(CH2CH2O)~
5CH2CH2N(C3H7)2■ CI, -C1(CH2NH(CH,CH20)~,,
CH2CH2NHCH2C)l=cCH2■ C)I=CCH2NH(CH2CH20)~, ,CH
xCHJHCFI2CmiCH■-28 (CJs)2N(CHzC)IzO)J■-29 (CaH+y)2N(CH2CH20)zHV-30 (C+Jzi)zN(CH2CH20)JV-31 (Ph C) (z)2N(CHzCHzO) J■-3
2 (C4Hs)iN(CH2CHzO)zcHzcHxN
(CJs)iIV-33- (CaH+ y)2N(CH2CHzO)tcHzcH
tN(CsH+ J*■-34 (FloC)1.CH2), N(CH,CH2O)2C
H, CH, N (CH, CO20H)! (C3H,), N
(CH2Cl(20)~, ,CH,CH2N(C3H
r) 2IV -15 (CJr)zN(CH2CHzO) ~ 32CH2CH2
N(CJy)zN-16 (CJJzN(CHzCHzO)~5cn2cuzN(
c4ns)2■-18 (C,HI)2N(CH2CH2O)~++CHzCH
zN(CJe)zN-21 C8H□, NH(CH,C)120)~+4CHzC
HzNHCJx t -22 C, H,, NH (CH, CH20) ~ + 4 CH2C
Hx NHCt H1*■-23 (HOCHzCHz)zN(CH,CHzO)～+ *
CHzCHzN(CH2CH20H)zN-35 (CHz-CHzCHz)zN(CHzCHzO)2H
■-36 (CH2 fable CHC) 1. )2N(CH,CH,○)zc
HxcH2N(CHzCH-CHz)zN-37 C@H+sCJ+3 ■-38 CH, -Ph CH, -Ph General formula (V) -a V-a-1 (CH3)2N(CH2)3NHCONH(CH2)8
CH-CHCsHl 7-a-2 Rl+Rz, Rs represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group.
但し、Ｒｌ、Ｒ２，Ｒｓのうち少なくとも一つはアルケ
ニル基又はアルキニル基を表すか、又はＲ１＋Ｒ２のう
ち少なくとも一つはアリール基又はヘテロ環基を表すも
のとする。Ｒ、、Ｒ、、Ｌ 、Ｒ、で環を形成してもよ
い。Ｌは連結基を表す。However, at least one of R1, R2, and Rs represents an alkenyl group or an alkynyl group, or at least one of R1+R2 represents an aryl group or a heterocyclic group. R, , R, , L , and R may form a ring. L represents a linking group.
Ｒｌ＋Ｒ！、Ｒ１が表すアルキル基、アルケニル基、ア
ルキニル基、アリール基、ヘテロ環基としては、一般式
（１）のＲ＋、Ｒｚ、Ｒｓで挙げた基と同様のものが挙
げられる。Rl+R! Examples of the alkyl group, alkenyl group, alkynyl group, aryl group, and heterocyclic group represented by R1 include the same groups as those listed for R+, Rz, and Rs in general formula (1).
Ｒ、、Ｒ、、Ｌ 、ＲＳで形成し得る環としては、例え
ばピペリジン、モルホリン、ピロリジン等のへテロ環が
挙げられる。Examples of the ring that can be formed by R,, R,, L, and RS include heterocycles such as piperidine, morpholine, and pyrrolidine.
Ｌで表される連結基としては、例えば一般式（Ｉ［［）
で挙げた一Ａ−Ｙ−が挙げられる。As the linking group represented by L, for example, the general formula (I[[)
Examples include 1AY- listed above.
以下に代表的具体例を示す。Typical specific examples are shown below.
−ａ
−ａ−５
−ａ−６
−ａ−７
−ａ−８
（ＣｚＨ５）２Ｎ（ＣＨ２）、ＮＨｃｏ（ＣＨ２）７Ｃ
）Ｉ＝ＣＨＣｓＨ＋ ｙ（ＣＪｓ）ｚＮ（ＣＨ２）２０
ＣＯＮＨ（ＣＨ２）ａｃＨ＝ｃＨｃｓＨ＋ ７（Ｃ２Ｈ
ｓ）ｚＮ（ＣＨ２）ｓＮＨｃＯＯ（ＣＨ２）ｓｃＨ＝ｃ
ＨｃａＨ＋ ｙ−ａ−９
−ａ−１７
−ａ
（ＣｚＨｓ）ｚＮ（ＣＨｚ）ｘＯｃＯｃ＝ｃｃ６Ｈ＋
ｓ■
（ＣｚＨｓ）ｚＮ（ＣＨｚ）ｚＮＨｃＯＯｃＨ２Ｃ＝ｃ
ｃｙＨ，ｓ−ａ−１２
（Ｐｈ ＣＨｚ）ｚＮ（ＣＨｚ）ｚＯＣＯＮＨＣＨ２
Ｃ＝ＣＨ−ａ−１３
（Ｐｈ ＣＨｚ）ｚＮ（ＣＨｚ）ＪＨＣＯＮ（ＣＨ２
ＣＨ＝ＣＨ２）ｚ−ａ−１４
（Ｐｈ ＣＨｚ）ｚＮ（ＣＨｚ）３ＮＨＣＯＣ＝ＣＣ
ｓＨｔｓ−ａ−１５
（Ｐｈ ＣＨｚ）ｚＮ（ＣＨｚ）２ＮＨｃＯＯｃＨ２
ｃＨ−ＣＨｚ（ＣＨ２＝ＣＨＣＨｚ）ｔＮ（ＣＨ２）ｚ
ＮＨ５ｃｈＮ（ＣＨｚ Ｐｈ）ｚ−ａ−２２
（Ｃａｎｓ）ｔＮ（ＣＨｚ）ｓＮＨ５Ｏ＊Ｎ（ＣＨ２Ｃ
Ｈ−ＣＨ２）ｔ−ａ−２３
（Ｐｈ−ＣＨ，）２Ｎ（ＣＨ，）！ＮＨ３０，Ｎ（ＣＨ
２ＣＨ＝ＣＨ，）！Ｖ−ａ−２４
Ｖ−ａ−２５
一般式〔ｖ） −ｂ
は水素原子又は置換可能な基を表す。-a -a-5 -a-6 -a-7 -a-8 (CzH5)2N(CH2), NHco(CH2)7C
)I=CHCsH+ y(CJs)zN(CH2)20
CONH(CH2)acH=cHcsH+ 7(C2H
s)zN(CH2)sNHcOO(CH2)scH=c
HcaH+ y-a-9 -a-17 -a (CzHs)zN(CHz)xOcOc=cc6H+
s■ (CzHs)zN(CHz)zNHcOOcH2C=c
cyH, s-a-12 (Ph CHz)zN(CHz)zOCONHCH2
C=CH-a-13 (Ph CHz)zN(CHz)JHCON(CH2
CH=CH2)z-a-14 (Ph CHz)zN(CHz)3NHCOC=CC
sHts-a-15 (Ph CHz)zN(CHz)2NHcOOcH2
cH-CHz (CH2=CHCHz)tN(CH2)z
NH5chN(CHz Ph)z-a-22 (Cans)tN(CHz)sNH5O*N(CH2C
H-CH2) t-a-23 (Ph-CH,)2N(CH,)! NH30,N(CH
2CH=CH,)! Va-24 Va-25 General formula [v) -b represents a hydrogen atom or a substitutable group.
Ｌは連結基を表し、ｎはＯ又はｌの整数を表す。L represents a linking group, and n represents an integer of O or l.
Ｒ、、Ｒ、、Ｒ、、Ｌ 、Ｒ、で連結して環を形成して
もよい。R,,R,,R,,L,R,may be connected to form a ring.
Ｒ、、Ｒ、、Ｒ、で表されるアルキル基、アルケニル基
、アルキニル基、アリール基、ヘテロ環基としては、一
般式ＣＩ）のＲ、、Ｒ、、Ｒ、で説明したのと同様の基
が挙げられる。The alkyl group, alkenyl group, alkynyl group, aryl group, and heterocyclic group represented by R,, R,, R, are the same as those explained for R,, R,, R, of the general formula CI). Examples include groups.
Ｒ８で表される基のうち置換可能な基としては、例えば
アルキル、アルケニル、アルキニル、アリール、ヘテロ
環等の多基であり、上述したと同様の基が挙げられる。Examples of substitutable groups among the groups represented by R8 include polygroups such as alkyl, alkenyl, alkynyl, aryl, and heterocycle, including the same groups as mentioned above.
Ｌは連結基を表すが、例えば−Ｃｏ −−Ｃｏｏ−、
−ＣＯＮＲ＠ ＋、 −ｓｏ！−、−５ｏ、ＮＲ６−等
の基を表す。Ｒ１は水素原子又は置換可能な基を表す。L represents a linking group, for example -Co--Coo-,
-CONR@+, -so! -, -5o, NR6-, etc. group. R1 represents a hydrogen atom or a substitutable group.
Ｒｒ 、 Ｒｚ 、 Ｒｓ 、Ｌ 、 Ｒ４で形成し得
る環としては、例えばピペリジン、モルホリン等のへテ
ロ環が挙げられる。Examples of the ring that can be formed by Rr, Rz, Rs, L, and R4 include heterocycles such as piperidine and morpholine.
Ｒ、、Ｒ、、Ｒ、はアルキル基、アルケニル基、アルキ
ニル基、アリール基、ヘテロ環基を表し、Ｒ３−ｂ−８
（ＣＨｓ）＊ＮＮＨＳＯｚＣ＋ｓＨ３゜−ｂ−４
−ｂ
−ｂ−ａ
（ＣＨｉ）＊ＮＮＨＳＯ＊（ＣＨｘ Ｐｈ）ｚ−ｂ−
１２
（ＣＨ２−ＣＯＣＨ２）２ＮＮＨ５Ｏｉｃｔ□Ｈ□−ｂ
−１３
しＨ，−Ｆｔｌ
ｖ−ｂ−ｔ４
Ｖ−ｂ−１５
−ｂ−１６
（Ｐｈ−ＣＨ，）、ＮＮＨＳＯ□ＣａＨＩ？−ｂ−１７
ＣＨ，−Ｐｈ
−ｂ−１８
−ｂ
−ｂ
−ｂ−２８
−ｂ−２９
■
■
一般式〔ｖ〕
Ｒ・→、−＼（１）。−８゜
Ｒ１は水素原子又は置換基を表し、Ｒ２はアルキル、ア
ルケニル、アルキニル、アリール、ヘテロ環基の６基を
表す。Ｌは連結基を表す。R,,R,,R represent an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, and R3-b-8 (CHs)*NNHSOzC+sH3°-b-4 -b -b-a (CHi )*NNHSO*(CHx Ph)z-b-
12 (CH2-COCH2)2NNH5Oict□H□-b
-13 ShiH, -Ftl v-b-t4 V-b-15 -b-16 (Ph-CH,), NNHSO□CaHI? -b-17 CH, -Ph -b-18 -b -b -b-28 -b-29 ■ ■ General formula [v] R・→, -\(1). -8°R1 represents a hydrogen atom or a substituent, and R2 represents six groups: alkyl, alkenyl, alkynyl, aryl, and heterocyclic group. L represents a linking group.
