JPH0285846A - Silver halide photographic sensitive material having high sensitivity and improved graininess - Google Patents
Silver halide photographic sensitive material having high sensitivity and improved graininessInfo
- Publication number
- JPH0285846A JPH0285846A JP23822588A JP23822588A JPH0285846A JP H0285846 A JPH0285846 A JP H0285846A JP 23822588 A JP23822588 A JP 23822588A JP 23822588 A JP23822588 A JP 23822588A JP H0285846 A JPH0285846 A JP H0285846A
- Authority
- JP
- Japan
- Prior art keywords
- silver
- silver halide
- emulsion
- present
- grain
- 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 83
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 75
- 239000004332 silver Substances 0.000 title claims abstract description 75
- 239000000463 material Substances 0.000 title claims abstract description 25
- 230000035945 sensitivity Effects 0.000 title abstract description 14
- 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 claims abstract description 35
- 229910021612 Silver iodide Inorganic materials 0.000 claims abstract description 35
- 229940045105 silver iodide Drugs 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 34
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 11
- 238000006467 substitution reaction Methods 0.000 claims abstract description 9
- 125000005843 halogen group Chemical group 0.000 claims abstract 2
- 239000002245 particle Substances 0.000 abstract description 24
- 239000008384 inner phase Substances 0.000 abstract description 4
- 239000000839 emulsion Substances 0.000 description 61
- 239000000243 solution Substances 0.000 description 16
- 239000012071 phase Substances 0.000 description 15
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 15
- 150000001875 compounds Chemical class 0.000 description 11
- 239000010410 layer Substances 0.000 description 10
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 10
- 238000012545 processing Methods 0.000 description 10
- 150000002367 halogens Chemical group 0.000 description 8
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- 108010010803 Gelatin Proteins 0.000 description 7
- 229920000159 gelatin Polymers 0.000 description 7
- 239000008273 gelatin Substances 0.000 description 7
- 235000019322 gelatine Nutrition 0.000 description 7
- 235000011852 gelatine desserts Nutrition 0.000 description 7
- 206010070834 Sensitisation Diseases 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 230000008313 sensitization Effects 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000006866 deterioration Effects 0.000 description 4
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000000084 colloidal system Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000001235 sensitizing effect Effects 0.000 description 3
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 239000006224 matting agent Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- UVLIQKQFNOFCPP-UHFFFAOYSA-N 1-phenyl-3-sulfanyl-2h-tetrazole Chemical compound C1=NN(S)NN1C1=CC=CC=C1 UVLIQKQFNOFCPP-UHFFFAOYSA-N 0.000 description 1
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 description 1
- PXDAXYDMZCYZNH-UHFFFAOYSA-N 3-methyl-2h-1,3-benzothiazole Chemical compound C1=CC=C2N(C)CSC2=C1 PXDAXYDMZCYZNH-UHFFFAOYSA-N 0.000 description 1
- JIGUICYYOYEXFS-UHFFFAOYSA-N 3-tert-butylbenzene-1,2-diol Chemical compound CC(C)(C)C1=CC=CC(O)=C1O JIGUICYYOYEXFS-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- 102000009027 Albumins Human genes 0.000 description 1
- 108010088751 Albumins Proteins 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 239000004593 Epoxy Substances 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
- LEVWYRKDKASIDU-IMJSIDKUSA-N L-cystine Chemical compound [O-]C(=O)[C@@H]([NH3+])CSSC[C@H]([NH3+])C([O-])=O LEVWYRKDKASIDU-IMJSIDKUSA-N 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- SJOOOZPMQAWAOP-UHFFFAOYSA-N [Ag].BrCl Chemical compound [Ag].BrCl SJOOOZPMQAWAOP-UHFFFAOYSA-N 0.000 description 1
- HOLVRJRSWZOAJU-UHFFFAOYSA-N [Ag].ICl Chemical compound [Ag].ICl HOLVRJRSWZOAJU-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- HTKFORQRBXIQHD-UHFFFAOYSA-N allylthiourea Chemical compound NC(=S)NCC=C HTKFORQRBXIQHD-UHFFFAOYSA-N 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000002583 angiography Methods 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 238000010420 art technique Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- JOILQYURMOSQTJ-UHFFFAOYSA-N azanium;2,4-dihydroxybenzenesulfonate Chemical compound [NH4+].OC1=CC=C(S([O-])(=O)=O)C(O)=C1 JOILQYURMOSQTJ-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001661 cadmium Chemical class 0.000 description 1
- 150000001718 carbodiimides Chemical class 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 229960003067 cystine Drugs 0.000 description 1
- 238000011033 desalting Methods 0.000 description 1
- AFOSIXZFDONLBT-UHFFFAOYSA-N divinyl sulfone Chemical compound C=CS(=O)(=O)C=C AFOSIXZFDONLBT-UHFFFAOYSA-N 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 150000002503 iridium Chemical class 0.000 description 1
- 159000000014 iron salts Chemical class 0.000 description 1
- CTAPFRYPJLPFDF-UHFFFAOYSA-N isoxazole Chemical compound C=1C=NOC=1 CTAPFRYPJLPFDF-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-N methanesulfonic acid Substances CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- HKOOXMFOFWEVGF-UHFFFAOYSA-N phenylhydrazine Chemical compound NNC1=CC=CC=C1 HKOOXMFOFWEVGF-UHFFFAOYSA-N 0.000 description 1
- 229940067157 phenylhydrazine Drugs 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 229920002401 polyacrylamide 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
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000001397 quillaja saponaria molina bark Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 150000003283 rhodium Chemical class 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229930182490 saponin Natural products 0.000 description 1
- 150000007949 saponins Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000009518 sodium iodide Nutrition 0.000 description 1
- AMZPPWFHMNMIEI-UHFFFAOYSA-M sodium;2-sulfanylidene-1,3-dihydrobenzimidazole-5-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=C2NC(=S)NC2=C1 AMZPPWFHMNMIEI-UHFFFAOYSA-M 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 150000003475 thallium Chemical class 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-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
- G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
Landscapes
- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、ハロゲン化銀写真感光材料に関し、特に高感
度かつ粒状性の改良されたハロゲン化銀写真感光材料に
関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a silver halide photographic material, and particularly to a silver halide photographic material having high sensitivity and improved graininess.
近年、写真技術の発達に伴い、ハロゲン化銀写真感光材
料の高感度化・高画質化が強く望まれている。これらの
要請に対し、沃化銀含有率の高い沃臭化銀相を有するコ
ア/シェル型のハロゲン化銀粒子から成る乳剤がさかん
に研究されてきた。In recent years, with the development of photographic technology, there has been a strong desire for higher sensitivity and higher image quality of silver halide photographic materials. In response to these demands, emulsions comprising core/shell type silver halide grains having a silver iodobromide phase with a high silver iodide content have been extensively studied.
特に粒子内部に10モル%以上の高沃化銀含有率相を有
するコア/シェル型粒子含有の沃臭化銀乳剤に関しては
多くの研究がなされてきた。例えば、特開昭60−14
3331号、特開昭62−3247号、特開昭62−7
039号各公報には、コア部の沃化銀含有率の高いコア
/シェル型乳剤が開示されている。In particular, much research has been conducted on silver iodobromide emulsions containing core/shell type grains having a high silver iodide content phase of 10 mol % or more inside the grains. For example, JP-A-60-14
3331, JP-A-62-3247, JP-A-62-7
Each publication No. 039 discloses a core/shell type emulsion having a high silver iodide content in the core portion.
