JP3150478B2 - X-ray silver halide photographic material having suitable image tone and surface glare - Google Patents
X-ray silver halide photographic material having suitable image tone and surface glareInfo
- Publication number
- JP3150478B2 JP3150478B2 JP04598693A JP4598693A JP3150478B2 JP 3150478 B2 JP3150478 B2 JP 3150478B2 JP 04598693 A JP04598693 A JP 04598693A JP 4598693 A JP4598693 A JP 4598693A JP 3150478 B2 JP3150478 B2 JP 3150478B2
- Authority
- JP
- Japan
- Prior art keywords
- silver
- emulsion
- silver halide
- film
- gelatin
- 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.)
- Expired - Fee Related
Links
- -1 silver halide Chemical class 0.000 title claims description 87
- 229910052709 silver Inorganic materials 0.000 title claims description 83
- 239000004332 silver Substances 0.000 title claims description 83
- 239000000463 material Substances 0.000 title claims description 46
- 230000004313 glare Effects 0.000 title description 6
- 239000000839 emulsion Substances 0.000 claims description 101
- 108010010803 Gelatin Proteins 0.000 claims description 55
- 229920000159 gelatin Polymers 0.000 claims description 55
- 239000008273 gelatin Substances 0.000 claims description 55
- 235000019322 gelatine Nutrition 0.000 claims description 55
- 235000011852 gelatine desserts Nutrition 0.000 claims description 55
- 239000013078 crystal Substances 0.000 claims description 46
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 42
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 21
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 claims description 19
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 16
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 16
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 11
- 238000012545 processing Methods 0.000 claims description 11
- SJOOOZPMQAWAOP-UHFFFAOYSA-N [Ag].BrCl Chemical compound [Ag].BrCl SJOOOZPMQAWAOP-UHFFFAOYSA-N 0.000 claims description 9
- 239000000084 colloidal system Substances 0.000 claims description 5
- 230000001617 migratory effect Effects 0.000 claims description 2
- 230000026030 halogenation Effects 0.000 claims 1
- 238000005658 halogenation reaction Methods 0.000 claims 1
- 239000010410 layer Substances 0.000 description 28
- 150000001875 compounds Chemical class 0.000 description 21
- 238000000034 method Methods 0.000 description 17
- 238000001556 precipitation Methods 0.000 description 17
- 239000003795 chemical substances by application Substances 0.000 description 16
- 239000000243 solution Substances 0.000 description 16
- 238000005406 washing Methods 0.000 description 14
- 239000011248 coating agent Substances 0.000 description 12
- 238000000576 coating method Methods 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 238000007792 addition Methods 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 9
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 239000001045 blue dye Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 230000005070 ripening Effects 0.000 description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 239000002202 Polyethylene glycol Substances 0.000 description 6
- 238000011161 development Methods 0.000 description 6
- 229920001223 polyethylene glycol Polymers 0.000 description 6
- 239000004094 surface-active agent Substances 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000015271 coagulation Effects 0.000 description 5
- 238000005345 coagulation Methods 0.000 description 5
- 239000000975 dye Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 230000035945 sensitivity Effects 0.000 description 5
- 239000003381 stabilizer Substances 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- IJHIIHORMWQZRQ-UHFFFAOYSA-N 1-(ethenylsulfonylmethylsulfonyl)ethene Chemical compound C=CS(=O)(=O)CS(=O)(=O)C=C IJHIIHORMWQZRQ-UHFFFAOYSA-N 0.000 description 4
- 206010070834 Sensitisation Diseases 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 4
- 229910052737 gold Inorganic materials 0.000 description 4
- 239000010931 gold Substances 0.000 description 4
- 150000004820 halides Chemical class 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000005855 radiation Effects 0.000 description 4
- 238000002601 radiography Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 230000008313 sensitization Effects 0.000 description 4