吠５ｊは含窒素へテロ環を表す。ｎはＯ又はＩの整数を
表す。Ｒ１は 杓 ｊと共に環を形成してもよい。5j represents a nitrogen-containing heterocycle. n represents an integer of O or I. R1 may form a ring with j.
Ｒ２で表されるアルキル、アルケニル、アルキニル、ア
リール、ヘテロ環の６基としては、般式（Ｉ）のＲ、、
Ｒ、、Ｒ、で説明したものと同様の基が挙げられる。Ｒ
１で表される基のうち置換基としては、例えば上記Ｒ２
で説明したものと同様の基が挙げられる。The six groups of alkyl, alkenyl, alkynyl, aryl, and heterocycle represented by R2 include R of general formula (I),
Examples include the same groups as those explained for R, ,R. R
As a substituent among the groups represented by 1, for example, the above R2
Examples include groups similar to those explained in .
成し得るヘテロ環としては、例えばキヌクリジン、ピペ
リジン、ピラゾリジン等のへテロ環が挙げられる。Examples of possible heterocycles include heterocycles such as quinuclidine, piperidine, and pyrazolidine.
して表される連結基としては、 例えば一般式 ［［） のＹで表されるものと同様のものが挙げられる。The linking group represented by For example, general formula [[) Examples include those similar to those represented by Y in .
以下に代表的具体例を示す。Typical specific examples are shown below.
■
■
■
−ｃ−４
−ｃ
■
彊
Ｃ１（２ＣＨ＝ＣＨ２
Ｃ）１３
■
Ｊｓ
−ｃ
Ｖ −ｃ −２９
Ｖ−ｃ−２５
−ｃ−３０
Ｖ−ｃ −２６
−ｃ−３１
−ｃ−２７
−ｃ−２８
−Ｃ−３２
−ｃ−３３
−ｃ−３４
一般式（ＶＩ） −ａ
Ｒ１，Ｒｚはアルキル基、アルケニル基、アルキニル基
、アリール基、ヘテロ環基を表し、Ｒ３は水素原子又は
置換基を表す。■ ■ ■ -c-4 -c ■ Js C1 (2CH=CH2 C)13 ■ Js -c V -c -29 V-c-25 -c-30 V-c -26 -c-31 -c-27 -c-28 -C-32 -c-33 -c-34 General formula (VI) -a R1 and Rz represent an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group, and R3 is a hydrogen atom or Represents a substituent.
される基を少なくとも一つ含む基である。Ｒは水素原子
又はアルキル基を表し、Ｘは０．Ｓ又はＮＨ基を表し、
Ｙは水素原子又はＯＨ基を表し、ｎは２以上の整数を表
す。Ｒ、、Ｒ２，Ｒ１，Ｒ、で連結して環を形成しても
よい。A group containing at least one group. R represents a hydrogen atom or an alkyl group, and X is 0. Represents S or NH group,
Y represents a hydrogen atom or an OH group, and n represents an integer of 2 or more. R,, R2, R1, and R may be connected to form a ring.
Ｒ□＋ Ｒ２で表されるアルキル基、アルケニル基、ア
ルキニル基、アリール基、ヘテロ環基としては、一般式
（Ｉ）のＲ、、Ｒ、、Ｒ、の同様の基で説明したものと
同じものが挙げられる。The alkyl group, alkenyl group, alkynyl group, aryl group, and heterocyclic group represented by R□+ R2 are the same as those explained for the similar groups of R, , R, , R in general formula (I). Things can be mentioned.
Ｒ１で表される基のうち置換基としては、例えばアルキ
ル基、アルケニル基、アルキニル基、アリール基、ヘテ
ロ環基、アシル基、スルホニル基、オキシカルボニル基
、カルバモイル基等が挙げられる。Ｒ５で表される置換
基のうち、アルキル基、アルケニル基、アルキニル基、
アリール基、ヘテロ環基としては、一般式ＣＩ）のＲＩ
ＲＩＲｓで説明したのと同様の基が挙げられる。Examples of substituents among the groups represented by R1 include alkyl groups, alkenyl groups, alkynyl groups, aryl groups, heterocyclic groups, acyl groups, sulfonyl groups, oxycarbonyl groups, and carbamoyl groups. Among the substituents represented by R5, alkyl groups, alkenyl groups, alkynyl groups,
As the aryl group and heterocyclic group, RI of the general formula CI)
The same groups as those explained for RIRs can be mentioned.
アシル基としては、アセチル、ベンゾイル等が挙げられ
、スルホニル基としては、メタンスルホニル、トルエン
スルホニル等が挙げられ、オキシカルボニル基としては
、エトキシカルボニル、フェノキシカルボニル等が挙げ
られ、カルバモイル基としては、メチルカルバモイル、
フェニルカルバモイル等が挙げられる。Acyl groups include acetyl, benzoyl, etc., sulfonyl groups include methanesulfonyl, toluenesulfonyl, etc., oxycarbonyl groups include ethoxycarbonyl, phenoxycarbonyl, etc., and carbamoyl groups include methyl carbamoyl,
Examples include phenylcarbamoyl.
ＲＩＲ、、Ｒｓ、Ｒａで形成し得る環としては、ピペリ
ジン、モルホリン等の環が挙げられる。Examples of the ring that can be formed by RIR, Rs, and Ra include rings such as piperidine and morpholine.
Ｒで表される基のうちアルキル基はメチル、エチル等で
あり、メチル基が好ましい。Among the groups represented by R, the alkyl group is methyl, ethyl, etc., and the methyl group is preferable.
以下に代表的具体例を示す。Typical specific examples are shown below.
１−ａ−１
’ＩＩ−ａ
（Ｃ２１（Ｓ）２Ｎ
Ｃ２Ｈ５ＣｚＨｓ
Ｎ（ＣＨ２ＣＨ２０）〜ｘｚＣＨ２ＣＨｚＮＮ（Ｃ２Ｈ
ｓ）ｚ（Ｐｈ ＣＨｚ）ｚＮＮＨ（ＣＨ：ＣＨｚＯ）−
ｒ−ＣＨ２ＣＨｚＮＨＮ（ＣＨ＝ Ｐｈ）ｚ（ＣＨ，
）、ＮＮＨ（ＣＨ，ＣＨ，Ｏ）〜。ＨＶｌ−ａ−２
ＣＨ，−Ｐｈ
ＣＯＣＨｓ Ｃ０ＣＨｓ（＋ Ｃ５
Ｈｒ）ｘＮ ＮＣＣＨｘＣＨｘＯ）−ｒａｃＨ２ｃＨ
２Ｎ Ｎ（Ｃ３Ｈ７（ＣＨ３）２Ｎ Ｎ（ＣＨ２Ｃ
Ｈ２Ｏ）ＪＩ−ａ−３
１−ａ−４
（ＣＨ３）２ＮＮＨ（ＣＨ，ＣＨ２０）〜１４ｃＨ２ｃ
Ｈ２ＮＨＮ（ＣＨ３）２ＣＨ，ＣＨ。1-a-1 'II-a (C21(S)2N C2H5CzHs N(CH2CH20)~xzCH2CHzNN(C2H
s)z(Ph CHz)zNNH(CH:CHzO)-
r-CH2CHzNHN(CH= Ph)z(CH,
), NNH(CH,CH,O)~. HVl-a-2 CH, -Ph COCHs C0CHs (+ C5
Hr)xN NCCHxCHxO)-racH2cH
2N N(C3H7(CH3)2N N(CH2C
H2O) JI-a-3 1-a-4 (CH3)2NNH(CH,CH20)~14cH2c
H2NHN(CH3)2CH,CH.
（ＣＨ２−ＣＨＣＨｚ）２ＮＮ（ＣＨ２ＣＨ２０）−ｘ
ａｃＨｚｃＨｚＮ Ｎ（ＣＨ２Ｃ）Ｉ−ＣＨｚ）ｔ（Ｃ
Ｊｙ）ｚＮＮＨ（ＣＨ２ＣＨ２Ｏ）〜、ＣＨ２ｈ
■
ＣＨ，ＣＦＩ。(CH2-CHCHz)2NN(CH2CH20)-x
acHzcHzN N(CH2C)I-CHz)t(C
Jy)zNNH(CH2CH2O)~, CH2h ■ CH, CFI.
（ＣＨ，）ｚＮＮｌ（（ＣＨｚＣＨＯ）−ａｃＨｚｃＨ
ＮＨＮ（ＣＨｉ）ｚＣＨ，−Ｐｈ
（ＣＦｌ、）２Ｎ−Ｎ（ＣＨ，ＣＨＣＨ！Ｏ）〜６ＨＨ
Ｖｌ−ａ
ＣＨｇ −Ｐｈ
―
（Ｐｈ ＣＨｚ）ｚＮ Ｎ（ＣＨ２ＣＨ２０）−ｔ
＋ｃＨｚ ＰｈＣＨ。(CH,)zNNl((CHzCHO)-acHzcH
NHN(CHi)zCH, -Ph (CFl,)2N-N(CH,CHCH!O) ~6HH Vl-a CHg -Ph - (Ph CHz)zN N(CH2CH20)-t
+cHz PhCH.
（ＣＨ３）２ＮＮＨ（ＣＨ２ＣＨ２）−１ｚ（ＣＨ２Ｃ
Ｈ２Ｈ２０）−ｓＨＨ
（Ｐｈ−ＣＨ２）２ＮＮＩｌ（ＣＨ２ＣＨ２Ｈ２０）−
１、ＨＨ
Ｖｌ−ａ−１５
Ｖｌ−ａ−２３
（Ｐｈ ＣＨ２）ｘＮＮＨ（ＣＨ２ＣＨ２Ｏ）ｚｃＨ２
ｃＨ２ＮＨＮ（ＣＨｚ Ｐｈ）ｚＶｌ−ａ−１７
（Ｐｈ−ＣＨり３ＮＮＨ（ＣＨ，ＣＨ，Ｏ）〜、。ＨＶ
ｌ−ａ−１８
ＣＨ。(CH3)2NNH(CH2CH2)-1z(CH2C
H2H20)-sHH (Ph-CH2)2NNIl(CH2CH2H20)-
1, HH Vl-a-15 Vl-a-23 (Ph CH2)xNNH(CH2CH2O)zcH2
cH2NHN(CHz Ph)zVl-a-17 (Ph-CHri3NNH(CH,CH,O)~,.HV
l-a-18 CH.