一方、感光材料については、処理の迅速化の要請が大き
い。特に近年では、感光材料の消費量の増大に伴って、
短時間での迅速処理化が強く要求されるようになってい
る。これはどの感光材料の分野でも言えることであるが
、例えば医療用X線感光材料の分野では、診断回数の急
増や検査項目の増加により、X線写真逼影枚数が増加し
ている一方、診断結果をできるだけ早く受診者に知らせ
る必要があり、このため迅速処理化が望まれている。特
に血管造影盪影、術中撮影等は、本質的に少しでも短時
間で写真を見る必要がある。On the other hand, there is a strong demand for faster processing of photosensitive materials. Especially in recent years, with the increase in consumption of photosensitive materials,
There is a strong demand for rapid processing in a short time. This can be said in any field of photosensitive materials, but for example, in the field of medical X-ray photosensitive materials, the number of X-ray photographs is increasing due to a rapid increase in the number of diagnoses and an increase in the number of test items. It is necessary to notify the examinee of the results as soon as possible, and therefore rapid processing is desired. In particular, for angiography, intraoperative photography, etc., it is essentially necessary to view the photographs as quickly as possible.
このような背景で、迅速処理技術が種々試みられ、例え
ば画像形成処理において、高pH1高温(30〜40℃
)で現像処理することにより処理を促進することなどが
試みられているが、このような高pH1高温条件では、
得られる写真画像の劣化を招いていた。特に自動現像機
で処理を行う場合、上記条件では、感光材料の耐圧性が
劣化し、搬送ローラーの圧力によりいわゆるローラーマ
ークが発生し、これによる画質の劣化を招くことがあっ
た。Against this background, various rapid processing technologies have been attempted. For example, in image forming processing, high pH and high temperature (30 to 40 °C
) Attempts have been made to accelerate processing by developing with
This resulted in deterioration of the photographic images obtained. In particular, when processing is performed using an automatic processor, under the above conditions, the pressure resistance of the photosensitive material deteriorates, and so-called roller marks are generated due to the pressure of the conveying roller, which may lead to deterioration of image quality.
このように、頭書した高感度化、高画質化の流れととも
に、上記迅速処理化の要請に関連して、ハロゲン化銀写
真感光材料における圧力特性の良化に対する要請も、従
来以上に高まってきている。In this way, along with the trend toward higher sensitivity and higher image quality as mentioned above, and in conjunction with the above-mentioned demand for faster processing, the demand for improved pressure characteristics in silver halide photographic materials has also increased more than ever before. There is.
このため以前から様々な手段により圧力特性を改良する
ことが検討されてきており、例えば可塑剤を添加する等
添加剤を用いる技術が試みられている。しかしこのよう
な手段よりも、ハロゲン化銀粒子自体の耐圧力性を向上
させる技術の方が実用上好ましく、また効果も大きいと
いう見方が有力である。このような観点から生まれた従
来技術として、例えば特開昭60−35726号公報、
特開昭60−198324号公報に開示の技術が知られ
ている。いずれもコア/シェル型の乳剤で、粒子内部に
沃化物によるハロゲン置換を施した相を含有している。For this reason, various methods have been considered for improving the pressure characteristics, and techniques using additives, such as adding plasticizers, have been attempted. However, the prevailing view is that a technique for improving the pressure resistance of the silver halide grains itself is more practically preferable than such means, and is also more effective. Examples of prior art developed from this perspective include Japanese Patent Application Laid-Open No. 60-35726,
A technique disclosed in Japanese Unexamined Patent Publication No. 198324/1983 is known. Both are core/shell type emulsions and contain a phase substituted with halogen by iodide inside the grains.
これらの従来技術に示される如く、沃化物によるハロゲ
ン置換法によって得られたハロゲン化銀粒子は確かに圧
力特性において改良がなされているが、他方では粒子内
全体の平均沃化銀含有率が比較的低く、現像性が速すぎ
るため、粒状性が劣化するという欠点があり、必ずしも
満足すべきものではない。粒状性の劣化は写真性能上重
要な問題であり、例えば盪影したフィルムで直接読影す
るX線写真においては誤診につながることもあり得る。As shown in these prior art techniques, silver halide grains obtained by the halogen substitution method using iodide certainly have improved pressure characteristics, but on the other hand, the average silver iodide content of the entire grain is comparatively low. It has the drawbacks of poor graininess, poor development performance, and deterioration of graininess, so it is not necessarily satisfactory. Deterioration of graininess is an important problem in terms of photographic performance, and may lead to misdiagnosis, for example, in X-ray photographs that are directly interpreted using a shadowed film.
よって上記のような問題をもつ粒子を含有する乳剤は、
例えばX線写真用感光材料等粒状性が大きな問題となる
感光材料用の乳剤として好ましくない。Therefore, emulsions containing grains with the above problems are
For example, it is not preferred as an emulsion for light-sensitive materials in which graininess is a serious problem, such as light-sensitive materials for X-ray photography.
本発明は、上記従来技術の問題点を解決し、高感度であ
りかつ粒状性の改良された感光材料で、従って例えば迅
速処理した場合でも粒状性の良い画像が得られるハロゲ
ン化銀写真感光材料を提供することを目的とする。The present invention solves the above-mentioned problems of the prior art, and is a silver halide photographic light-sensitive material that is highly sensitive and has improved graininess, and therefore can produce images with good graininess even when processed rapidly, for example. The purpose is to provide
本発明の目的は、下記ハロゲン化銀粒子を含有するハロ
ゲン化銀写真感光材料によって、達成された。即ち、本
発明のハロゲン化銀写真感光材料は、沃化銀含有率が1
0モル%以上の沃臭化銀からなる粒子内部相と、沃化銀
含有率が7モル%以下の沃臭化銀からなる粒子外殻とを
少なくとも有し、かつ平均沃化銀含有率が1.5モル%
以上であるハロゲン化銀粒子であって、該粒子内部相成
長の50%までにハロゲン置換法によって該粒子内部相
中の沃化銀の80%以上を形成することによって得られ
るハロゲン化銀粒子を含有するものである。本発明者は
このようなハロゲン化銀粒子(以下適宜「本発明に係る
ハロゲン化銀粒子」などと称することもある)を含有す
る感光材料が本発明の目的に合致することを見出して、
本発明を完成するに至ったのである。The object of the present invention was achieved by a silver halide photographic material containing the following silver halide grains. That is, the silver halide photographic material of the present invention has a silver iodide content of 1
It has at least an internal grain phase consisting of silver iodobromide with a silver iodide content of 0 mol% or more, and a grain outer shell consisting of silver iodobromide with a silver iodide content of 7 mol% or less, and has an average silver iodide content. 1.5 mol%
The above silver halide grains are obtained by forming 80% or more of the silver iodide in the internal phase of the grain by a halogen substitution method by 50% of the growth of the internal phase of the grain. It contains. The present inventor has discovered that a photosensitive material containing such silver halide grains (hereinafter also referred to as "silver halide grains according to the present invention") meets the object of the present invention,
This led to the completion of the present invention.
以下本発明について更に詳述する。まず、本発明の感光
材料に含有させるハロゲン化銀粒子について説明する。The present invention will be explained in more detail below. First, the silver halide grains contained in the light-sensitive material of the present invention will be explained.