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 4
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-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
- 229910021612 Silver iodide Inorganic materials 0.000 description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 239000006224 matting agent Substances 0.000 description 3
- 230000006911 nucleation Effects 0.000 description 3
- 238000010899 nucleation Methods 0.000 description 3
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 3
- 229940005642 polystyrene sulfonic acid Drugs 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 229940045105 silver iodide Drugs 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 2
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- GGZHVNZHFYCSEV-UHFFFAOYSA-N 1-Phenyl-5-mercaptotetrazole Chemical compound SC1=NN=NN1C1=CC=CC=C1 GGZHVNZHFYCSEV-UHFFFAOYSA-N 0.000 description 2
- WUIJTQZXUURFQU-UHFFFAOYSA-N 1-methylsulfonylethene Chemical compound CS(=O)(=O)C=C WUIJTQZXUURFQU-UHFFFAOYSA-N 0.000 description 2
- JAAIPIWKKXCNOC-UHFFFAOYSA-N 1h-tetrazol-1-ium-5-thiolate Chemical compound SC1=NN=NN1 JAAIPIWKKXCNOC-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- 241001479434 Agfa Species 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N alpha-ketodiacetal Natural products O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- 229920006318 anionic polymer Polymers 0.000 description 2
- 239000002216 antistatic agent Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000008119 colloidal silica Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000009977 dual effect Effects 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
- 229910052751 metal Chemical class 0.000 description 2
- 239000002184 metal Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 238000009659 non-destructive testing Methods 0.000 description 2
- QUBQYFYWUJJAAK-UHFFFAOYSA-N oxymethurea Chemical compound OCNC(=O)NCO QUBQYFYWUJJAAK-UHFFFAOYSA-N 0.000 description 2
- 229950005308 oxymethurea Drugs 0.000 description 2
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 239000004848 polyfunctional curative Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 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 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 238000000108 ultra-filtration Methods 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical class OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- LUMLZKVIXLWTCI-NSCUHMNNSA-N (e)-2,3-dichloro-4-oxobut-2-enoic acid Chemical compound OC(=O)C(\Cl)=C(/Cl)C=O LUMLZKVIXLWTCI-NSCUHMNNSA-N 0.000 description 1
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical class C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 description 1
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 1
- IBABXJRXGSAJLQ-UHFFFAOYSA-N 1,4-bis(2,6-diethyl-4-methylanilino)anthracene-9,10-dione Chemical compound CCC1=CC(C)=CC(CC)=C1NC(C=1C(=O)C2=CC=CC=C2C(=O)C=11)=CC=C1NC1=C(CC)C=C(C)C=C1CC IBABXJRXGSAJLQ-UHFFFAOYSA-N 0.000 description 1
- YLVACWCCJCZITJ-UHFFFAOYSA-N 1,4-dioxane-2,3-diol Chemical compound OC1OCCOC1O YLVACWCCJCZITJ-UHFFFAOYSA-N 0.000 description 1
- SIQZJFKTROUNPI-UHFFFAOYSA-N 1-(hydroxymethyl)-5,5-dimethylhydantoin Chemical compound CC1(C)N(CO)C(=O)NC1=O SIQZJFKTROUNPI-UHFFFAOYSA-N 0.000 description 1
- FYBFGAFWCBMEDG-UHFFFAOYSA-N 1-[3,5-di(prop-2-enoyl)-1,3,5-triazinan-1-yl]prop-2-en-1-one Chemical compound C=CC(=O)N1CN(C(=O)C=C)CN(C(=O)C=C)C1 FYBFGAFWCBMEDG-UHFFFAOYSA-N 0.000 description 1
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- YGDWUQFZMXWDKE-UHFFFAOYSA-N 1-oxido-1,3-thiazole Chemical class [O-]S1=CN=C=C1 YGDWUQFZMXWDKE-UHFFFAOYSA-N 0.000 description 1
- HAZJTCQWIDBCCE-UHFFFAOYSA-N 1h-triazine-6-thione Chemical compound SC1=CC=NN=N1 HAZJTCQWIDBCCE-UHFFFAOYSA-N 0.000 description 1
- YKUDHBLDJYZZQS-UHFFFAOYSA-N 2,6-dichloro-1h-1,3,5-triazin-4-one Chemical compound OC1=NC(Cl)=NC(Cl)=N1 YKUDHBLDJYZZQS-UHFFFAOYSA-N 0.000 description 1
- PHPYXVIHDRDPDI-UHFFFAOYSA-N 2-bromo-1h-benzimidazole Chemical compound C1=CC=C2NC(Br)=NC2=C1 PHPYXVIHDRDPDI-UHFFFAOYSA-N 0.000 description 1
- AYPSHJCKSDNETA-UHFFFAOYSA-N 2-chloro-1h-benzimidazole Chemical compound C1=CC=C2NC(Cl)=NC2=C1 AYPSHJCKSDNETA-UHFFFAOYSA-N 0.000 description 1