（ＣＨ３）２ＮＮＨ（ＣＨＩＣＩＯ）〜１゜Ｈ（ＣＨ３
）！Ｎ−Ｎ（（ＣＨ２ＣＨ２Ｏ）−ｔｏＨ）ｘ（ＣＪｓ
）Ｊ ＮＲ（ＣＨｚＣＨｚＮＨ）−＋ｏＨＶｌ−ａ−
２６
（Ｐｈ ＣＨＪｚＮＮ）ｌ（ＣＨｚＣＨｇＮＨ）〜１
４Ｈ（Ｐｈ−ＣＨ２）２Ｎ−Ｎ（ＣＩ（２ＣＨ２０）−
１、ＣＨ２ＣＩ（２Ｎ−Ｎ（Ｃ１（２ｐｈ）２
ＶＴ−ａ−２７
Ｖｌ−ａ−３５
（Ｐｈ ＣＨｚ）ｚＮ Ｎ（（ＣＨ２ＣＨ２ＳＨ）
〜、Ｈ）２０ＣＨ３
Ｖｌ−ａ−２８
（Ｐｈ ＣＨ２）２Ｎ
Ｎ（Ｃ）Ｉ２ＣＨ，Ｏ）〜、、Ｃ）Ｉ、 −Ｐｈ（ＣＨ
ｚ）ｚＮＮＨ（ＣＨ２ＣＨ２Ｓ）ｓｃＴｏｃ［（２Ｎ）
ＩＮ（ＣＨｚ）ｚ■
Ｖｌ−ａ−２９
ＯＣＨ３
α℃Ｈ３
（Ｐｈ−ＣＨ２）２Ｎ−Ｎ（ＣＨ２ＣＨ２Ｓ）−＠ＣＨ
２ＣＨ２Ｎ−Ｎ（ＣＨｘＰｈ）２
Ｖｌ−ａ−３０
ＣｚＨｓ
ＣＢ。(CH3)2NNH(CHICIO)~1°H(CH3
)! N-N((CH2CH2O)-toH)x(CJs
)J NR(CHzCHzNH)-+oHVl-a-
26 (Ph CHJzNN)l (CHzCHgNH) ~1
4H(Ph-CH2)2N-N(CI(2CH20)-
1, CH2CI(2N-N(C1(2ph)2 VT-a-27 Vl-a-35 (Ph CHz)zN N((CH2CH2SH)
~,H)20CH3 Vl-a-28 (Ph CH2)2N N(C)I2CH,O)~,,C)I, -Ph(CH
z)zNNH(CH2CH2S)scToc[(2N)
IN(CHz)z■ Vl-a-29 OCH3 α℃H3 (Ph-CH2)2N-N(CH2CH2S)-@CH
2CH2N-N(CHxPh)2 Vl-a-30 CzHs CB.
（Ｐｈ−ＣＩ（、）、Ｎ−Ｎ（Ｃ）１２Ｃ）ＩＣ）１２
０）−１０（ＣＨ２Ｃ）１０）−、、）１Ｈ
■
Ｖｌ−ａ−３１
（ＣＨｘ）ｚＮＮＨ（ＣＨｚＣｔ（ｚｃＨｚｏ）−ｓＨ
ｃｏｘ −ｐｈ Ｃ１２−Ｐｈ
Ｈ（ｏｃＨ，ｃＨｘ）〜工、Ｎ
ＮＣＣＨ，ＣＨ，Ｏ）〜１４Ｈ
Ｈ
■
（Ｃ４Ｈｓ ）ｚＮＮＨ（ＣＨｚＣ）Ｉ ｚｃＨｚｏ）
−＊ ｏｃＨ２ｃＨｚｃＨ２Ｎ）ＩＮ（Ｃ４Ｈ＊ ）２
（ＣＨＩ）２Ｎ Ｎ（ＣＨ２ＣＨ２０）−ｓｚｃＨ２
ＧＨｚＮ Ｎ（ＣＨｓ）ｚ（ＣＪｓ）２Ｎ Ｎ（Ｃ
ＨｚＣｌ（２ＣＨｚＯ）−ｓｃＨ２ｃＨｚｃＨ２Ｎ
Ｎ（ＣＪａ）ｚ又は
ＮＨ基を表し、
Ｙは水素原子又は
０Ｈ基を表
し、
は２以上の整数を表す。(Ph-CI(,), N-N(C)12C)IC)12
0)-10(CH2C)10)-,,)1H ■ Vl-a-31 (CHx)zNNH(CHzCt(zcHzo)-sH
cox -ph C12-Ph H (ocH, cHx) ~ engineering, N NCCH, CH, O) ~ 14H H ■ (C4Hs )zNNH (CHzC) I zcHzo)
-*ocH2cHzcH2N)IN(C4H*)2
(CHI)2N N(CH2CH20)-szcH2
GHzN N(CHs)z(CJs)2N N(C
HzCl(2CHzO)-scH2cHzcH2N
represents N(CJa)z or an NH group, Y represents a hydrogen atom or an OH group, and represents an integer of 2 or more.
但し、
Ｒが水素原
（Ｐｈ ＣＨ２）２Ｎ Ｎ（ＣＨ２ＣＨ２ＣＨ２０
）−１６（ＣＨ２ＣＨ２Ｈ２０）−１１１８子の時、
ＸはＳ又は
ＮＨ基を表すものとする。However, R is a hydrogen atom (Ph CH2)2N N(CH2CH2CH20
)-16(CH2CH2H20)-1118, X represents an S or NH group.
Ｈ
Ｒ１，Ｒ２で表される基のうち、
アルキル基、
ア
ルケニル基、アルキニル基、アリール基、ヘテロ（Ｐｈ
−ＣＨ２）２Ｎ−Ｎ（ＣＨ２ＣＨ２ＣＨ２０）−ｓｃＨ
ｚｃＨｚｃＨｚＮ Ｎ（ＣＨｚ Ｐｈ）２環基とし
ては、
一般式
のＲ、、Ｒ、、Ｒ、で説
明したものと同様の基か挙げられる。Among the groups represented by H R1 and R2, alkyl groups, alkenyl groups, alkynyl groups, aryl groups, hetero (Ph
-CH2)2N-N(CH2CH2CH20)-scH
Examples of the zcHzcHzN N (CHz Ph) 2-ring group include the same groups as those explained for R, , R, , R in the general formula.
Ｒ、、Ｒ２，Ｔで形成し得る環と
しては、
ピペリジ
ン、モルホリン、キヌクリジン、ピラゾリジン等のヘテ
ロ環が挙げられる。Examples of the ring that can be formed by R, , R2, and T include heterocycles such as piperidine, morpholine, quinuclidine, and pyrazolidine.
一般式 ［） Ｒで表されるアルキル基としてはメチル、エチ ル等であり、 メチル基が好ま しい。general formula [) The alkyl group represented by R is methyl, ethyl Le et al. Methyl group is preferred Yes.
以下に代表的具体例を示す。Typical specific examples are shown below.
Ｒ１，Ｒ２ は水素原子、 アルキル基、 アルケニル ■ 基、 アルキニル基、 ア リール基、 ヘテロ環基を表し、 ＣＨ。R1, R2 is a hydrogen atom, alkyl group, alkenyl ■ base, alkynyl group, a reel group, Represents a heterocyclic group, CH.
Ｒｒ、Ｒｚ、Ｔで環を形成してもよい。Rr, Rz, and T may form a ring.
（Ｃ，Ｉ７）２Ｎ（ＣＨ２ＣＨ２）〜６Ｈ■−ｂ ＣＨ。(C, I7)2N(CH2CH2)~6H■-b CH.
（ＣｚＨｓ） ２Ｎ（ＣＨｚＣＨＯ） ｓＨされる基を
少なく
とも一つ含む基である。(CzHs) 2N(CHzCHO) A group containing at least one group that undergoes sH.
Ｒは水素原子又はアルキル基を表し、
Ｘは０゜
（ＣｚＨｓ）ｚＮ（ＣＨｚＣＨＯ）〜ｒ ４ＧＨｚＣＨ
Ｎ（ＣｚＨｓ）ｚｖ＋−ｂ
■
ＣＨ。R represents a hydrogen atom or an alkyl group, and X is 0゜(CzHs)zN(CHzCHO)~r 4GHzCH
N(CzHs)zv+-b ■ CH.
ＣＨ。CH.
Ｃ，Ｈ，、ＮＨ（ＣＨ，ＣＨＯ）−、、ＣＨ２ＣＨＮＩ
（Ｃ５８，１■
ＣＨ。C,H,,NH(CH,CHO)-,,CH2CHNI
(C58, 1■ CH.
ＣＨ。CH.
ｖ＋−ｂ
（ＣＨｘ ＝ ＣＨＣＨｚ）Ｊ（Ｃ）ｌｚｃＨｏ）−ｓ
ｃＨ＊ｃＨＮ（ＣＨｚＣＨＣＨｘ）ｘ
■
ＣＨ。v+-b (CHx = CHCHz)J(C)lzcHo)-s
cH*cHN(CHzCHCHx)x ■ CH.
ノ
（Ｃ，Ｈ，、）、Ｎ（ＣＨ，Ｃｌ０）２ＨＶＴ−ｂ−１
０
ＣＨ，ＣＨ３
（Ｐｈ−ＣＨ２）２Ｎ（ＣＨ，ＣＨＯ）、ＣＨ，ＣＨＮ
（Ｃ）Ｉ。ノ(C,H,,),N(CH,Cl0)2HVT-b-1
0 CH, CH3 (Ph-CH2)2N (CH, CHO), CH, CHN
(C)I.
Ｐｈ） ２
ｙ＋−ｂ
Ｃ，Ｈ，、ＮＨ（ＣＨ，ＣＩ（ＣＨ，Ｏ）〜１２８Ｈ
■
■
■
■−ｂ
（Ｃ，Ｈ，）２Ｎ（ＣＨ，ＣＨＣＨ２０）−１ＨＨ
■
（Ｃ，）ｌ□７）、ＮＣＣＨ２ＣＨＣＨ２０）〜１４Ｈ
Ｈ
Ｔ／Ｉ−ｂ−２１
（ＣＨｚ−ＣＨＣＨｚ）２Ｎ（ＣＨ２ＣＨＣＨｚＯ）〜
□。ＨＨ
しＨ８
■
■
（Ｐｈ−Ｃ）１２）２Ｎ（ＣＨ，ＣＨＣＨ２０）〜、Ｈ
Ｈ
Ｖｌ−ｂ−２９
ＣＨ。Ph) 2 y+-b C,H,,NH(CH,CI(CH,O)~128H ■ ■■ ■-b (C,H,)2N(CH,CHCH20)-1HH ■ (C,)l□ 7), NCCH2CHCH20) ~ 14H
H T/I-b-21 (CHz-CHCHz)2N(CH2CHCHzO)~
□. HH ShiH8 ■ ■ (Ph-C) 12) 2N (CH, CHCH20) ~, H
H Vl-b-29 CH.