ハロゲン化銀粒子は一般に、該粒子を含有するハロゲン
化銀乳剤の形で製造され、使用される。Silver halide grains are generally produced and used in the form of silver halide emulsions containing the grains.
本発明に係るハロゲン化銀粒子は、沃化銀含有率が10
モル%以上の沃臭化銀から成る粒子内部相を有する。こ
こで粒子内部相とは、このような高沃度含有率の内部領
域をいう。該内部相の沃化銀含有率は、好ましくは10
〜45モル%であり、特に好ましくは15〜40モル%
である。The silver halide grains according to the present invention have a silver iodide content of 10
The grain has an internal phase consisting of silver iodobromide in a mole % or more. The term "internal phase of the grain" as used herein refers to such an internal region having a high iodine content. The silver iodide content of the internal phase is preferably 10
-45 mol%, particularly preferably 15-40 mol%
It is.
また本発明に係るハロゲン化銀粒子は、沃化銀金を率が
7モル%以下の沃臭化銀から成る粒子外殻を有する。粒
子外殻とは、粒子の表面側に存在する層である。該粒子
外殻の沃化銀金を率は、より好ましくは5モル%以下で
ある。Further, the silver halide grains according to the present invention have a grain outer shell composed of silver iodobromide containing 7 mol % or less of silver gold iodide. A particle outer shell is a layer existing on the surface side of a particle. The silver iodide content in the outer shell of the grains is more preferably 5 mol % or less.
上記内部相及び外殻を構成する沃臭化銀は、実質的に沃
臭化銀であるものをいい、沃臭化銀の性質を阻害しない
程度の他の物質(他のハロゲン化銀など)が混入するこ
とは妨げない。The silver iodobromide constituting the inner phase and outer shell is essentially silver iodobromide, and may include other substances (such as other silver halides) to the extent that they do not inhibit the properties of silver iodobromide. It does not prevent the mixture of
本発明に係るハロゲン化銀粒子の平均沃化銀含有率は1
.5モル%以上である。好ましくは1.5〜30モル%
である。The average silver iodide content of the silver halide grains according to the present invention is 1
.. It is 5 mol% or more. Preferably 1.5-30 mol%
It is.
本発明に係るハロゲン化銀粒子は、粒子全体としても実
質的に沃臭化銀から成ることが好ましい。The silver halide grains according to the present invention preferably consist essentially of silver iodobromide as a whole.
但し本発明の効果を損なわない範囲で他の組成のハロゲ
ン化銀、例えば、塩化銀等を含有させることができる。However, silver halide of other compositions, such as silver chloride, may be contained within a range that does not impair the effects of the present invention.
また本発明に係るハロゲン化銀粒子は、この粒子を含有
するハロゲン化銀乳剤の形で好ましく用いられるが、乳
剤も実質的に沃臭化銀乳剤であることが好ましい。但し
、本発明に係るハロゲン化銀粒子以外の粒子を含有させ
てもよく、あるいは本発明に係るハロゲン化銀粒子を含
有する乳剤とそれ以外の乳剤とを混合して用いるのでも
よい。Further, the silver halide grains according to the present invention are preferably used in the form of a silver halide emulsion containing the grains, but the emulsion is preferably also substantially a silver iodobromide emulsion. However, grains other than the silver halide grains according to the present invention may be contained, or an emulsion containing the silver halide grains according to the present invention and other emulsions may be mixed and used.
本発明に係るハロゲン化銀粒子を含有する乳剤を得るに
当たって、特開昭60−138538号公報記載の方法
のようにコア/シェル型ハロゲン化銀乳剤を種粒子から
出発して成長させる手段を用いることもでき、この場合
、粒子中心部に上記粒子内部相をなすコアとは異なるハ
ロゲン化銀組成領域(種粒子の組成領域)をもつことが
あり得る。このような場合、種粒子のハロゲン化銀組成
は、臭化銀、沃臭化銀、塩沃化銀、塩臭化銀、塩化銀等
の任意の組成のものを用いうるが、沃化銀の含有率が1
0モル%以下の沃臭化銀、または臭化銀が好ましい。ま
たこの場合、種粒子の全ハロゲン化銀粒子中に占める割
合は、50%以下が好ましく、10%以下が特に好まし
い。In obtaining the emulsion containing silver halide grains according to the present invention, a method is used in which a core/shell type silver halide emulsion is grown starting from seed grains, as in the method described in JP-A-60-138538. In this case, the grain center may have a silver halide composition region (composition region of the seed grain) different from the core forming the internal phase of the grain. In such a case, the silver halide composition of the seed grains may be any composition such as silver bromide, silver iodobromide, silver chloroiodide, silver chlorobromide, silver chloride, etc. The content rate of
Silver iodobromide or silver bromide of 0 mol % or less is preferred. In this case, the proportion of the seed grains in all silver halide grains is preferably 50% or less, particularly preferably 10% or less.
本発明に係るハロゲン化銀粒子は、上記粒子内部層と粒
子外殻層とを必ず有するが、その他両者の間に一層また
は多層の中間層を有してもよい。The silver halide grains according to the present invention necessarily have the above grain inner layer and grain outer shell layer, but may also have one or more intermediate layers between them.
また、上記外殻層の外側にきわめて薄い最表層を有する
ことを妨げない。Further, it is possible to have an extremely thin outermost layer on the outside of the outer shell layer.
本発明に係るハロゲン化銀粒子における沃化銀の分布状
態は、各種の物理的測定法によって検知することができ
、例えば日本写真学会・昭和56年度年次大会講演要旨
集に記載されているような、低温でのルミネッセンスの
測定やX線回折法によって調べることができる。The distribution state of silver iodide in the silver halide grains according to the present invention can be detected by various physical measurement methods. This can be investigated by measuring luminescence at low temperatures or by X-ray diffraction.
X線回折法として標準的な測定法は、ターゲットとして
Cuを用い、Cuのにαの線を線源とし、管電圧40に
ν、管電流100mAとしてハロゲン化銀の(420)
面の回折曲線を粉末法によって求める方法である。一般
に測定器の分解能を高めるためにスリットの幅、走査記
録速度を適切に選び、またゴニオメータのステップ角度
を0.02度とし、シリコンなどの標準試料を入れて回
折温度を補正する必要がある。またハロゲン化銀乳剤サ
ンプルは通常ゼラチンを酵素によって除去し、乾燥して
用いる。The standard measurement method for X-ray diffraction is to use Cu as the target, use α rays as the radiation source, set the tube voltage at 40 ν, and the tube current at 100 mA to measure silver halide (420).
This method uses the powder method to obtain the diffraction curve of a surface. Generally, in order to improve the resolution of the measuring instrument, it is necessary to appropriately select the slit width and scanning recording speed, set the step angle of the goniometer to 0.02 degrees, and correct the diffraction temperature by inserting a standard sample such as silicon. Furthermore, silver halide emulsion samples are usually used after gelatin is removed using enzymes and dried.
例えばコアが5モル%以上の沃化銀含有率であることは
、ハロゲン化銀乳剤のX線回折曲線において5モル%以
上の沃臭化銀のCuのにα、線に対応する回折強度領域
の任意の1点において回折角度がピーク強度に対して1
0%以上存在することによって確認できる。For example, the fact that the core has a silver iodide content of 5 mol% or more means that in the X-ray diffraction curve of the silver halide emulsion, the diffraction intensity region corresponds to the α line for Cu of 5 mol% or more of silver iodobromide. At any one point, the diffraction angle is 1 with respect to the peak intensity.