- KRTDQDCPEZRVGC-UHFFFAOYSA-N 2-nitro-1h-benzimidazole Chemical compound C1=CC=C2NC([N+](=O)[O-])=NC2=C1 KRTDQDCPEZRVGC-UHFFFAOYSA-N 0.000 description 1
- YZEUHQHUFTYLPH-UHFFFAOYSA-N 2-nitroimidazole Chemical compound [O-][N+](=O)C1=NC=CN1 YZEUHQHUFTYLPH-UHFFFAOYSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N 2-propanol Substances CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- CBHTTYDJRXOHHL-UHFFFAOYSA-N 2h-triazolo[4,5-c]pyridazine Chemical compound N1=NC=CC2=C1N=NN2 CBHTTYDJRXOHHL-UHFFFAOYSA-N 0.000 description 1
- OCVLSHAVSIYKLI-UHFFFAOYSA-N 3h-1,3-thiazole-2-thione Chemical compound SC1=NC=CS1 OCVLSHAVSIYKLI-UHFFFAOYSA-N 0.000 description 1
- NYYSPVRERVXMLJ-UHFFFAOYSA-N 4,4-difluorocyclohexan-1-one Chemical compound FC1(F)CCC(=O)CC1 NYYSPVRERVXMLJ-UHFFFAOYSA-N 0.000 description 1
- UTMDJGPRCLQPBT-UHFFFAOYSA-N 4-nitro-1h-1,2,3-benzotriazole Chemical compound [O-][N+](=O)C1=CC=CC2=NNN=C12 UTMDJGPRCLQPBT-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
- GIQKIFWTIQDQMM-UHFFFAOYSA-N 5h-1,3-oxazole-2-thione Chemical compound S=C1OCC=N1 GIQKIFWTIQDQMM-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229920001817 Agar Polymers 0.000 description 1
- 102000009027 Albumins Human genes 0.000 description 1
- 108010088751 Albumins Proteins 0.000 description 1
- KLSJWNVTNUYHDU-UHFFFAOYSA-N Amitrole Chemical compound NC1=NC=NN1 KLSJWNVTNUYHDU-UHFFFAOYSA-N 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
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical class C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- UZGAHOUBWQDOGQ-UHFFFAOYSA-N Cl[IH]I Chemical compound Cl[IH]I UZGAHOUBWQDOGQ-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 1
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical class OCC1CO1 CTKINSOISVBQLD-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
- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 238000001016 Ostwald ripening Methods 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- ASZXGHPTTZYFFA-UHFFFAOYSA-N S[N] Chemical compound S[N] ASZXGHPTTZYFFA-UHFFFAOYSA-N 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 1
- 241001061127 Thione Species 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- USDJGQLNFPZEON-UHFFFAOYSA-N [[4,6-bis(hydroxymethylamino)-1,3,5-triazin-2-yl]amino]methanol Chemical compound OCNC1=NC(NCO)=NC(NCO)=N1 USDJGQLNFPZEON-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 150000001346 alkyl aryl ethers Chemical class 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000001000 anthraquinone dye Substances 0.000 description 1
- 230000002180 anti-stress Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- XHLMRAUSOZPJEM-UHFFFAOYSA-N benzenesulfonothioamide Chemical compound NS(=O)(=S)C1=CC=CC=C1 XHLMRAUSOZPJEM-UHFFFAOYSA-N 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical class C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 150000001565 benzotriazoles Chemical class 0.000 description 1
- 150000003842 bromide salts Chemical class 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 150000001661 cadmium Chemical class 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N cinnamic acid Chemical class OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 238000011026 diafiltration Methods 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 150000002012 dioxanes Chemical class 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 150000002019 disulfides Chemical class 0.000 description 1
- AFOSIXZFDONLBT-UHFFFAOYSA-N divinyl sulfone Chemical compound C=CS(=O)(=O)C=C AFOSIXZFDONLBT-UHFFFAOYSA-N 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 150000002344 gold compounds Chemical class 0.000 description 1
- 239000003966 growth inhibitor Substances 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 150000002429 hydrazines Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 1
- AKCUHGBLDXXTOM-UHFFFAOYSA-N hydroxy-oxo-phenyl-sulfanylidene-$l^{6}-sulfane Chemical compound SS(=O)(=O)C1=CC=CC=C1 AKCUHGBLDXXTOM-UHFFFAOYSA-N 0.000 description 1
- WYASEAQTEQVOJE-UHFFFAOYSA-N hydroxy-phenyl-sulfanylidene-$l^{4}-sulfane Chemical compound OS(=S)C1=CC=CC=C1 WYASEAQTEQVOJE-UHFFFAOYSA-N 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 1
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 1
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 1