（Ｃ，ＨＩ）２Ｎ（０日２ＣＨＯ）〜１（ＣＨ２ＣＨ２
Ｈ２０）〜１゜ＨＨ
■−ｂ
しＩ′１３
ＣＨ。(C, HI) 2N (0 day 2 CHO) ~ 1 (CH2CH2
H20) ~ 1°HH ■-b I'13 CH.
ＣＣＨ２−ＣＨＣＨ２）２Ｎ（ＣＨ２’ＣＨＣＨ２０）
〜１゜（ＣＨ２ＣＨ２）〜、。Ｈ■
Ｈ
ＣａＨ＋ ｙＮＨ（ＣＨｚＣＨＯ）−＋ ＋（ＣＨｚＣ
ＨＣＨｚＯ）−ｚｏＨＨ
Ｖｌ−ｂ−３９
■
■
（Ｃ，Ｈ７）２Ｎ（ＣＨ２ＣＨ２Ｓ）〜ＩＣＨ２ＣＨ２
Ｎ（Ｃ３Ｈ，）！■
（ＣＨ，ＣＨ２ＣＨ２Ｈ，）、Ｎ（ＣＨ２ＣＨ，５）−
１゜ＣＨ２Ｃｌ（２Ｎ（ＣＩ（、ＣＨＣＨＣＨ、）２
■−ｂ−４１
■−ｂ
（ＣＪ６）２Ｎ（ＣＨ２ＣＨ２ＮＨ）〜１４ＨＣｉＨ＋
３ＮＨ（ＣＨ２ＣＨ２Ｓ）〜ＩｚＣＨ２ＣＨ２ＮＨＣ
ｓＨ＋ ｓ■
ｖｔ−ｂ−５０
（ＣＨ２＝ＣＨＣＦ１２）２Ｎ（ＣＨ，ＣＩ（２Ｎ）ｌ
）−２゜Ｈ■
ｃ、ｎ、 ７ＮＨ（ＣＨ２ＣＨ！ＮＯ）〜□、ＨＶＩ−
ｂ−５１
ｖｔ−ｂ
■
Ｖｌ−ｂ−４５
■
■
ＣＨミＣＣＨ２ＮＨ（ＣＨ２ＣＨ２Ｓ）〜２゜ＣＨ２Ｃ
Ｈ２ＮＨＣＨ２ＣＥＥＣＨ■−ｂ
ＶＴ−ｂ−６３
Ｖｌ−ｂ−５６
Ｃ）ｌ、−ＣＨ２Ｈ２Ｎ（ＣＨ２ＣＨ２Ｓ）〜１゜ＣＨ
ｘＣＨｚＮＣＦ１２ＣＨ−ＣＨ２Ｖｌ−ｂ−６４
しＩ′ｌ３
Ｖｌ−ｂ−５８
（Ｃ４）１１）２Ｎ（ＣＨ２ＣＨ２ＣＨｆｆＯ）〜、Ｈ
Ｖｌ−ｂ−５９
（ＣＨ２−ＣＨＣＨｚ）２Ｎ（ＣＨｚＣＨｘＣＨ２０）
〜１゜ＨＶｌ−ｂ−６０
ＣＪｓ
ＣＨｊＣＣＨ，Ｎ（Ｃ）１２ＣＨ２ＣＨ，Ｏ）〜１４Ｈ
Ｖｌ−ｂ−６５
ＶＩ−ｂ−６６
ｖ＋−ｂ−６７
Ｖｌ−ｂ−６２
ＣｓＨ＋ ＋ＮＨ（ＣＨｚＣＨｚＣＨｚＯ）〜１□ＨＨ
Ｖ［−ｂ−６８
（ＣＪｓ）ｚＮ（ＣＨｚＣＨｚＣＨｚＯ）−ｚｏｃＨ２
ｃＨｚｃＨｚＮ（ＣＪｓ）ｚ一般式Ｃ■）−ｃ
載されている。CCH2-CHCH2)2N(CH2'CHCH20)
〜1゜(CH2CH2)〜,. H■ H CaH+ yNH(CHzCHO)-+ +(CHzC
HCHzO)-zoHH Vl-b-39 ■ ■ (C,H7)2N(CH2CH2S)~ICH2CH2
N(C3H,)! ■ (CH,CH2CH2H,), N(CH2CH,5)-
1゜CH2Cl(2N(CI(,CHCHCH,)2 ■-b-41 ■-b (CJ6)2N(CH2CH2NH)~14HCiH+
3NH (CH2CH2S) ~ IzCH2CH2NHC
sH+ s■ vt-b-50 (CH2=CHCF12)2N(CH,CI(2N)l
)-2゜H■ c, n, 7NH (CH2CH!NO) ~□, HVI-
b-51 vt-b ■ Vl-b-45 ■ ■ CHmiCCH2NH (CH2CH2S) ~ 2°CH2C
H2NHCH2CEECH■-b VT-b-63 Vl-b-56 C)l, -CH2H2N(CH2CH2S) ~ 1°CH
xCHzNCF12CH-CH2Vl-b-64 I'l3 Vl-b-58 (C4)11) 2N(CH2CH2CHffO) ~, H
Vl-b-59 (CH2-CHCHz)2N (CHzCHxCH20)
〜1゜HVl-b-60 CJs CHjCCH,N(C)12CH2CH,O)〜14H
Vl-b-65 VI-b-66 v+-b-67 Vl-b-62 CsH+ +NH(CHzCHzCHzO)~1□HH V[-b-68 (CJs)zN(CHzCHzCHzO)-zocH2
cHzcHzN(CJs)zGeneral formulaC■)-c is listed.
π値が−０，５〜−１，０の置換基としては、例えばＲ
、、Ｒ２は水素原子、アルキル基、アルケニル基、アル
キニル基、アリール基、ヘテロ環基を表し、Ｒ，、Ｒ，
、Ｇで環を形成してもよい。Examples of substituents with a π value of -0,5 to -1,0 include R
,,R2 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, and R,,R,
, G may form a ring.
Ｇは−（ＣｌｈＣＨｚ）「で表される基を少なくとも一
つ含み、かつ疎水性置換基定数π値が−０，５〜−１，
０の置換基を少なくとも二つ含むか、又はπ値が−１，
０より小の置換基を少なくとも一つ含むものとする。ｎ
は２以上の整数を表す。G contains at least one group represented by -(ClhCHz) and has a hydrophobic substituent constant π value of -0,5 to -1,
Contains at least two substituents of 0, or has a π value of -1,
It shall contain at least one substituent smaller than 0. n
represents an integer greater than or equal to 2.
Ｒ、、Ｒ１で表される基のうち、アルキル、アルケニル
、アルキニル、アリール、ヘテロ環の６基としては、一
般式（１）のＲ、、Ｒ、、Ｒ、で説明したのと同様の基
が挙げられる。Among the groups represented by R, , R1, the six groups of alkyl, alkenyl, alkynyl, aryl, and heterocycle include the same groups as explained for R, , R, , R in general formula (1). can be mentioned.
Ｒ、、Ｒ！、Ｇで形成し得る環としては、例えばピペリ
ジン、キヌクリジン、モルホリン等の環が挙げられる。R,,R! , G include, for example, rings such as piperidine, quinuclidine, and morpholine.
疎水性置換基定数Ｋについては、薬物の構造活性相関（
南江堂）、７９〜１０３頁（昭和５４年）に記ＮＨＣＯ
ＣＨ３，−＜Ｉ＞ 等の基が挙げられ、Ｋ値が−１
，０より小の置換基としては、例えば−ＣＯＮＦＩ！。Regarding the hydrophobic substituent constant K, the structure-activity relationship of the drug (
Nankodo), pp. 79-103 (1978) NHCO
Groups such as CH3, -<I> are mentioned, and the K value is -1
, as a substituent smaller than 0, for example -CONFI! .
Ｃ０ＮＨＯＨ，Ｃ０ＮＨＣＨｓ、 −ＮＨ２，ＮＨＣＯ
ＮＨ２，−ＮＨＣＯＮＨ２゜−ＮＨＣＯＮＨ２、−ＮΦ
（ＣＨ３）！、 −０’、 −０ＣＯＮＨ２，−５Ｏ３
ｅ−５ＯＪＨ３，−５ＯＣＨ３，５ｏ２ＣＨ３，−Ｃｏ
ｏｅ等（１）１＆カ挙Ｉｆられる。C0NHOH, C0NHCHs, -NH2, NHCO
NH2, -NHCONH2゜-NHCONH2, -NΦ
(CH3)! , -0', -0CONH2, -5O3
e-5OJH3, -5OCH3, 5o2CH3, -Co
oe, etc. (1) 1 & number If.
以下に代表的具体例を示す。Typical specific examples are shown below.
１−ｃ−１
（ｉ Ｃｌ７）ｉＮ（ＣＨｚＣＩｂＯ）ｓｃＨｚｃＯ
ＮＨｚ１−ｃ−２
（ｉ−Ｃ，Ｈ，）、Ｎ（ＣＨ２ＣＨ２０）、ＣＨ，ＣＯ
ＯＮａＩ−ｃ−３
（Ｃ２Ｈ５）２Ｎ（ＣＨ２ＣＨ２Ｏ）３ＣＯＮＨ。1-c-1 (iCl7)iN(CHzCIbO)scHzcO
NHz1-c-2 (i-C,H,), N(CH2CH20), CH,CO
ONaI-c-3 (C2H5)2N(CH2CH2O)3CONH.
１−ｃ−４
（ＨＯＣＨ，ＣＨ２Ｃｌり２Ｎ（ＣＨ，ＣＨ２Ｏ）、Ｈ
Ｖｌ−ｃ−５
（ＣＨ２ＣＨＣＨｚ）２Ｎ（ＣＨｚＣＨｚＯ）〜ａｃＨ
２ｃＯＮＨｚＶｌ−ｃ−６
ＣＨ２＝ＣＨＣＨ２ＮＨＣＣＨｘＣＨｚＯ）〜６ＧＨｚ
ｃｏＯＫ■
（ＣＨ：ＣＣ１（、）２Ｎ（ＣＨ２ＣＨ２０）〜、ＣＨ
２Ｃ０ＮＨｚＣＨ，＝ ＣＨＣ）ｌ、Ｎ（ＣＨ２ＣＨ２
Ｏ）〜、ＣＨ２Ｃ０ＮＨＣＨ３■
ＣＨ。1-c-4 (HOCH, CH2Cl2N(CH, CH2O), H
Vl-c-5 (CH2CHCHz)2N(CHzCHzO) ~ acH
2cONHzVl-c-6 CH2=CHCH2NHCCHxCHzO)~6GHz
coOK■ (CH:CC1(,)2N(CH2CH20)~,CH
2C0NHzCH,=CHC)l,N(CH2CH2
O) ~, CH2C0NHCH3■ CH.