This can be confirmed by the presence of 0% or more.
本発明に係るハロゲン化銀粒子の形状、結晶形態、晶癖
等は任意である。例えば、正常晶、即ち立方体、14面
体、8面体、12面体等のような正常晶であってもよく
、その他任意の形態をとることができる。The shape, crystal form, crystal habit, etc. of the silver halide grains according to the present invention are arbitrary. For example, it may be a normal crystal, ie, a normal crystal such as a cube, a tetradecahedron, an octahedron, a dodecahedron, etc., or may take any other form.
本発明に係るハロゲン化銀粒子は、上記粒子内部相成長
の50%までにハロゲン置換法によって内部相中の沃化
銀の80%以上が形成される。本発明におけるハロゲン
置換法とは、主として沃化物を添加することによりハロ
ゲン置換を起こさせる方法を意味しており、添加する化
合物としては例えば沃化カリウム、沃化ナトリウム、沃
化鋼(II)(Culz)、それらの水溶液、沃化銀(
沃化銀は、沃化銀を形成して添加するのでもよいし、銀
イオンと沃素イオンとの添加、例えば硝酸銀溶液と沃化
物溶液とを同時に混合しつつ添加することによるのでも
よい)、沃化銀乳剤等が挙げられる。沃化物の添加位置
(添加する時点)としては、内部相成長の50%までの
時期であればどの位置であってもよいし、また、この時
期のうち、2ケ所以上の位置で添加を行ってもよい、沃
化物の添加時間としては、短時間で全沃化物を添加する
ラッシュ添加でもよ(、また数分以上の時間をかけて添
加するのでもよい。In the silver halide grains according to the present invention, 80% or more of the silver iodide in the internal phase is formed by the halogen substitution method by 50% of the growth of the internal phase of the grain. The halogen substitution method in the present invention mainly means a method of causing halogen substitution by adding iodide, and the compounds to be added include, for example, potassium iodide, sodium iodide, iodized steel (II) ( Culz), their aqueous solutions, silver iodide (
Silver iodide may be added by forming silver iodide, or may be added by adding silver ions and iodide ions, for example, by mixing a silver nitrate solution and an iodide solution at the same time), Examples include silver iodide emulsion. The iodide addition position (point of time of addition) may be any position as long as it is up to 50% of the internal phase growth, and the iodide may be added at two or more positions within this period. The iodide addition time may be rush addition in which all iodide is added in a short time (or it may be added over several minutes or more).
本発明に係るハロゲン化銀粒子の内部相成長時のpAg
値としては、8.4以下が好ましく、さらに好ましくは
、7以上8.4以下がよい。また、内部相成長時のpH
値としては、9.8以上が好ましく、更に好ましくは、
10以上11以下がよい。pAg during internal phase growth of silver halide grains according to the present invention
The value is preferably 8.4 or less, more preferably 7 or more and 8.4 or less. In addition, the pH during internal phase growth
The value is preferably 9.8 or more, more preferably,
It is preferably 10 or more and 11 or less.
本発明のハロゲン化銀粒子含有の乳剤の製造の際、また
は併用する本発明以外のハロゲン化銀粒子を含有する乳
剤(以下の乳剤の記載について、同様)の製造に際して
、特開昭60−138538号記載の方法のように、コ
ア/シェル型ハロゲン化銀乳剤を種粒子から出発して成
長させる手段を用いることができることは前記のとおり
である。When producing an emulsion containing silver halide grains of the present invention, or when producing an emulsion containing silver halide grains other than the present invention to be used together (the same applies to the description of emulsions below), JP-A-60-138538 As mentioned above, it is possible to use a method of growing a core/shell type silver halide emulsion starting from seed grains, as in the method described in the above-mentioned patent.
またハロゲン化銀粒子含有の乳剤の調製に当たって、粒
子の成長時にアンモニア、チオエーテル、チオ尿素等の
公知のハロゲン化銀溶剤を存在させることができる。Further, in preparing an emulsion containing silver halide grains, a known silver halide solvent such as ammonia, thioether, thiourea, etc. can be present during grain growth.
更にハロゲン化銀粒子は、粒子を形成する過程及び/ま
た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種の金属イオンを添加し、粒子内部に及び/
または粒子表面層にこれらの金属元素を含有させること
ができ、また適当な還元的雰囲気におくことにより、粒
子内部及び/または粒子表面に還元増感核を付与できる
。Furthermore, silver halide grains are treated with cadmium salts, zinc salts, lead salts,
At least one metal ion selected from thallium salts, iridium salts (including complex salts), rhodium salts (including complex salts), and iron salts (including complex salts) is added to the inside of the particles and/or
Alternatively, these metal elements can be contained in the particle surface layer, and reduction sensitizing nuclei can be provided inside and/or on the particle surface by placing the particle in an appropriate reducing atmosphere.
ハロゲン化銀乳剤は、ハロゲン化銀粒子の成長の終了後
に不要な可溶性塩類を除去してもよいし、あるいは含有
させたままでもよい。該塩類を除去する場合には、リサ
ーチ・ディスクロージャー(Research Dis
closure以下RDと略す> 17643号■項に
記載の方法に基づいて行うことができる。Unnecessary soluble salts may be removed from the silver halide emulsion after the growth of silver halide grains is completed, or they may be left contained. When removing the salts, Research Disclosure (Research Disclosure) is required.
Closure (hereinafter abbreviated as RD)> This can be carried out based on the method described in No. 17643, Section 3.
ハロゲン化銀粒子は、潜像が主として表面に形成される
粒子あるいは主として粒子内部に形成される粒子のいず
れであってもよく、ハロゲン化銀粒子のサイズとしては
、0.05〜30μm、好ましくは0.1〜20μm1
更に好ましくは0.2〜10μmのものである。The silver halide grains may be grains in which latent images are mainly formed on the surface or grains in which latent images are mainly formed inside the grains, and the size of the silver halide grains is preferably 0.05 to 30 μm, preferably 0.1-20μm1
More preferably, the thickness is 0.2 to 10 μm.
本発明の感光材料に用いるハロゲン化銀写真乳剤として
は、粒子サイズ分布の広い多分散乳剤、粒子サイズ分布
の狭い単分散乳剤など任意のものを用いることができ、
それぞれが単独であっても、これらを数種類混合したも
のであってもよい。尚本発明を実施する際には単分散乳
剤が好ましい。As the silver halide photographic emulsion used in the light-sensitive material of the present invention, any one can be used, such as a polydisperse emulsion with a wide grain size distribution or a monodisperse emulsion with a narrow grain size distribution.
Each may be used alone, or a mixture of several types may be used. In carrying out the present invention, monodispersed emulsions are preferred.
単分散のハロゲン化銀乳剤としては、平均粒径fを中心
に、20%の粒径範囲内に含まれるハロゲン化銀重量が
、全ハロゲン化銀粒子重量の60%以上であるものが好
ましく、より好ましくは70%以上、更に好ましくは8
0%以上である。The monodisperse silver halide emulsion is preferably one in which the weight of silver halide contained within a 20% range of grain sizes centered on the average grain size f is 60% or more of the weight of all silver halide grains. More preferably 70% or more, still more preferably 8
It is 0% or more.
ここに、平均粒径fとは、粒径riを有する粒子の頻度
niとri3との積n1Xri”が最大となるときの粒
径riと定義する(有効数字3桁、最小桁数字は4捨5
人する)。Here, the average particle diameter f is defined as the particle diameter ri when the product n1 5
people).