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000002730 mercury Chemical class 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 229930182817 methionine Natural products 0.000 description 1
- 238000000386 microscopy Methods 0.000 description 1
- ZAKLKBFCSHJIRI-UHFFFAOYSA-N mucochloric acid Natural products OC1OC(=O)C(Cl)=C1Cl ZAKLKBFCSHJIRI-UHFFFAOYSA-N 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000004010 onium ions Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 125000000612 phthaloyl group Chemical group C(C=1C(C(=O)*)=CC=CC1)(=O)* 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000191 poly(N-vinyl pyrrolidone) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- UGZVCHWAXABBHR-UHFFFAOYSA-O pyridin-1-ium-1-carboxamide Chemical class NC(=O)[N+]1=CC=CC=C1 UGZVCHWAXABBHR-UHFFFAOYSA-O 0.000 description 1
- HBCQSNAFLVXVAY-UHFFFAOYSA-N pyrimidine-2-thiol Chemical compound SC1=NC=CC=N1 HBCQSNAFLVXVAY-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229930182490 saponin Natural products 0.000 description 1
- 150000007949 saponins Chemical class 0.000 description 1
- 235000017709 saponins Nutrition 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 230000035807 sensation Effects 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Substances [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 1
- 241000894007 species Species 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical class C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 125000004964 sulfoalkyl group Chemical group 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- JJJPTTANZGDADF-UHFFFAOYSA-N thiadiazole-4-thiol Chemical compound SC1=CSN=N1 JJJPTTANZGDADF-UHFFFAOYSA-N 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 230000000007 visual effect Effects 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
- G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
- G03C1/825—Photosensitive materials characterised by the base or auxiliary layers characterised by antireflection means or visible-light filtering means, e.g. antihalation
- G03C1/83—Organic dyestuffs therefor
- G03C1/832—Methine or polymethine dyes
-
- 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
-
- 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
- G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
- G03C5/16—X-ray, infrared, or ultraviolet ray processes
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
Description
【０００１】本発明は好ましい像色調を有する工業用放
射線写真用の写真材料に関する。The present invention relates to a photographic material for industrial radiography having a favorable image tone.
【０００２】工業用放射線写真、特に非破壊試験用の分
野で、調査される材料の信頼性のある検査は、現像後得
られる像が良好な品質、即ち鮮鋭度及び粒状度を有する
ときにのみ可能である。[0002] industrial radiography, especially the field of non-destructive testing, inspection reliable material to be investigated is only when the image obtained after development is good with quality, i.e. sharpness and granularity It is possible .
【０００３】さもなければ、像色調及び像まぶしさが、
観察を容易にするため一定でかつ受け入れられることが
試験する者にとって非常に重要である。非破壊目的のた
め、試験者は、好ましくは僅かに青色調で充分なまぶし
さを有する冷黒調像に慣れている。[0003] Otherwise, the image tone and the image glare are
Constant and acceptable for facilitating observation is very important for the tester. For non-destructive purposes, the tester is accustomed to a cool black-tone image, preferably with a slight blue tint and sufficient glare.
【０００４】かかるＸ線写真材料においては、下記の理
由のため像形成材料として立方晶臭沃化銀粒子を有する
ハロゲン化銀乳剤結晶が使用される。特に直接レントゲ
ンに応用するため不可欠の利点である高フィルム速度を
達成するため、露光放射線の効率的な吸収が第一の条件
である。Oxford の Pergamom Press １９５７年発
行、J. Thewlis 著 Encyclopaedic Dictionary of
Physics 、Vol.７，ｐ．７８７（１０版）に記載されて
いる如く、Ｘ線に対しては、質量吸収係数は原子番号Ｚ
のべきに比例することが実験的に示されている。これは
例えば臭素（Ｚ＝３５）又は沃素（Ｚ＝５４）に比較し
て塩素（Ｚ＝１７）の使用を非常に好ましくないものに
している。或いは、立方晶癖が有利である。これは前記
結晶を露光したとき良好な吸収特性を得るハロゲン化銀
結晶の容積効果のためである。In such X-ray photographic materials, silver halide emulsion crystals having cubic silver bromoiodide grains are used as image-forming materials for the following reasons. Efficient absorption of exposure radiation is a primary requirement, especially in order to achieve high film speeds, an essential advantage for direct radiographic applications. Oxford's Pergamom Press, 1957, Encyclopaedic Dictionary of J. Thewlis
Physics, Vol. 7, p. As described in 787 (10th edition), for X-rays, the mass absorption coefficient is represented by atomic number Z.