Ｖｌ−ｃ
ＶＴ−ｃ−２３
Ｖｌ−ｃ−２４
■
■
一１５
Ｖｌ−ｃ−１６
■
ＶＩ−ｃ−１８
■
（ＨＯＣＨｚＣＨｚ） ｚＮ（Ｃ）ｌｚｃＨ２０）−ｒ
４ＣＩ（ｘｃＨｚＮ（ＣＨｚＣＩｂＯＨ）ｚ■−ｃ
−３２
■−ｃ−３４
Ｖｌ−ｃ−３５
ＶＴ−ｃ−３６
Ｖｌ−ｃ−３７
本発明を適用した高コントラストな画像を得ることかで
きるハロゲン化銀写真感光材料中には、上記一般式〔Ａ
〕及び〔Ｂ〕で表されるヒドラジン化合物が少なくとも
１種及びＣＩ）〜ＣＶＩ）で表される造核促進化合物の
少なくとも１種が含有されるが、該写真感光材料に含ま
れる一般式〔Ａ〕。Vl-c VT-c-23 Vl-c-24 ■ ■ -15 Vl-c-16 ■ VI-c-18 ■ (HOCHzCHz) zN(C)lzcH20)-r
4CI(xcHzN(CHzCIbOH)z■-c
-32 ■-c-34 Vl-c-35 VT-c-36 Vl-c-37 Silver halide photographic materials capable of obtaining high-contrast images to which the present invention is applied include compounds of the general formula [ A
] and [B] and at least one nucleation-promoting compound represented by CI) to CVI). ].
〔Ｂ〕及び（１）〜［’ＶＩ）の化合物の量は、写真感
光材料中に含有されるハロゲン化銀１モル当たり５ Ｘ
１０−’モル−５Ｘ １０−’モルであることが好ま
しい。・特に５ Ｘ １０−’モル〜Ｉ Ｘ １０−”
モルの範囲とすることが好ましい。The amount of the compounds [B] and (1) to ['VI) is 5X per mole of silver halide contained in the photographic light-sensitive material.
Preferably 10-' moles-5X 10-' moles. - Especially 5 X 10-' mol to I X 10-''
Preferably, the amount is in the molar range.
本発明のハロゲン化銀写真感光材料は、少なくとも一層
のハロゲン化銀乳剤層を有する。すなわちハロゲン化銀
乳剤層は、支持体の片面に少なくとも一層設けられてい
ることもあるし、支持体の両面に少なくとも一層設けら
れていることもある。The silver halide photographic material of the present invention has at least one silver halide emulsion layer. That is, at least one silver halide emulsion layer may be provided on one side of the support, or at least one silver halide emulsion layer may be provided on both sides of the support.
そして、このハロゲン化銀乳剤は支持体上に直接塗設さ
れるか、あるいは他の層例えばハロゲン化銀乳剤を含ま
ない親水性コロイド層を介して塗設されることができ、
さらにハロゲン化銀乳剤層の上には、保護層としての親
水性コロイド層を塗設してもよい。又、ハロゲン化銀乳
剤層は、異なる感度、例えば高感度及び低感度の各／％
ロゲン化銀乳剤層に分けて塗設してもよい。この場合、
各ハロゲン化銀乳剤層の間に、中間層を設けてもよい。Then, this silver halide emulsion can be coated directly on the support, or it can be coated via another layer such as a hydrophilic colloid layer that does not contain the silver halide emulsion.
Furthermore, a hydrophilic colloid layer as a protective layer may be coated on the silver halide emulsion layer. Additionally, the silver halide emulsion layers may have different sensitivities, e.g. high and low sensitivity/%.
The silver halide emulsion layer may be coated separately. in this case,
An intermediate layer may be provided between each silver halide emulsion layer.
すなわち必要に応じて親水性コロイドから成る中間層を
設けてもよい。又、ハロゲン化銀乳剤層と保護層との間
に、中間層、保護層、アンチハレーション層、バッキン
グ層などの非感光性親水性コロイド層を設けてもよい。That is, an intermediate layer made of hydrophilic colloid may be provided if necessary. Further, a non-photosensitive hydrophilic colloid layer such as an intermediate layer, a protective layer, an antihalation layer, a backing layer, etc. may be provided between the silver halide emulsion layer and the protective layer.
一般式〔Ａ〕、ＣＢ）、 〔■）〜［ＶＩ〕で表される
化合物は本発明のハロゲン化銀写真感光材料中のハロゲ
ン化銀乳剤層または該ハロゲン化銀乳剤層に隣接する親
水性コロイド層に含有させる。The compounds represented by the general formulas [A], CB), [■) to [VI] are hydrophilic in the silver halide emulsion layer or adjacent to the silver halide emulsion layer in the silver halide photographic light-sensitive material of the present invention. Contained in the colloid layer.
次に本発明のハロゲン化銀写真感光材料に用いるハロゲ
ン化銀について説明する。ハロゲン化銀としては、４モ
ル％以下の沃化銀、好ましくは３モル％以下の沃化銀を
含む塩沃臭化銀、もしくは沃臭化銀である。このハロゲ
ン化銀の粒子の平均径は０．０５〜０．５μｍの範囲の
ものが好ましく用いられるが、なかでも０，１０〜０４
４０μｍのものが好適である。Next, the silver halide used in the silver halide photographic material of the present invention will be explained. The silver halide is silver chloroiodobromide or silver iodobromide containing 4 mol % or less of silver iodide, preferably 3 mol % or less of silver iodide. The average diameter of the silver halide particles is preferably in the range of 0.05 to 0.5 μm, particularly 0.10 to 0.04 μm.
A thickness of 40 μm is suitable.
本発明で用いるハロゲン化銀粒子の粒径分布は任意であ
るが、以下定義する単分散度の値が１〜２０％のものか
好ましく、更に好ましくは５〜１５％の範囲となるよう
に調整する。The particle size distribution of the silver halide grains used in the present invention is arbitrary, but it is preferably adjusted so that the monodispersity value defined below is in the range of 1 to 20%, more preferably in the range of 5 to 15%. do.
ここで単分散度は、粒径の標準偏差を平均粒径で割った
値（変動係数）を１００倍した数値（％）として定義さ
れるものである。なおハロゲン化銀粒子の粒径は、便宜
上、立方晶粒子の場合は稜長で表し、その他の粒子（８
面体、１４面体等）は、投影面積の平方根で算出する。Here, the monodispersity is defined as a value (%) obtained by multiplying by 100 the value obtained by dividing the standard deviation of particle diameter by the average particle diameter (coefficient of variation). For convenience, the grain size of silver halide grains is expressed by the edge length in the case of cubic grains, and is expressed by the edge length for other grains (8
(hedron, tetradecahedron, etc.) is calculated by the square root of the projected area.
本発明を実施する場合、例えばハロゲン化銀の粒子とし
て、その構造が少なくとも２層の多層積層構造を有する
タイプのものを用いることができ、例えばコア部に沃臭
化銀、シェル部が臭化銀である沃臭化銀粒子から成るも
のを用いることができる。このとき、沃素を任意の層に
５モル％以内で含有させることができる。When carrying out the present invention, for example, silver halide grains having a multilayer structure of at least two layers can be used, for example, silver iodobromide in the core and bromide in the shell. Those consisting of silver iodobromide grains, which are silver, can be used. At this time, iodine can be contained in any layer within 5 mol%.
本発明のハロゲン化銀乳剤に用いられるハロゲン化銀粒
子は、粒子を形成する過程及び／又は成長させる過程で
、カドミウム塩、亜鉛塩、鉛塩、タリウム塩、イリジウ
ム塩（錯塩を含む）、ロジウム塩（錯塩を含む）及び鉄
塩（錯塩を含む）から選ばれる少なくとも１種を用いて
金属イオンを添加し、粒子内部に及び／又は粒子表面に
これらの金属元素を含有させることができ、又、適当な
還元的雰囲気におくことにより、粒子内部及び／又は粒
子表面に還元増感核を付与できる。The silver halide grains used in the silver halide emulsion of the present invention are formed by cadmium salts, zinc salts, lead salts, thallium salts, iridium salts (including complex salts), rhodium salts, Metal ions can be added using at least one selected from salts (including complex salts) and iron salts (including complex salts) to contain these metal elements inside the particles and/or on the particle surfaces, and By placing the particles in a suitable reducing atmosphere, reduction sensitizing nuclei can be provided inside the particles and/or on the particle surfaces.
更に又、ハロゲン化銀は種々の化学増感剤によって増感
することができる。その増感剤として、例えば、活性ゼ
ラチン、硫黄増感剤（チオ硫酸ソーダ、アリルチオカル
バミド、チオ尿素、アリルインチアシネート等）、セレ
ン増感剤（Ｎ、Ｎ−ジメチルセレノ尿素、セレノ尿素等
）、還元増感剤（トリエチレンテトラミン、塩化銀１ス
ズ等）、例えばカリウムクロロオーライト、カリウムオ
ーリチオシアネート、カリウムクロロオーレート、２−
オーロスルホペンゾチアゾールメチルクロライド、ア・
ンモニウムクロロバラデート、カリウムクロロブラチ不
一ト、ナトリウムクロロバラダイト等で代表される各種
貴金属増感剤等をそれぞれ単独で、あるいは２種以上併
用して用いることかできる。Furthermore, silver halide can be sensitized with various chemical sensitizers. Examples of the sensitizers include activated gelatin, sulfur sensitizers (sodium thiosulfate, allylthiocarbamide, thiourea, allyl inthiacinate, etc.), selenium sensitizers (N,N-dimethylselenourea, selenourea, etc.) ), reduction sensitizers (triethylenetetramine, silver chloride, etc.), such as potassium chlorooleite, potassium aurithiocyanate, potassium chlorooleate, 2-
Aurosulfopenzothiazole methyl chloride, a.
Various noble metal sensitizers represented by ammonium chlorovaladate, potassium chlorobratate, sodium chlorovaladite, etc. can be used alone or in combination of two or more.
なお金増感剤を使用する場合は助剤的にロダンアンモン
を使用することもできる。When using a metal sensitizer, rhodanammonium can also be used as an auxiliary agent.
本発明に用いるハロゲン化銀粒子は、内部の感度より表
面感度の高い粒子、謂ゆるネガ画像を与えるハロゲン化
銀粒子に好ましく適用することができるので上記化学増
感剤で処理することにより性能を高めることができる。The silver halide grains used in the present invention can be preferably applied to grains whose surface sensitivity is higher than their internal sensitivity, so-called silver halide grains that give negative images. can be increased.