粒径riとは、球状のハロゲン化銀粒子の場合は、その
直径、また球状以外の形状の粒子の場合は、その投影像
を同面積の円像に換算した時の直径である。In the case of spherical silver halide grains, the grain size ri is the diameter thereof, and in the case of grains having shapes other than spherical, it is the diameter when the projected image thereof is converted into a circular image of the same area.
粒径は、例えば該粒子を電子顕微鏡で1万倍から5万倍
に拡大して撮影し、そのプリント上の粒子直径または投
影時の面積を実測することによって得ることができる(
測定粒子個数は無差別に1゜000個以上有ることとす
る)。The particle size can be obtained, for example, by photographing the particle with an electron microscope at a magnification of 10,000 to 50,000 times and measuring the particle diameter or projected area on the print (
The number of particles to be measured shall be 1°000 or more indiscriminately).
特に好ましい高度の単分散乳剤は
によって分布の広さを定義したときこれが20%以下の
ものであり、更に好ましくは15%以下のものである。Particularly preferred highly monodisperse emulsions are those with a distribution width of 20% or less, more preferably 15% or less.
ここに平均粒径及び標準偏差は、上記定義したriから
求めるものとする。Here, the average particle diameter and standard deviation are determined from ri defined above.
単分散乳剤を得る方法としては、種粒子を含むゼラチン
溶液中に、水溶性銀塩溶液と水溶性ハライド溶液をpA
g及びpHの制御下ダブルジェット法によって加えるこ
とによって得る方法があり、このような手段を用いるこ
とができる。A method for obtaining a monodispersed emulsion is to add a water-soluble silver salt solution and a water-soluble halide solution to a gelatin solution containing seed particles at pA
There is a method of adding by double jet method under the control of g and pH, and such means can be used.
添加速度の決定に当たっては、特開昭54−48521
号、同5B−49938号を参考にできる。In determining the addition rate, refer to JP-A-54-48521.
No. 5B-49938.
更に高度な単分散乳剤を得る方法として特開昭60−1
22935号に開示されたテトラザインデン存在本発明
の実施に際して用いられるハロゲン化銀乳剤は、ハロゲ
ン化銀粒子の成長の終了後に、適当な方法によって化学
増感に適するpAgイオン濃度にすることができる。例
えば凝集法やヌードル水洗法など、リサーチ・ディスク
ロージャー17643号(Research Disc
losure 17643号)記載の方法で行うことが
できる。As a method for obtaining a more advanced monodispersed emulsion, JP-A-60-1
The silver halide emulsion used in the practice of the present invention, which contains the tetrazaindene disclosed in No. 22935, can be brought to a pAg ion concentration suitable for chemical sensitization by an appropriate method after the growth of silver halide grains is completed. . For example, research disclosure No. 17643 (Research Disc.
Losure No. 17643).
化学増感する場合は、通常のイオウ増感、還元増感、貴
金属増感及びそれらの組み合わせが用いられる。さらに
具体的な化学増感剤と°しては、アリルチオカルバミド
(Allyl thiocarbamide) 、チオ
尿素、チオサルフェート、チオエーテルやシスチンなど
の硫黄増感剤;ボタシウムクロロオーレイト、オーラス
チオサルフェートやポタシウムクロロバラデート(Po
tassilIlchloro palladate)
などの貴金属増感剤;塩化スズ、フェニルヒドラジンや
レタクトンなどの還元増感剤などを挙げることができる
。In the case of chemical sensitization, ordinary sulfur sensitization, reduction sensitization, noble metal sensitization, and combinations thereof are used. More specific chemical sensitizers include sulfur sensitizers such as Allyl thiocarbamide, thiourea, thiosulfate, thioether and cystine; Rose date (Po
tassililchlororo palladate)
and reduction sensitizers such as tin chloride, phenylhydrazine, and retactone.
本発明の実施に際して用いられる写真乳剤は、シアニン
色素類その他によって分光増感されてもよい。増感色素
は単独に用いてよいが、それらの組み合わせを用いても
よく、増悪色素の組み合わせは特に強色増感の目的でし
ばしば用いられる。Photographic emulsions used in the practice of this invention may be spectrally sensitized with cyanine dyes and others. Sensitizing dyes may be used alone or in combination, and combinations of enhancing dyes are often used particularly for the purpose of supersensitization.
本発明に用いる写真乳剤中には、各種の親水性コロイド
を結合剤として使用することができる。Various hydrophilic colloids can be used as binders in the photographic emulsion used in the present invention.
この目的に用いられるコロイドとしては、例えばゼラチ
ン、コロイド状アルブミン、ポリサンカライド、セルロ
ーズ誘導体、合成樹脂、例えばポリビニルアルコール誘
導体を含むポリビニル化合物、アクリルアミドポリマー
等、−iに写真分野で使用せられる親水性コロイドを挙
げることができる。Colloids used for this purpose include, for example, gelatin, colloidal albumin, polysancharides, cellulose derivatives, synthetic resins, polyvinyl compounds including polyvinyl alcohol derivatives, acrylamide polymers, etc. Colloids can be mentioned.
本発明のハロゲン化銀感光材料は、その塗布液中に通常
用いられる写真用硬膜剤、例えばアルデヒド系、アジリ
ジン系(例えばPBレボ−目9,921、米国特許第2
,950.197号、同第2.964.404号、同第
2,983.611号、同第3.271.175号の各
明細書、特公昭46−40898号、特開昭51−91
315号の各公報に記載のもの)、イソオキサゾール系
(例えば米国特許第331,609号明細書に記載のも
の)、エポキシ系(例えば米国特許第3,047,39
4号、西独特許筒1,085,663号、英国特許第1
,033,518号の各明細書、特公昭48−3549
ili号公報に記載のもの)、ビニールスルホン系(例
えばPBレポート19,920、西独特許筒1,100
,942号、英国特許第1,251,091号、特願昭
45−54236号、同4B−110996号、米国特
許第353.964号、同第3,490,911号の各
明細書に記載のもの)、アクリロイル系(例えば特願昭
48−27949号、米国特許第3,640,720号
の各明細書に記載のもの)、カルボジイミド系(例えば
米国特許第2,938.892号明細書、特公昭46−
38715号公報、特願昭49−15095号明細書に
記載のもの)、その他マレイミド系、アセチレン系、メ
タンスルホン酸エステル系、トリアジン系、高分子型の
硬膜剤が使用できる。また、増粘剤として例えば米国特
許第3,167.410号、ベルギー国特許第558.
143号の各明細書に記載のもの、ゼラチン可塑剤とし
てポリオール類(例えば米国特許第2,960,404
号明細書、特公昭43−4939号、特開昭48−63
715号の各公報のもの)、さらにはラテックス類とし
て米国特許第766、979号、フランス特許節1,3
95,544号の各明細書、特公昭48−43125号
公報に記載されるもの、マット剤として英国特許第1,
221,980号明細書に記載のものなどを用いること
ができる。The silver halide photosensitive material of the present invention can be prepared by using a photographic hardening agent commonly used in its coating solution, such as an aldehyde-based hardening agent or an aziridine-based hardening agent (for example, PB Rev. 9,921, U.S. Pat.
, No. 950.197, No. 2.964.404, No. 2,983.611, No. 3.271.175, Japanese Patent Publication No. 46-40898, Japanese Unexamined Patent Publication No. 51-91
No. 315), isoxazole systems (e.g., those described in U.S. Pat. No. 331,609), and epoxy systems (e.g., U.S. Pat. No. 3,047,39).