It has been shown experimentally to be proportional to the power of This makes the use of chlorine (Z = 17) very undesirable compared to, for example, bromine (Z = 35) or iodine (Z = 54). Alternatively, a cubic habit is advantageous . This is due to the volume effect of the silver halide crystal which obtains good absorption characteristics when the crystal is exposed.
【０００５】球状臭沃化銀結晶に対しては、０．３０μ
ｍより小さい直径に粒度を下げることにより、現像を工
業用のための代表的な処理順序で行ったとき、純黒色か
ら褐色味に像色調が変化することが実験的に確立されて
いる。For a spherical silver bromoiodide crystal, 0.30 μm
It has been experimentally established that by reducing the particle size to a diameter smaller than m, the image tone changes from pure black to brown when developed in a typical processing sequence for industrial use.
【０００６】最近の特許文献から、Ｘ線材料を処理した
とき平板結晶がかかる褐色味の像色調を示すことが良く
知られている。この問題のための解決はＵＳ−Ｐ４８１
８６７５に記載されている如くマゼンタ染料の如き化合
物の添加、特願平１−２９８３８に記載されている如く
アンスラキノン染料及び四級アンモニウム塩の添加によ
って見出されている。他の解決法は、特願平１−３１２
５３６に記載されている如く乳剤製造中の洗浄工程中で
加えた増感染料、特願昭６１−１７０７３９に記載され
ている如きメルカプトテトラゾールもしくは特願昭６３
−１５５１４０に記載されている如きメルカプト窒素含
有複素環化合物、特願平１−１７０４４に記載されてい
る如くメルカプトアルキルスルホン酸もしくはプソイド
チオウロニウム分子内塩誘導体、特願昭６３−２７１４
４３に記載されている如き還元分解によって発生する染
料放出レドックス化合物、特願昭６３−１８０９４４及
び特願昭６３−１８０９４５に記載されている如き特殊
処理したゼラチン、特願平１−９１１３２に記載されて
いる如きポリアクリルアミド誘導体又はその共重合体、
及びエチレン系不飽和化合物の如き新規な色調変性剤プ
リカーサーの添加によって見出されている。It is well known from recent patent literature that tabular crystals exhibit such a brownish image tone when X-ray materials are processed. The solution to this problem is US-P481
It has been found by the addition of a compound such as a magenta dye as described in JP 8675, and the addition of an anthraquinone dye and a quaternary ammonium salt as described in Japanese Patent Application No. 1-29838. Another solution is disclosed in Japanese Patent Application No. Hei.
No. 536, sensitizing dye added during the washing step during emulsion production, mercaptotetrazole as described in Japanese Patent Application No. 61-170739 or Japanese Patent Application No. Sho 63
-155140, a mercapto nitrogen-containing heterocyclic compound as described in JP-A-155140, a mercaptoalkylsulfonic acid or a pseudothiouronium inner salt derivative as described in Japanese Patent Application No. 1-17044, JP-A-63-2714.
43, a dye-releasing redox compound generated by reductive decomposition, specially treated gelatin as described in Japanese Patent Application Nos. 63-180944 and 63-180945, and described in Japanese Patent Application No. 1-91132. A polyacrylamide derivative or a copolymer thereof,
And the addition of novel color modifier precursors such as ethylenically unsaturated compounds.
【０００７】医学用Ｘ線及び工業用Ｘ線材料の何れに対
しても、球状ハロゲン化銀結晶について、望ましからぬ
像色調の問題は述べられておらず、従って特許文献には
そのための解決は見出されていない。[0007] Neither medical X-rays nor industrial X-ray materials describe the problem of undesired image tones with spherical silver halide crystals, and therefore the patent literature does not address the problem. Has not been found.
【０００８】それ以外に、輸送適性、粘着現象等の如き
物理特性を改良するため、ハロゲン化銀写真材料の親水
性層中に、艶消剤を存在させることが好ましいことは良
く知られている。これらの艶消層の不利な効果は、銀像
の明澄度又は光沢にある。In addition, it is well known that a matting agent is preferably present in the hydrophilic layer of a silver halide photographic material in order to improve physical properties such as transportability and sticking phenomenon. . A disadvantage of these matte layers is the clarity or gloss of the silver image.