又、本発明に用いられるハロゲン化銀乳剤は、メルカプ
ト類（ｌ−フェニル−５−メルカプトテトラゾール、２
−メルカプトベンツチアゾール）、ベンゾトリアゾール
類（５−ブロムベンゾトリアゾール−５−メチルベンゾ
トリアゾール）、ベンツイミダゾール類（６−ニドロペ
ンツイミダゾール）などを用いて安定化又はカブリ抑制
を行うことができる。Further, the silver halide emulsion used in the present invention contains mercapto compounds (l-phenyl-5-mercaptotetrazole, 2
-Mercaptobenzthiazole), benzotriazoles (5-brombenzotriazole-5-methylbenzotriazole), benzimidazoles (6-nidropenzimidazole), etc. can be used to stabilize or suppress fog.
感光性ハロゲン化銀乳剤層又はその隣接層には、感度上
昇、コントラスト上昇または現像促進の目的でリサーチ
・ディスクロージャー（Ｒｅ５ｅａｒｃｈＤｉｓｃｌｏ
ｕｓｕｒｅ） １７４６３号のＸＸＩ）ＥＪＢ−Ｄ項に
記載されている化合物を添加することができる。The photosensitive silver halide emulsion layer or its adjacent layer may contain research disclosure materials for the purpose of increasing sensitivity, increasing contrast, or promoting development.
The compounds described in section XXI) EJB-D of No. 17463 can be added.
又、下記の一般式ＣＰ）で表される化合物を添加するこ
とが好ましい。Further, it is preferable to add a compound represented by the following general formula CP).
一般式ＣＰ）
Ｒ，−０−（ＣＢ、ＣＨ２■τＨ
〔式中Ｒ１は水素原子、あるいは無置換又は置換基をも
つ芳香族環を表し、ｎは１０〜２００までの整数を表す
。〕
まず、一般式（Ｐ）で表される化合物より好ましい具体
例をあげる。分子量は１５００以上のものが好ましいが
、これらに限定されるものではない。General formula CP) R, -0-(CB, CH2■τH [In the formula, R1 represents a hydrogen atom or an unsubstituted or substituted aromatic ring, and n represents an integer from 10 to 200.] First , specific examples more preferable than the compounds represented by general formula (P) will be given.The molecular weight is preferably 1500 or more, but is not limited thereto.
Ｐ −Ｉ ＨＯ（ＣＨ２ＣＨ２０）ｎＨｎ＝ｌ
０Ｐ ２ ＨＯ（ＣＨ２ＣＨ２０）ｎ Ｈｎ
” ３０Ｐ −３ＨＯ（ＣＨ，ＣＨｚＯ）ｎＨｎ＝５
０Ｐ ４ ＨＯ（ＣＨ２ＣＨ２０）ｎ Ｈｎ
＝ ７０Ｐ ５ ＨＯ（ＣＨｚＣＨｚＯ）
ｎＨｎ＝１５０Ｐ ６ ＨＯ（ＣＨｉＣＨｚ
Ｏ）ｎＨ’ ｎ＝２００Ｈ
これらの化合物は、市販されており容易に入手すること
ができる。これらの化合物はハロゲン化銀１モルに対し
０．０１〜４．０モル添加するのが好ましく、０．０２
〜２モル′がより好ましい。又、乳剤層中に含有させる
ことが好ましい。又、ｎの値が異なる２種以上の化合物
を含んでも構わない。P-I HO(CH2CH20)nHn=l
0P 2 HO(CH2CH20)n Hn
”30P-3HO(CH,CHzO)nHn=5
0P 4 HO(CH2CH20)n Hn
= 70P 5 HO (CHzCHzO)
nHn=150P 6 HO (CHiCHz
O) nH' n=200H These compounds are commercially available and can be easily obtained. It is preferable to add these compounds in an amount of 0.01 to 4.0 mol per mol of silver halide, and 0.02 mol.
-2 mol' is more preferred. It is also preferable to include it in the emulsion layer. Further, two or more types of compounds having different values of n may be included.
本発明に用いられるハロゲン化銀乳剤には、増感色素、
可塑剤、帯電防止剤、界面活性剤、硬膜剤などを加える
こともできる。The silver halide emulsion used in the present invention includes a sensitizing dye,
Plasticizers, antistatic agents, surfactants, hardeners, etc. can also be added.
本発明に係る一般式（Ａ：］、ＣＢ）、（Ｉ）〜（Ｖｌ
）の化合物を親水性コロイド層に添加する場合、該親水
性コロイド層のバインダーとしてはゼラチンが好適であ
るが、ゼラチン以外の親水性コロイドも用いることがで
きる。これらの親水性バインダーは支持体の両面にそれ
ぞれｌｏｇ／ｍ２以下で塗設することが好ましい。General formula (A:], CB), (I) to (Vl) according to the present invention
) is added to a hydrophilic colloid layer, gelatin is suitable as the binder for the hydrophilic colloid layer, but hydrophilic colloids other than gelatin can also be used. These hydrophilic binders are preferably coated on both sides of the support at log/m2 or less.
本発明の実施に際して用い得る支持体としては、例えは
バライタ紙、ポリエチレン被覆紙、ポリプロピレン合成
紙、ガラス板、セルロースアセテート、セルロースナイ
トレート、例えばポリエチレンテレフタレートなどのポ
リエステルフィルムを挙げることができる。これらの支
持体は、それぞれハロゲン化銀写真感光材料の使用目的
に応じて適宜選択される。Supports that can be used in the practice of the present invention include, for example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper, glass plates, cellulose acetate, cellulose nitrate, and polyester films such as polyethylene terephthalate. These supports are appropriately selected depending on the intended use of the silver halide photographic material.
本発明のハロゲン化銀写真感光材料を現像処理するには
、例えば以下の現像主薬が用いられる。For developing the silver halide photographic material of the present invention, the following developing agents are used, for example.
ＨＯ−（ＣＨ＝ ＣＨ）ｎ −ＯＨ型現像主薬の代表的
なものとしては、ハイドロキノンがあり、その他にカテ
コール、ピロガロールなどがある。Typical examples of HO-(CH=CH)n-OH type developing agents include hydroquinone, and others such as catechol and pyrogallol.
又、ＨＯ−（ＣＨ−ＣＨ）ローＮＨ，型現像剤としては
、オルト及びバラのアミノフェノール又はアミノピラゾ
ロンが代表的なもので、Ｎ−メチル−ｐ−アミノフェノ
ール、Ｎ−β−ヒドロキシエチル−ｐ−アミンフェノー
ル、ｐ−ヒドロキシフェニルアミノ酢酸、２−アミノナ
フトール等がある。In addition, typical HO-(CH-CH) rho-NH type developers include ortho and rose aminophenols or aminopyrazolones, N-methyl-p-aminophenol, N-β-hydroxyethyl- Examples include p-aminephenol, p-hydroxyphenylaminoacetic acid, and 2-aminonaphthol.
ヘテロ環型現像剤としては、■−フェニルー３−ピラゾ
リドン、１−７エニルー４．４−ジメチル−３−ピラゾ
リドン、１−フェニル−４−メチル−４−しドロキシメ
チル−３−ピラゾリドン、１−フェニル−４−メチル−
４−ヒドロキシメチル−３−ピラゾリドンのような３−
ピラゾリドン類等を挙げることができる。Examples of the heterocyclic developer include ■-phenyl-3-pyrazolidone, 1-7enyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-droxymethyl-3-pyrazolidone, and 1-phenyl-4-dimethyl-3-pyrazolidone. 4-methyl-
3- such as 4-hydroxymethyl-3-pyrazolidone
Examples include pyrazolidones and the like.
その他、Ｔ、Ｈ，ジェームス著ザ・セオリイ・オブ・ザ
・ホトグラフインク・プロセス第４版（Ｔｈｅ Ｔｈｅ
ｏｒｙ ｏｆ ｔｈｅ Ｐｈｏｔｏｇｒａｐｈｉｃ Ｐ
ｒｏｃｅｓｓ。Other books include The Theory of the Photographic Ink Process, 4th edition, by T. H. James.
ory of the Photographic P
rocess.
Ｆｏｕｒｔｈ Ｅｄｉｔｉｏｎ）第２９１〜３３４頁及
びジャーナル・オブ・ザ・アメリカン・ケミカル・ソサ
エティ（Ｊｏｕｒｎａｌ ｏｆ ｔｈｅ Ａｍｅｒｉｃ
ａｎ Ｃｈｅｍｉｃａｌ ５ｏｃｉｅｔｙ）７３巻、３
．１００頁（１９５１）に記載されている如き現像剤が
本発明に有効に使用し得るものである。これらの現像剤
は単独で使用しても２種以上組み合わせてもよいが、２
種以上を組み合わせて用いる方が好ましい。Fourth Edition, pages 291-334 and Journal of the American Chemical Society.
an Chemical 5ociety) Volume 73, 3
．． Developers such as those described on page 100 (1951) can be effectively used in the present invention. These developers may be used alone or in combination of two or more, but
It is preferable to use a combination of two or more species.
又、本発明の感光材料の現像に使用する現像液には保恒
剤として、例えば亜硫酸ソーダ、亜硫酸カリ等の亜硫酸
塩を用いても、本発明の効果が損なわれることはない。Furthermore, even if a sulfite salt such as sodium sulfite or potassium sulfite is used as a preservative in the developer used for developing the photosensitive material of the invention, the effects of the invention will not be impaired.
又、保恒剤としてヒドロキシルアミン、ヒドラジド化合
物を用いてもよい。Furthermore, hydroxylamine and hydrazide compounds may be used as preservatives.
その他一般白黒現像液で用いられるような苛性アルカリ
、炭酸アルカリ又はアミンなどによるｐＨの調整とバッ
ファー機能をもたせることができる。In addition, pH adjustment and buffer functions can be provided using caustic alkali, carbonate alkali, or amine, which are used in general black and white developers.
本発明に用いられる現像液はｐＨ１１未満のものが使用
できるのが特徴である。又現像液にはブロムカリなど無
機現像抑制剤及び５−メチルベンゾトリアゾール、５−
メチルベンツイミダゾール、５−二トロインタソール、
アデニン、グアニン、ｌ−フェニル−５−メルカプトテ
トラゾールなどの有機現像抑制剤、エチレンジアミン四
酢酸等の金属イオン捕捉剤、メタノール、エタノール、
ベンジルアルコール、ポリアルキレンオキシド等の現像
促進剤、アルキルアリールスルホン酸ナトリウム、天然
のサポニン、糖類または前記化合物のアルキルエステル
物等の界面活性剤、グルタルアルデヒド、ホルマリン、
グリオキザール等の硬膜剤、硫酸ナトリウム等のイオン
強度調整剤等の添加を行うことは任意である。The developer used in the present invention is characterized in that a developer having a pH of less than 11 can be used. In addition, the developer contains an inorganic development inhibitor such as brompotash, 5-methylbenzotriazole, 5-
Methylbenzimidazole, 5-nitrointasol,
Organic development inhibitors such as adenine, guanine, l-phenyl-5-mercaptotetrazole, metal ion scavengers such as ethylenediaminetetraacetic acid, methanol, ethanol,
Development accelerators such as benzyl alcohol and polyalkylene oxide, sodium alkylarylsulfonate, natural saponins, surfactants such as sugars or alkyl esters of the above compounds, glutaraldehyde, formalin,
It is optional to add a hardening agent such as glyoxal, an ionic strength regulator such as sodium sulfate, etc.