No. 4, West German Patent No. 1,085,663, British Patent No. 1
, 033,518, Japanese Patent Publication No. 48-3549
ili), vinyl sulfone type (e.g. PB report 19,920, West German patent cylinder 1,100)
, 942, British Patent No. 1,251,091, Japanese Patent Application No. 45-54236, Japanese Patent Application No. 4B-110996, and US Patent No. 353.964, and US Patent No. 3,490,911. acryloyl type (e.g., those described in Japanese Patent Application No. 48-27949 and U.S. Pat. No. 3,640,720), carbodiimide type (e.g., U.S. Pat. No. 2,938,892) ,Special Public Service 1977-
38715 and Japanese Patent Application No. 49-15095), maleimide-based, acetylene-based, methanesulfonic acid ester-based, triazine-based, and polymer hardening agents can be used. In addition, as a thickening agent, for example, US Pat. No. 3,167.410, Belgian Patent No. 558.
No. 143, polyols as gelatin plasticizers (e.g., U.S. Pat. No. 2,960,404)
specification, Japanese Patent Publication No. 43-4939, Japanese Patent Publication No. 48-63
715), and as latexes, U.S. Patent Nos. 766 and 979, and French Patent Sections 1 and 3.
95,544, those described in Japanese Patent Publication No. 48-43125, and the matting agent described in British Patent No. 1,
221,980 and the like can be used.
また、本発明のハロゲン化銀写真感光材料の構成要素層
中には、所望の塗布助剤を用いることができ、例えばサ
ポニン或いはスルホコハク酸系界面活性剤として例えば
英国特許第548.532号、特願昭47−89630
号の各明細書などに記載のもの、あるいはアニオン性界
面活性剤として例えば特公昭43−18166号公報、
米国特許節3,514,293号、フランス特許節2,
025,688号の各明細書、特公昭43−10247
号公報などに記載のものが使用できる。Furthermore, desired coating aids can be used in the component layers of the silver halide photographic material of the present invention, such as saponin or sulfosuccinic acid surfactants, such as those described in British Patent No. Gansho 47-89630
or as anionic surfactants such as those described in Japanese Patent Publication No. 43-18166,
U.S. Patent Section 3,514,293, French Patent Section 2,
Specifications of No. 025,688, Japanese Patent Publication No. 43-10247
Those described in the No. 1 publication can be used.
上記の写真乳剤には感光材料の製造工程、保存中或いは
処理中の感度低下やカブリの発生を防ぐために種々の化
合物を添加することができる。それらの化合物は4−ヒ
ドロキシ−6−メチル−1゜3.3a、7−チトラザイ
ンデン、3−メチル−ベンゾチアゾール、1−フェニル
−3−メルカプトテトラゾールをはじめ、多くの複素環
化合物、含水銀化合物、メルカプト化合物、金属塩類な
ど極めて多くの化合物が古くから知られている。Various compounds can be added to the above-mentioned photographic emulsion in order to prevent a decrease in sensitivity and the occurrence of fog during the manufacturing process, storage or processing of the light-sensitive material. These compounds include 4-hydroxy-6-methyl-1°3.3a, 7-chitrazaindene, 3-methyl-benzothiazole, 1-phenyl-3-mercaptotetrazole, many heterocyclic compounds, mercury-containing compounds, A large number of compounds such as mercapto compounds and metal salts have been known for a long time.
使用できる化合物の一例は、ケイ・ミース(K。An example of a compound that can be used is K. Mies (K.
Mees)著ザ・セオリー・オブ・ザ・フォトグラフィ
ク・プロセス(The Theory of the
PhotographicProcess) (第3版
、1966年)に原文献を挙げて記されているほか、特
開昭49−81024号、同5o−6306号、同50
−19429号、米国特許3,850,639号に記載
されているような当業界でよく知られたがぶり防止剤は
いずれも用いることができる。The Theory of the Photographic Process
Photographic Process) (3rd edition, 1966) lists the original documents, as well as JP-A Nos. 49-81024, 5o-6306, and 50
Any of the antifogging agents well known in the art, such as those described in No. 19429 and US Pat. No. 3,850,639, can be used.
その他、本発明の実施に際しては、写真技術において用
いられる各種の技術を適用することができる。In addition, various techniques used in photography can be applied when implementing the present invention.
(実施例〕
以下本発明の実施例について説明する。なお、当然のこ
とながら、本発明は以下述べる実施例により限定される
ものではない。(Examples) Examples of the present invention will be described below.It should be noted that, as a matter of course, the present invention is not limited to the Examples described below.
実施例−1
反応釜の条件として60℃、pAg=8、そしてpH=
2に保ちつつ、ダブルジェット法により平均粒径0.3
μmの沃化銀2モル%を含む沃臭化銀の単分散立方晶乳
剤を得た。電子顕微鏡観察によれば、双晶の発生率は個
数で1%以下であった。Example-1 Reaction vessel conditions: 60°C, pAg=8, and pH=
While maintaining the average particle size of 0.3 using the double jet method,
A monodisperse cubic emulsion of silver iodobromide containing 2 mol % of silver iodide in micrometers was obtained. According to electron microscopic observation, the incidence of twins was 1% or less in number.
この乳剤を種晶として、さらに以下のように成長させた
。Using this emulsion as a seed crystal, it was further grown as follows.
■比較乳剤Em−1の調製
反応釜内に2χゼラチン水溶液を40℃に保って、それ
に上記種晶を溶解し、さらにアンモニア水と酢酸を加え
て、pH=9.5に調整した。アンモニア性銀イオン液
にてpAg7.3に調整後、pH及びpAgを一定に保
ちつつ、アンモニア性根イオン液と臭化カリウムと沃化
カリウムを含む溶液をダブルジェット法で添加し、沃化
銀30モル%を含む沃臭化銀層を形成せしめた(工程−
1)。(2) Preparation of Comparative Emulsion Em-1 A 2χ gelatin aqueous solution was kept at 40 DEG C. in a reaction vessel, the above seed crystals were dissolved therein, and aqueous ammonia and acetic acid were added to adjust the pH to 9.5. After adjusting the pAg to 7.3 with an ammoniacal silver ion solution, while keeping the pH and pAg constant, a solution containing an ammoniacal silver ion solution, potassium bromide, and potassium iodide was added using a double jet method, and silver iodide was adjusted to 30. A silver iodobromide layer containing mol% was formed (step -
1).
次に、pH=9、pAg=9.0に調整した後に、アン
モニア性銀イオン液と臭化カリウムとを同時に添加し、
成長後、更に粒径の90%にあたるまで成長させた。こ
の時pHは9.0〜8.20まで徐々に下げた(工程−
2)。Next, after adjusting the pH to 9 and pAg to 9.0, an ammoniacal silver ion solution and potassium bromide were added at the same time,
After the growth, the particles were further grown to 90% of the particle size. At this time, the pH was gradually lowered from 9.0 to 8.20 (step-
2).
臭化カリウム液を加えpAg=11とした後に、更にア
ンモニア性根イオン液と臭化カリウムとを加えてpHを
徐々に8まで下げながら成長せしめ、平均粒径0.7μ
m、沃化銀2モル%を含む沃臭化銀乳剤を得た(工程−
3)。After adding potassium bromide solution to set pAg to 11, ammoniacal root ion solution and potassium bromide were further added to grow while gradually lowering the pH to 8, and the average particle size was 0.7μ.
m, a silver iodobromide emulsion containing 2 mol% of silver iodide was obtained (step -
3).