【０００９】レゾルシノール、シリカ及びポリ−Ｎ−ビ
ニルピロリドンを含有する二重Ｘ線材料の艶消層中の濁
度を避けるため、ＵＳ−Ｐ３６５６９５４に解決が与え
られており、スルホン化スチルベン、トリアジン又はナ
フタレン化合物の使用をしている。上塗層及び少なくと
も一つの他の層中に特定粒度の艶消剤を含有する材料に
対して、表面まぶしさ（及び接着性）における改良が特
願昭６２−２７５２４０に記載されている。像銀のさえ
の改良も、特願昭６２−２８６８３９に記載されている
如く、０．２〜０．６μｍの平均直径を有し、５より大
なる平均アスペクト比を有する平板粒子乳剤を含有する
ハロゲン化銀写真材料のため、フィルム硬化剤の濃度の
調整を制御することによっても得ることができる。好ま
しい硬化剤はジメチロール尿素及びトリメチロールメラ
ミンである。To avoid turbidity in the matte layer of dual X-ray materials containing resorcinol, silica and poly-N-vinylpyrrolidone, a solution is given in US Pat. No. 3,656,954, wherein sulfonated stilbene, triazine or triazine is used. Naphthalene compounds are used. An improvement in surface glare (and adhesion) for materials containing a specific particle size matting agent in the overcoat layer and at least one other layer is described in Japanese Patent Application No. 62-275240. Improvements in even image silver include tabular grain emulsions having an average diameter of 0.2 to 0.6 .mu.m and an average aspect ratio of greater than 5 as described in Japanese Patent Application No. 62-286839. For silver halide photographic materials, it can also be obtained by controlling the adjustment of the concentration of the film hardener. Preferred curing agents are dimethylol urea and trimethylol melamine.
【００１０】又表面まぶしさの現象に関しては、文献で
は、ハロゲン化銀写真材料の少なくとも一つの親水性層
中の艶消剤及び球状結晶を含むハロゲン化銀写真材料に
対して殆ど関心を示していない。Also with regard to the phenomenon of surface glare, the literature has shown little interest in silver halide photographic materials containing matting agents and spherical crystals in at least one hydrophilic layer of the silver halide photographic material. Absent.
【００１１】本発明の第一の目的は、試験されるべき現
像されたフィルムに有利な像色調及び表面まぶしさ特性
を与える工業用放射線写真のためのハロゲン化銀写真材
料を提供することにある。It is a first object of the present invention to provide a silver halide photographic material for industrial radiography which gives the developed film to be tested advantageous image tone and surface glare characteristics. .
【００１２】本発明の第二の目的は、すぐれた像品質、
特に像鮮鋭性、及び良好な物理的性質を有する工業用写
真材料を提供することにある。A second object of the present invention is to provide excellent image quality,
In particular, it is an object of the present invention to provide an industrial photographic material having image sharpness and good physical properties.
【００１３】他の目的は以下の説明から明らかになるで
あろう。[0013] Other objects will become apparent from the following description.
【００１４】 前記目的は、フィルム支持体及びその一側
又は両側に少なくとも一つのハロゲン化銀乳剤層を含む
工業用放射線写真用写真ハロゲン化銀材料において、各
ハロゲン化銀乳剤層が、化学的に熟成した立方晶単分散
臭沃化銀、及び化学的に熟成した立方晶単分散塩化銀及
び／又は塩臭化銀及び／又は塩臭沃化銀乳剤結晶の混合
物を含有すること、前記材料が、硝酸銀として表わした
ハロゲン化銀に対するゼラチンの重量比０．３〜１．２
を有すること、及び前記材料が処理サイクルの終りの洗
浄後に、それがゼラチン１ｇについて水２．５ｇ未満を
吸収する程度に硬化されていることを特徴とする写真ハ
ロゲン化銀材料によって達成される。 The object is to provide an industrial radiographic photographic silver halide material comprising a film support and at least one silver halide emulsion layer on one or both sides thereof, wherein each silver halide emulsion layer is chemically Comprising a mixture of aged cubic monodispersed silver bromoiodide and chemically aged cubic monodispersed silver chloride and / or silver chlorobromide and / or silver chlorobromoiodide emulsion crystals; Weight ratio of gelatin to silver halide expressed as silver nitrate 0.3-1.2
And a photographic silver halide material characterized in that after washing at the end of the processing cycle, the material has been hardened to an extent that it absorbs less than 2.5 g of water per gram of gelatin.
【００１５】元の臭沃化銀乳剤結晶に加えて、塩化銀含
有乳剤結晶は、球状臭沃化銀乳剤結晶の大きさより大き
さにおいて大きくても３０％であるか、それより小さい
結晶直径及び立方晶癖を有する化学的に熟成された乳剤
であり、前記臭沃化銀結晶は、０．３０μｍ以下の平均
結晶直径を有する。In addition to the original silver bromoiodide emulsion crystals, the silver chloride-containing emulsion crystals have a crystal diameter and diameter of at most 30% or less in size than that of the spherical silver bromoiodide emulsion crystals. A chemically ripened emulsion having a cubic habit, wherein the silver bromoiodide crystals have an average crystal diameter of 0.30 μm or less.