本発明において使用される現像液には、有機溶媒として
ジェタノールアミンやトリエタノールアミン等のアルカ
ノールアミン類やジエチレングリコール、トリエチレン
グリコール等のグリコール類、又、ジエチルアミノ−１
，２−プロパンジオール、ブチルアミツブロバノール等
のアルキルアミノアルコール類を含有させてもよい。The developing solution used in the present invention includes alkanolamines such as jetanolamine and triethanolamine, glycols such as diethylene glycol and triethylene glycol, and diethylamino-1
, 2-propanediol, butylamitubrobanol, and other alkylamino alcohols may be included.
以下に本発明の具体的実施例を述べるが、本発明の実施
の態様はこれらに限定されない。Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited thereto.
実施例１
（ハロゲン化銀乳剤Ａの調製）
同時混合法を用いて沃臭化銀乳剤（銀１モル当たり沃化
銀２モル％）を調製した。この混合時にに２！ｒＣＱ＝
を銀１モル当たり８Ｘ １０−’モル添加した。Example 1 (Preparation of Silver Halide Emulsion A) A silver iodobromide emulsion (2 mol % of silver iodide per 1 mol of silver) was prepared using a simultaneous mixing method. 2 when mixing this! rCQ=
was added at 8X 10-' moles per mole of silver.
得られた乳剤は、平均粒径０．２０μｍの立方体単分散
粒子（変動係数９．５％）からなる乳剤であった。The obtained emulsion was an emulsion consisting of cubic monodisperse grains (coefficient of variation 9.5%) with an average grain size of 0.20 μm.
この乳剤に銀１モル当たり６．５ｍＲの１％沃化カリウ
ム水溶液を添加した後、変成ゼラチン（特願平１−１８
０７８７号の例示化合物Ｇ−８）を加え、特願平１−１
８９０７８７号の実施例１と同様の方法で水洗、脱塩し
た。脱塩後の４０℃でのＩＩ）Ａｇは８．０であった。After adding a 1% aqueous potassium iodide solution of 6.5 mR per mole of silver to this emulsion, modified gelatin (Japanese Patent Application No. 1992-18
By adding exemplified compound G-8) of No. 0787, patent application No. 1-1
It was washed with water and desalted in the same manner as in Example 1 of No. 890787. II) Ag at 40°C after desalting was 8.0.
更に再分散時に抗菌剤として下お化合物〔Ａ〕、〔Ｂ〕
、〔Ｃ〕の混合物を添加した。In addition, when redispersing, use the antibacterial compounds [A] and [B] as antibacterial agents.
, [C] was added.
〔Ａ〕 〔Ｂ〕 〔Ｃ〕
（ハロゲン化銀写真感光材料の作製）
両面に厚さ０．１μｍの下塗層（特開昭５９−１９９４
１号の実施例１参照）を施した厚さ１００μｍのポリエ
チレンテレフタートフィルムの一方の下塗層上に、下記
処方（１）のハロゲン化銀乳剤層をゼラチン量が２．０
ｇ／ｍ”、銀量が３．２ｇ／＋ｍ２になるように塗設し
、更にその上に下記処方（２）の乳剤保護層をゼラチン
量が１．ｏｇ／ｍ”になるように塗設し、又、反対側の
もう一方の下塗層上には下記処方（３）のバッキング層
をゼラチン量が２．４ｇ／ｍ”になるように塗設し、更
にその上に下記処方（４）のバッキング保護層をゼラチ
ン量が１．Ｏｇ／ｍ”になるように塗設して試料１〜３
０を得た。[A] [B] [C] (Preparation of silver halide photographic light-sensitive material) Undercoat layer with a thickness of 0.1 μm on both sides (Japanese Patent Application Laid-Open No. 1983-1994
A silver halide emulsion layer having the following formulation (1) with a gelatin amount of 2.0 was applied on one undercoat layer of a 100 μm thick polyethylene tereftate film coated with a polyethylene tereftate film (see Example 1 of No. 1).
g/m", silver amount is 3.2g/+m2, and on top of that, an emulsion protective layer of the following formulation (2) is coated so that the gelatin amount is 1.og/m". In addition, on the other undercoat layer on the opposite side, a backing layer of the following formulation (3) is coated so that the amount of gelatin is 2.4 g/m'', and on top of that, the following formulation (4) is applied. ) was coated with a backing protective layer with a gelatin amount of 1.0g/m'' for samples 1 to 3.
I got 0.
処方（１）（ハロゲン化銀乳剤層組成）ゼラチン
２．０ｇ／ｍ２ハロゲン化銀乳
剤Ａ（銀量） 、３．２ｇ／ｍ”増感色素：
界面活性剤： ５−１
８．０ｍｇ／ｍ”
ＣＨ２Ｃ００（ＣＨ２）ＩＣｌ３
Ｎａ０ｓＳ ＣＨＣＯ○（ＣＨ２）２ＣＨ（ＣＨ３）
２本発明に係るヒドラジン誘導体
本発明に係る造核促進化合物
ラテックスポリマー：
３０ｍｇ／ｍ’
１００ｍｇ／ｍ２
１ｇ／ｍ２
ｍ ： ｎ ＝５０： ５０
ポリ工チレングリコール分子量４０００ ０．１ｇ／ｍ
２硬膜剤：Ｈ−１
安定剤：４−メチル−６−ヒドロキシ−１，３，３ａ、
？−テトラザインデン
カブリ防止剤：アデニン
界面活性剤：サポニン
３０ｍｇ／ｍ２
１０ ｍｇ／ｍ”
０−１ｇ／ｍ”
処方（２）（乳剤保護層組成）
ゼラチン
０．９ｇ／ｍ２
界面活性剤：Ｓ−２
Ｃ２Ｈ。Prescription (1) (Silver halide emulsion layer composition) Gelatin
2.0g/m2 Silver halide emulsion A (silver amount), 3.2g/m" Sensitizing dye: Surfactant: 5-1 8.0mg/m" CH2C00(CH2)ICl3 Na0sS CHCO○(CH2)2CH (CH3)
2 Hydrazine derivative according to the present invention Nucleation promoting compound according to the present invention Latex polymer: 30 mg/m' 100 mg/m2 1 g/m2 m: n = 50: 50 Polyethylene glycol molecular weight 4000 0.1 g/m
2 Hardener: H-1 Stabilizer: 4-methyl-6-hydroxy-1,3,3a,
? -Tetrazainden antifoggant: Adenine Surfactant: Saponin 30mg/m2 10 mg/m"0-1g/m" Prescription (2) (emulsion protective layer composition) Gelatin 0.9g/m2 Surfactant: S- 2 C2H.
し２１′Ｉｓ
マット剤：平均粒径３．５μ閣のシリカ硬膜剤： ホル
マリン
界面活性剤：Ｓ−３
処方
（バッキング層組成）
ｏ ３Ｎａ
３ｍｇ／ｍ’
３０ｍｇ／ｍ”
ｌＱｍｇ／ｍ”
ゼラチン ２．４ｇ／ｍ２界
面活性剤： Ｓ −１６，０ｍｇ／ｍ”：サポニン
０．１ｇ／ｍ”処方（４）（バッキング保護
層組成）
ゼラチン Ｉｇ／ｍ”マ
ット剤：平均粒径３．０〜５．０ｐｍのポリメチルメタ
クリレート １５ｍｇ／ｍ２界面活性剤：Ｓ ２
１０ｍｇ／ｍ”硬膜剤：グリオキザール
２５ｍｇ／ｍ２／／ ：Ｈ−１３５ｍｇ
／ｍ”
得られた試料について、下記の方法による網点品質試験
を行った。21'Is Matting agent: Silica hardening agent with average particle size of 3.5 μm: Formalin surfactant: S-3 Prescription (backing layer composition) o 3Na 3mg/m'30mg/m"1Qmg/m" Gelatin 2 .4g/m2 Surfactant: S-16.0mg/m”: Saponin
0.1 g/m" formulation (4) (backing protective layer composition) Gelatin Ig/m" Matting agent: Polymethyl methacrylate with average particle size of 3.0 to 5.0 pm 15 mg/m2 Surfactant: S 2
10mg/m” Hardening agent: Glyoxal
25mg/m2// :H-135mg
/m'' The resulting sample was subjected to a halftone quality test using the method described below.
（網点品質試験方法）
ステップウェッジに網点面積５０％の返し網スクリーン
（１５０線／インチ）を一部付して、これに試料を密着
させてキセノン光源で５秒間露光を与え、この試料を下
記現像液、下記定着液を投入した迅速処理用自動現像機
にて下記の条件で現像旭理を行い、試料の網点品質を１
００倍のルーペで観察し、網点品質の高いものを「５」
ランクとし、以下「４」、「３」、「２」、ｒｌＪと、
そのランクを順次下げて評価した。尚、ランク「１」及
び「２」は実用上好ましくないレベルである。(Half dot quality test method) A part of the step wedge is attached with a halftone screen (150 lines/inch) with a halftone dot area of 50%, and the sample is placed in close contact with this and exposed to a xenon light source for 5 seconds. The sample was developed in an automatic developing machine for quick processing using the following developer and fixer under the following conditions, and the halftone dot quality of the sample was 1.
Observe with a 00x magnifying glass and rate the one with high halftone quality as "5"
Ranked below as "4", "3", "2", rlJ,
The ranking was lowered sequentially and evaluated. Incidentally, ranks "1" and "2" are levels that are practically unfavorable.
又、網点中のカブリも同様に評価し、網点中に全く黒ピ
ンの発生していないものを最高ランク「５」とし、網点
中に発生する黒ピンの発生度に応じてランク「４」、「
３」、「２」、ｒｌＪとそのランクを順次下げて評価し
た。尚、ランクｒｌＪ及び「２」では黒ビンも大きく実
用上好ましくないレベルである。Fog in the halftone dots is also evaluated in the same way, and the highest rank is "5" when there are no black pins in the halftone dots, and the rank is "5" depending on the degree of occurrence of black pins in the halftone dots. 4", "
3", "2", and rlJ, and their ranks were sequentially lowered for evaluation. Incidentally, in ranks rlJ and "2", the black bins are also large, which is at a level that is not desirable for practical use.