次に下記に示すように、過剰塩をとり除く脱塩工程を行
った。Next, as shown below, a desalting step was performed to remove excess salt.
ハロゲン化銀乳剤溶液を40℃に保ち、下記化合物(a
)(特開昭58−140322号中に示しである例示化
合物■−1)を加えてハロゲン化銀粒子を沈降せしめ、
上澄液を排出後に更に40℃の純水を加える。そして硫
酸マグネシウム(MgSO3)を添加し再度ハロゲン化
銀粒子を沈降せしめ、上澄液をとりさる。これをもう−
度行い、ゼラチンを15g/AgX1モル加え、pH=
6.0、I)Ag=8.5の乳剤を得た(工程−4)。The silver halide emulsion solution was kept at 40°C, and the following compound (a
) (exemplary compound ■-1 shown in JP-A-58-140322) to precipitate silver halide grains,
After draining the supernatant, add pure water at 40°C. Then, magnesium sulfate (MgSO3) is added to precipitate the silver halide grains again, and the supernatant liquid is removed. Have this again-
Repeatedly, 15g/AgX1 mol of gelatin was added, pH=
6.0, I) An emulsion with Ag=8.5 was obtained (Step-4).
(なおAgXはハロゲン化銀を示す。以下同じ)。これ
を乳剤Em−1とする。(Note that AgX represents silver halide. The same applies hereinafter). This is designated as emulsion Em-1.
化合物(a)
■比較乳剤Em−2〜8及び本発明に係る乳剤Em−9
〜18の調製
前記乳剤Em−1の調製における工程−1において、表
−1に示すようにpH,pAgを調整後、pH及びpA
gを一定に保ちつつ、アンモニア性根イオン液と臭化カ
リウム溶液をダブルジェット法で添加しつつ、表−1に
示す方法で沃化カリウム水溶液を添加速度を変えて添加
して、ハロゲン置換法によって沃化銀30モル%を含む
沃臭化銀層を形成せしめた。その後上記乳剤Em−1と
同様に工程2〜4を行い、表−1に示すような乳剤Em
−2〜18を得た。Compound (a) ■ Comparative emulsions Em-2 to Em-8 and emulsion Em-9 according to the present invention
Preparation of ~18 In step-1 in the preparation of emulsion Em-1, after adjusting the pH and pAg as shown in Table-1, the pH and pA
While keeping g constant, ammoniacal root ion solution and potassium bromide solution were added using the double jet method, and potassium iodide aqueous solution was added at different addition speeds using the method shown in Table 1. A silver iodobromide layer containing 30 mol % of silver iodide was formed. Thereafter, steps 2 to 4 were carried out in the same manner as for the emulsion Em-1, and the emulsion Em-1 as shown in Table-1 was prepared.
-2 to 18 were obtained.
このとき、コア及びシェルの体積比は乳剤Em−1とは
変えず、平均粒径0.7μmにして、調製した。At this time, the volume ratio of core and shell was unchanged from that of emulsion Em-1, and the average grain size was set to 0.7 μm.
■比較乳剤E m −19〜25及び本発明に係る乳剤
Em−26〜35の8用型
上記■において、添加する沃化カリウム水溶液のかわり
に、沃化銀を表−2に示すように添加して、ハロゲン置
換法によって沃化銀30モル%を含む沃臭化銀層を形成
せしめた。その後乳剤Em−1と同様に工程2〜4を行
い、表−2に示すような乳剤Em−19〜35を得た。■ Comparative emulsions Em-19 to 25 and emulsions Em-26 to 35 according to the present invention for 8 types In the above ■, instead of the potassium iodide aqueous solution added, silver iodide was added as shown in Table 2. A silver iodobromide layer containing 30 mol % of silver iodide was then formed by a halogen substitution method. Thereafter, steps 2 to 4 were carried out in the same manner as for emulsion Em-1 to obtain emulsions Em-19 to 35 as shown in Table 2.
この場合も、コア及びシェルの体積比は、乳剤Em−1
とは変えず、平均粒径も0.7μmとして調製した。In this case as well, the volume ratio of core and shell is emulsion Em-1
The average particle size was also set to 0.7 μm.
上記■〜■で得られた乳剤Em−1〜35を55°Cに
保ち、塩化金酸、そしてハイポを加えて化学増感を行い
、更に下記の増感色素(A)及び(B)と沃化カリウム
を加えて最適に分光増感し、4ヒドロキシ−6−メチル
−1,3,3a、7−チトラザイデンを加えて感光性乳
剤を得た。The emulsions Em-1 to Em-35 obtained in steps 1 to 3 above were kept at 55°C and chemically sensitized by adding chloroauric acid and hypo, and then added with the following sensitizing dyes (A) and (B). Potassium iodide was added for optimal spectral sensitization, and 4hydroxy-6-methyl-1,3,3a,7-chitrazyden was added to obtain a photosensitive emulsion.
(CHz) 3SO3H(CI□)+5(hO・(cz
ns)J得られた感光性乳剤には添加剤として、ハロゲ
ン化?艮1モル当たり、
t−ブチル−カテコール 400 mg。(CHz) 3SO3H(CI□)+5(hO・(cz
ns) J The resulting photosensitive emulsion contains halogenated additives? 400 mg of t-butyl-catechol per mole of tuna.
ポリビニルピロリドン(分子量10,000) 1.0
g。Polyvinylpyrrolidone (molecular weight 10,000) 1.0
g.
スチレン−無水マレイン酸共重合体 2.5g。Styrene-maleic anhydride copolymer 2.5g.
トリメチロールプロパ7 10g。Trimethylol Propa 7 10g.
ジエチレングリコール 5g・ニトロ
フェニル−トリフェニルフォスフオニウムクロライド
50 mg。Diethylene glycol 5g/Nitrophenyl-triphenylphosphonium chloride
50 mg.
1.3−ジヒドロキシベンゼン−4−スルホン酸アンモ
ニウム 4 g。Ammonium 1.3-dihydroxybenzene-4-sulfonate 4 g.
2−メルカプトベンツイミダゾール−5−スルホン酸ソ
ーダ 5111g。Sodium 2-mercaptobenzimidazole-5-sulfonate 5111 g.
1.1−ジメチロール−1−ブロム−1−二トロメタン 10 mg。1.1-dimethylol-1-bromo-1-nitromethane 10 mg.
さらに保護層とともに、添加剤として下記の化合物をゼ
ラチン1g当たり下記の量加えた。Furthermore, along with the protective layer, the following compounds were added as additives in the following amounts per 1 g of gelatin.