【００１６】本発明により形成されるハロゲン化銀乳剤
は、臭沃化銀を含有する。好ましい臭沃化銀乳剤は多く
ても１０モル％の沃化銀、好ましくは多くても３モル
％、更に好ましくは１モル％の沃化銀を含有する。規則
形ハロゲン化銀結晶、特に工業用放射線写真材料に使用
される如き立方結晶晶癖を有する臭沃化銀乳剤は、高感
度について良好な現像特性を有することが知られてい
る。写真乳剤製造の沈澱段階中に立方結晶又は八面体結
晶が形成されるかどうかを決定するパラメーターは溶液
のｐＡｇである。The silver halide emulsion formed according to the present invention contains silver bromoiodide. Preferred silver bromoiodide emulsions contain at most 10 mol% silver iodide, preferably at most 3 mol%, more preferably 1 mol%. It is known that regular silver halide crystals, particularly silver bromoiodide emulsions having a cubic crystal habit as used in industrial radiographic materials, have good development characteristics with high sensitivity. The parameter that determines whether cubic or octahedral crystals are formed during the precipitation stage of photographic emulsion manufacture is the pAg of the solution.
【００１７】溶液のｐＡｇは、ＵＳ−Ｐ３８２１００２
に記載されている電子制御装置及び方法の如き乳剤製造
の技術で知られている任意の手段で調整できる。The pAg of the solution is US Pat.
The adjustment can be made by any means known in the art of emulsion production, such as the electronic control devices and methods described in.
【００１８】Bunsengesellschaft fuer physikalisch
e Chemie , Berichte ６７ ９４９〜９５７（１９６
３年）、Ｎｏ．９，１０の E. Moisar 及び E. Klein
の論文、Der Einfluss der Wachstumsbedingungen
auf die Kristalltrachtder Silberhalogenide （ハ
ロゲン化銀の結晶挙動についての生長条件の影響）か
ら、均質分散臭化銀乳剤の１４面体結晶を硝酸銀及び臭
化カリウムの溶液の制御された添加によって生長させる
とき、溶液相中での少し過剰の臭化カリウム濃度の条件
下に得られることが知られている。本発明により使用す
る乳剤を製造する好ましい実施態様では、二重ジェット
条件下に沈澱させることにより、これらのＸ線乳剤の如
き高感度臭沃化銀乳剤の製造を含む。均質ハロゲン化銀
乳剤の製造のための現在の方法は、形成されるハロゲン
化銀結晶の形を調整するため特別な制御装置の使用を
し、前記の形は反応容器中の温度及びｐＡｇ値によって
決るのであるが、銀イオンの濃度は、Research Disclo
sure Item １０３０８に記載されている如く特別な流
入技術の使用により沈澱中一定に保つことができる。Bunsengesellschaft fuer physikalisch
e Chemie, Berichte 67 949-957 (196
3 years), No. 9, 10 E. Moisar and E. Klein
Paper, Der Einfluss der Wachstumsbedingungen
From the auf die Kristalltrachtder Silberhalogenide (the effect of growth conditions on the crystal behavior of silver halide), the solution phase is developed when the tetradecahedral crystals of a homogeneously dispersed silver bromide emulsion are grown by the controlled addition of silver nitrate and potassium bromide solutions. It is known to be obtained under conditions of a slight excess of potassium bromide concentration in the medium. A preferred embodiment of preparing the emulsions used in accordance with the present invention involves the preparation of sensitive silver bromoiodide emulsions, such as these X-ray emulsions, by precipitation under double jet conditions. Current methods for the production of homogeneous silver halide emulsions use special controls to regulate the shape of the silver halide crystals formed, said shape being dependent on the temperature in the reaction vessel and the pAg value. Although it is decided, the concentration of silver ion depends on Research Disclo
It can be kept constant during precipitation by using special inflow techniques as described in sure Item 10308.