現像液処方 現像液ｌ
現像液２エチレンジアミン四酢酸ナトリウム塩
１ｇ １ｇ亜硫酸ナトリウム
６０ｇ ６０ｇ燐酸三ナトリウム（１
２水塩）７５ｇ
硼酸 −４０ｇ
ハイドロキノン ２２．５
ｇ ３５ｇ水酸化ナトリウム
８ｇ ８ｇ臭化ナトリウム
３ｇ ３ｇ５−メチルベンゾ
トリアゾール ０．２５ｇ ０．２ｇ
１−フェニル−５−メルカプトテトラゾール ０．
０８ｇ ０．０８ｇメトール
０．２５ｇ１−フェニル−４−メチル−４−
ヒドロキシメチル −０，２８３−ピラゾリドン
７エネチルピフリニウムブロマイド −２，
５ｇ水を加えて １１
２ １１２水酸化ナトリウムにてｐＨを調整
ｐＨ−１０，８ｐＨ＝ｌＯ，８定着液処方
（組成Ａ）
チオ硫酸アンモニウム（７２，５ｗ／ｖ％水溶液）
２４０ｍ１＋亜硫酸ナトリウム
１７ｇ酢酸ナトリウム・３水塩
６．５ｇ硼酸
６ｇクエン酸ナトリウム・２水塩
２ｇ（組成り）
純水（イオン交換水） １７
ｍＱ硫酸（５０％ｗ／ｖの水溶液）
４．７ｇ硫酸アルミニウム
２６．５ｇ（ＡＱ、０３換算含量が８−１ｍ／ｖ％
の水溶液）定着液の使用時に水５００ｍ＋２中に上記組
成Ａ１組成りの順に溶かし、Ｉ（＋に仕上げて用いた。Developer prescription Developer solution l
Developer 2 Ethylenediaminetetraacetic acid sodium salt
1g 1g sodium sulfite
60g 60g trisodium phosphate (1
dihydrate) 75g Boric acid -40g
Hydroquinone 22.5
g 35g sodium hydroxide
8g 8g Sodium Bromide
3g 3g5-Methylbenzotriazole 0.25g 0.2g
1-phenyl-5-mercaptotetrazole 0.
08g 0.08g metol
0.25g1-phenyl-4-methyl-4-
Hydroxymethyl -0,283-pyrazolidone 7enethylphifrinium bromide -2,
Add 5g water 11
2 Adjust pH with 112 sodium hydroxide
pH-10.8 pH=1O,8 Fixer formulation (composition A) Ammonium thiosulfate (72.5 w/v% aqueous solution)
240ml + sodium sulfite
17g Sodium acetate trihydrate
6.5g boric acid
6g Sodium citrate dihydrate
2g (composition) Pure water (ion exchange water) 17
mQ sulfuric acid (50% w/v aqueous solution)
4.7g aluminum sulfate
26.5g (AQ, 03 equivalent content is 8-1 m/v%
When using a fixer (aqueous solution of A1), the fixer was dissolved in 500 m+2 of water in the order of composition A1 and finished to I(+).
この定着液のｐｉ（は酢酸で４，８に調整した。The pi of this fixer was adjusted to 4.8 with acetic acid.
（現像処理条件）
（工 程） （温 度） （時 間）現 像
４０ ℃ １５ 秒定 着
３５ °Ｃ１５抄
本 洗 ３０ °Ｃｔｏ 秒乾 燥
５０ °Ｃ１０秒
尚、処方（１）におけるノ１０ゲン化銀乳剤層に添加し
た本発明のヒドラジン誘導体の比較化合物としては、以
下の（ａ）及び（ｂ）の化合物を添加しｔ二。(Development processing conditions) (Process) (Temperature) (Time) Development
Fix at 40℃ for 15 seconds
Wash the extract at 35 °C for 15 seconds. Dry at 30 °C for seconds.
50°C for 10 seconds As comparative compounds for the hydrazine derivative of the present invention added to the silver genide emulsion layer in formulation (1), the following compounds (a) and (b) were added.
化合物（ａ）
（ａ）
表＝１から明らかなように本発明に係る試料は、比較に
対して、網点品質と黒ピンが良いことがわかる。Compound (a) (a) As is clear from Table 1, the samples according to the present invention have better halftone dot quality and black pins than the comparison.
本発明により、ｐＨ１１未満の低ｐＨの現像液で処理し
ても、硬調でカブリが少なく網点性能の良好なハロゲン
化銀写真感光材料を提供することができＩこ。According to the present invention, it is possible to provide a silver halide photographic material that has high contrast, less fog, and good halftone dot performance even when processed with a developer having a low pH of less than pH 11.
Claims (2)
ロゲン化銀写真感光材料において、下記一般式〔Ａ〕及
び〔Ｂ〕で表されるヒドラジン化合物を少なくとも１種
含有し、かつアミン化合物、ヒドラジン化合物、四級オ
ニウム塩化合物から選ばれる少なくとも１種の造核促進
化合物を含有することを特徴とするハロゲン化銀写真感
光材料。 一般式〔Ａ〕 ▲数式、化学式、表等があります▼ 一般式〔Ｂ〕 ▲数式、化学式、表等があります▼ 〔式中、Ａｒはアリール基又は硫黄原子もしくは酸素原
子を少なくとも一つ含む複素環基を表し、ｎは１又は２
の整数を表す。ｎ＝１の時、Ｒ＿１及びＲ＿２は各々、
水素原子、アルキル基、アルケニル基、アルキニル基、
アリール基、複素環基、ヒドロキシル基、アルコキシ基
、アルケニルオキシ基、アルキニルオキシ基、アリール
オキシ基又は複素環オキシ基を表し、Ｒ＿１とＲ＿２は
窒素原子と共に環を形成してもよい。ｎ＝２の時、Ｒ＿
１及びＲ＿２は各々、水素原子、アルキル基、アルケニ
ル基、アルキニル基、アリール基、飽和もしくは不飽和
複素環基、ヒドロキシル基、アルコキシ基、アルケニル
オキシ基、アルキニルオキシ基、アリールオキシ基又は
複素環オキシ基を表す。ただし、ｎ＝２の時、Ｒ＿１及
びＲ＿２のうち少なくとも一方はアルケニル基、アルキ
ニル基、飽和複素環基、ヒドロキシル基、アルコキシ基
、アルケニルオキシ基、アルキニルオキシ基、アリール
オキシ基又は複素環オキシ基を表すものとする。Ｒ＿３
はアルキニル基又は飽和複素環基を表す。 一般式〔Ａ〕又は〔Ｂ〕で表される化合物には、式中の
−ＮＨＮＨ−の少なくともいずれかのＨが置換基で置換
されたものを含む。〕(1) A silver halide photographic light-sensitive material having at least one silver halide emulsion layer, which contains at least one hydrazine compound represented by the following general formulas [A] and [B], and which contains an amine compound, hydrazine 1. A silver halide photographic light-sensitive material comprising at least one nucleation-promoting compound selected from compounds and quaternary onium salt compounds. General formula [A] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula [B] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, Ar is an aryl group or a complex compound containing at least one sulfur atom or oxygen atom Represents a ring group, n is 1 or 2
represents an integer. When n=1, R_1 and R_2 are each
Hydrogen atom, alkyl group, alkenyl group, alkynyl group,
It represents an aryl group, a heterocyclic group, a hydroxyl group, an alkoxy group, an alkenyloxy group, an alkynyloxy group, an aryloxy group, or a heterocyclic oxy group, and R_1 and R_2 may form a ring together with a nitrogen atom. When n=2, R_
1 and R_2 are each a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a saturated or unsaturated heterocyclic group, a hydroxyl group, an alkoxy group, an alkenyloxy group, an alkynyloxy group, an aryloxy group, or a heterocyclic group. represents a group. However, when n=2, at least one of R_1 and R_2 is an alkenyl group, an alkynyl group, a saturated heterocyclic group, a hydroxyl group, an alkoxy group, an alkenyloxy group, an alkynyloxy group, an aryloxy group, or a heterocyclic group. shall be expressed. R_3
represents an alkynyl group or a saturated heterocyclic group. The compounds represented by the general formula [A] or [B] include compounds in which at least one H of -NHNH- in the formula is substituted with a substituent. ]
り、Ｒ＿１及びＲ＿２が各々、水素原子、アルキル基、
アルケニル基、アルキニル基、アリール基、飽和もしく
は不飽和複素環基、ヒドロキシル基又はアルコキシ基で
あり、かつＲ＿１及びＲ＿２のうち少なくとも一方はア
ルケニル基、アルキニル基、飽和複素環基、ヒドロキシ
ル基又はアルコキシ基であることを特徴とするハロゲン
化銀写真感光材料。(2) In the compound of general formula [A] of claim 1, n=2, and R_1 and R_2 are each a hydrogen atom, an alkyl group,
An alkenyl group, an alkynyl group, an aryl group, a saturated or unsaturated heterocyclic group, a hydroxyl group, or an alkoxy group, and at least one of R_1 and R_2 is an alkenyl group, an alkynyl group, a saturated heterocyclic group, a hydroxyl group, or an alkoxy group. A silver halide photographic material characterized by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2167972A JPH0456949A (en) | 1990-06-26 | 1990-06-26 | Silver halide photographic sensitive material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2167972A JPH0456949A (en) | 1990-06-26 | 1990-06-26 | Silver halide photographic sensitive material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0456949A true JPH0456949A (en) | 1992-02-24 |
Family
ID=15859441
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2167972A Pending JPH0456949A (en) | 1990-06-26 | 1990-06-26 | Silver halide photographic sensitive material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0456949A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5478697A (en) * | 1993-04-28 | 1995-12-26 | Fuji Photo Film Co., Ltd. | Method for forming an image |
| JP2008007443A (en) * | 2006-06-28 | 2008-01-17 | Shiseido Co Ltd | Cinnamic acid derivative, application of the same as ultraviolet ray absorber and ultraviolet ray absorbing composition formulated with the same, skin care preparation |
| WO2009031202A1 (en) * | 2007-09-04 | 2009-03-12 | Shiseido Company Ltd. | Cinnamic acid derivatives and use thereof as ultraviolet absorber |
-
1990
- 1990-06-26 JP JP2167972A patent/JPH0456949A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5478697A (en) * | 1993-04-28 | 1995-12-26 | Fuji Photo Film Co., Ltd. | Method for forming an image |
| JP2008007443A (en) * | 2006-06-28 | 2008-01-17 | Shiseido Co Ltd | Cinnamic acid derivative, application of the same as ultraviolet ray absorber and ultraviolet ray absorbing composition formulated with the same, skin care preparation |
| WO2009031202A1 (en) * | 2007-09-04 | 2009-03-12 | Shiseido Company Ltd. | Cinnamic acid derivatives and use thereof as ultraviolet absorber |
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