C1bCOO(CHz)9CH3
Na5Oz CHzCOO(CHz)zc41(CH
:+)zB
Na5Os CHCOOCllz(CJn)JCHz
COOCIIz (Czl14) J
5ntgFIQC90+CHzCHzO+r−
1fCHzCHz OH3mg平均粒径7μmのポリ
メチルメタノールからなるマット剤
7mg平均粒径0.013μのコロ
イダルシリカ 70mgホルマリン
29mgグリオキザール
30mg2−ヒドロキシ−4,6−シク
ロロトリアジンナトリウム
30mg上記のようにして乳剤Em−1〜35か
ら得た感光性乳剤を、厚さ180μの下引き処理ずみの
ブルーに着色したポリエチレンテレフタレートフィルム
ベース上に、両面に均一に塗布、乾燥して、試料1〜3
5を得た。C1bCOO(CHz)9CH3 Na5Oz CHzCOO(CHz)zc41(CH
:+)zB Na5Os CHCOOCllz(CJn)JCHz
COOCIIz (Czl14) J
5ntgFIQC90+CHzCHzO+r-
1fCHHzCHz OH3mg Matting agent made of polymethylmethanol with an average particle size of 7μm
7mg colloidal silica with average particle size of 0.013μ 70mg formalin
29mg glyoxal
30mg 2-hydroxy-4,6-cyclotriazine sodium
30 mg of the photosensitive emulsions obtained from emulsions Em-1 to Em-35 as described above were coated uniformly on both sides of a 180-μ thick undercoated blue-colored polyethylene terephthalate film base, and dried. Samples 1-3
Got 5.
得られた試料をX線写真用増感紙KS(コニカ株式会社
製)ではさみ、ベネトロメータB型(コニカメディカル
株式会社製)を介してX線照射後、コニカ株式会社製5
RX−501自動現像機を用いXD−90SR現像処理
にて45秒処理を行った。The obtained sample was sandwiched between X-ray photographic intensifying screens KS (manufactured by Konica Corporation) and irradiated with X-rays through a Venetrometer B type (manufactured by Konica Medical Corporation).
Processing was performed for 45 seconds using an RX-501 automatic developing machine and an XD-90SR development process.
上記のようにして現像した各試料について、感度を評価
した。感度は試料1がカブリ+1.0の濃度を与えるの
に要した爆射エネルギー量の逆数を100とした相対値
で示した。The sensitivity of each sample developed as described above was evaluated. Sensitivity was expressed as a relative value, with 100 being the reciprocal of the amount of irradiation energy required to give sample 1 a density of fog+1.0.
また、粒状性は、光で一面に露光し黒化濃度0゜6〜0
.8の領域の20cmX 20cm の現像試料で目
視評価を行った。5段階評価で、5:非常に良好、4:
良好、3:実用可、2:実用する範囲内でざらついてい
る、1:ザラつきひど(実用不可、とした。In addition, the graininess can be reduced by exposing the entire surface to light and achieving a blackening density of 0°6 to 0.
.. Visual evaluation was performed on a 20 cm x 20 cm developed sample in area No. 8. On a five-point scale, 5: Very good, 4:
Good, 3: Practical, 2: Roughness within a practical range, 1: Severe roughness (not practical).
測定結果を、表−3に示した。The measurement results are shown in Table-3.
表−3から理解されるように、本発明に係る試料である
試料患9〜18.26〜35は、いずれも感度が良好で
、かつ粒状性がすぐれている。As can be seen from Table 3, samples Nos. 9-18 and 26-35, which are samples according to the present invention, all have good sensitivity and excellent graininess.
表−1
表
表
実施例−2
実施例−1で作成した乳剤Em−12と同様の方法で、
表−4に示すようにコア部及びシェル部の沃化銀含有率
が異なる平均粒径0.7μmの沃臭化銀乳剤Em−36
〜44を得た。ただし、シェル部の沃臭化銀の形成は、
ハロゲン置換法を用いず、表−4に示すハロゲン化銀組
成となるようにハロゲンイオン溶液及び銀イオン溶液を
用いて、シェル部を形成した。Table-1 Table Example-2 In the same manner as emulsion Em-12 prepared in Example-1,
Silver iodobromide emulsion Em-36 with an average grain size of 0.7 μm and different silver iodide contents in the core and shell parts as shown in Table 4
~44 was obtained. However, the formation of silver iodobromide in the shell part
A shell portion was formed using a halogen ion solution and a silver ion solution so as to have the silver halide composition shown in Table 4 without using a halogen substitution method.
更に実施例−1と同様にして感光性乳剤を得、これを同
様にフィルムベース上に塗布、乾燥して、試料36〜4
4を得た。これらについて、感度、カブリ、粒状性に関
する評価を行った。感度の基準は実施例−1と同様であ
る。Furthermore, a photosensitive emulsion was obtained in the same manner as in Example 1, and this was coated on a film base in the same manner and dried to obtain Samples 36 to 4.
I got 4. These were evaluated regarding sensitivity, fog, and graininess. The sensitivity criteria are the same as in Example-1.
測定結果は、表−4に示した。The measurement results are shown in Table-4.
本実施例においても、本発明に係る試料(試料魚36
38.39.41〜43゜なお本発明に係る試料N11
12のデータも表−4中に掲げた)がすぐれていること
がわかる。Also in this example, the sample according to the present invention (sample fish 36
38.39.41-43°Sample N11 according to the present invention
It can be seen that the data of No. 12 (listed in Table 4) are excellent.
つづき 〔発明の効果〕 手 続 ネ甫 正 書(自発) 上述の如く、 本発明のハロゲン化銀写真感光材 平成元年3月1日 料は、 感度が高く、 かつ粒状性が良いという効果 を有する。Continued 〔Effect of the invention〕 hand Continued Neho Positive calligraphy (spontaneous) As mentioned above, Silver halide photographic material of the present invention March 1, 1989 The fee is High sensitivity, And the effect of good graininess has.
1、事件の表示
昭和63年特許願第238225号
2、発明の名称
高感度かつ粒状性の改良されたハロゲン化銀写真感光材
料
特
許
出
願
人
コ ニ
カ
株
式
3、補正をする者
代
理
人
フP
理
士
高
月
亨
事件との関係1. Indication of the case Patent Application No. 238225 filed in 1988 2. Name of the invention Patent for silver halide photographic light-sensitive material with high sensitivity and improved graininess Applicant: Konica Co., Ltd. 3. Attorney for the person making the amendment, F.P., Phys. Relationship with Toru Takatsuki Incident
Claims (1)
粒子内部相と、沃化銀含有率が7モル%以下の沃臭化銀
からなる粒子外殻とを少なくとも有し、かつ平均沃化銀
含有率が1.5モル%以上であるハロゲン化銀粒子であ
って、該粒子内部相成長の50%までにハロゲン置換法
によって該粒子内部相中の沃化銀の80%以上を形成す
ることによって得られるハロゲン化銀粒子を含有するこ
とを特徴とするハロゲン化銀写真感光材料。1. At least a grain internal phase made of silver iodobromide with a silver iodide content of 10 mol% or more and a grain outer shell made of silver iodobromide with a silver iodide content of 7 mol% or less, and silver halide grains having an average silver iodide content of 1.5 mol % or more, wherein 80% of the silver iodide in the grain internal phase is grown by a halogen substitution method by 50% of the internal phase growth of the grain. A silver halide photographic light-sensitive material characterized by containing silver halide grains obtained by forming the above.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP23822588A JPH0285846A (en) | 1988-09-22 | 1988-09-22 | Silver halide photographic sensitive material having high sensitivity and improved graininess |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP23822588A JPH0285846A (en) | 1988-09-22 | 1988-09-22 | Silver halide photographic sensitive material having high sensitivity and improved graininess |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH0285846A true JPH0285846A (en) | 1990-03-27 |
Family
ID=17027008
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP23822588A Pending JPH0285846A (en) | 1988-09-22 | 1988-09-22 | Silver halide photographic sensitive material having high sensitivity and improved graininess |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0285846A (en) |
-
1988
- 1988-09-22 JP JP23822588A patent/JPH0285846A/en active Pending
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