【００１９】本発明により作られるハロゲン化銀乳剤の
平均粒度は０．１〜０．３μｍの間にあるのが好まし
い。ハロゲン化銀粒子の粒度は通常の方法、例えば The
photographic Journal 、Vol.６９（１９３９年）
ｐ．３３０〜３３８に Trivelli及び M. Smithによ
り、 ASTM symposium on light microscopy １９５
３年、ｐ．９４〜１２２に、そして The theory of
the Photographic process（１９７７年）、第II章に
Mees 及びJames によって発表されている如き方法を用
いて測定できる。The average grain size of the silver halide emulsion prepared according to the present invention is preferably between 0.1 and 0.3 .mu.m. The size of the silver halide grains is determined by a conventional method, for example, The
photographic Journal, Vol. 69 (1939)
p. ASTM symposium on light microscopy 195 by Trivelli and M. Smith on 330-338.
3 years, p. 94-122, and the theory of
the Photographic process (1977), in Chapter II
It can be measured using methods as published by Mees and James.
【００２０】再現性ある結晶粒度を得るため、特に溶液
の流速及び濃度、温度及びｐＡｇは非常に注意して調整
しなければならない。粒子生長抑制剤又は促進剤を乳剤
結晶の製造開始から又は製造中に加えることができる。
沈澱中の初期条件によって、本発明にとって意のままに
単分散乳剤を作ることができる。不均質分散とは異な
り、単分散乳剤は、粒子の重量又は数の少なくとも９５
％が、平均粒子直径の約４０％内、好ましくは約３０％
内、更に好ましくは約１０〜２０％内にある直径を有す
る乳剤として当技術分野で特性づけられている。In order to obtain a reproducible grain size, in particular the flow rate and concentration of the solution, the temperature and the pAg must be adjusted very carefully. A grain growth inhibitor or accelerator can be added from the start of or during the preparation of the emulsion crystals.
Depending on the initial conditions during precipitation, a monodisperse emulsion can be made as desired for the present invention. Unlike heterodisperse, monodisperse emulsions have at least 95% by weight or number of grains.
% Is within about 40% of the average particle diameter, preferably about 30%
And more preferably in the art as an emulsion having a diameter within about 10-20%.
【００２１】非常に狭い粒度分布を有するハロゲン化銀
粒子は、従って二重ジェット法を用いてハロゲン化銀粒
子を製造する条件を厳密に制御することによって得るこ
とができる。かかる方法において、ハロゲン化銀粒子
は、ハロゲン化銀解膠剤、好ましくはゼラチン、ゼラチ
ン誘導体又は若干の他の蛋白質解膠剤の急速に撹拌した
水性溶液中に、水溶性銀塩、例えば硝酸銀、及び水溶性
ハロゲン化物、例えば臭化カリウムと沃化カリウムの混
合物の水性溶液を同時に流し入れることによって作られ
る。ヨーロッパ特許出願３９２０９２に記載されている
如く保護コロイドとしてコロイドシリカさえも使用でき
る。Silver halide grains having a very narrow size distribution can thus be obtained by strictly controlling the conditions for producing silver halide grains using the double jet method. In such a method, the silver halide grains are prepared by dissolving a water-soluble silver salt, such as silver nitrate, in a rapidly stirred aqueous solution of a silver halide deflocculant, preferably gelatin, a gelatin derivative or some other protein deflocculant. And an aqueous solution of a water-soluble halide, for example, a mixture of potassium bromide and potassium iodide. Even colloidal silica can be used as protective colloid as described in European Patent Application 392092.
【００２２】好ましい実施態様において、硝酸銀及びハ
ロゲン化物塩溶液の添加速度は、反応容器中で再核形成
が出現しないような方法で着実に増大させる。この方法
は、時間を節約するばかりでなく、沈澱中のハロゲン化
銀結晶の物理熟成、いわゆるオストワルド熟成現象（こ
れはハロゲン化銀結晶分布の拡大を生ぜしめる）を避け
るため特に推奨される。In a preferred embodiment, the rate of addition of the silver nitrate and halide salt solution is steadily increased in such a way that renucleation does not appear in the reaction vessel. This method is particularly recommended not only to save time, but also to avoid physical ripening of the silver halide crystals during precipitation, the so-called Ostwald ripening phenomenon, which causes an expansion of the silver halide crystal distribution.
【００２３】本発明によれば前述した臭沃化銀乳剤に加
える乳剤は塩化銀結晶、好ましくは２５モル％以下の沃
素イオン及び１モル％以下の沃素イオンを含む塩臭化銀
又は塩臭沃化銀結晶を含有する乳剤である。According to the present invention, the emulsion to be added to the above-mentioned silver bromoiodide emulsion is silver chloride crystals, preferably silver chlorobromide or chloroiodoiodide containing up to 25 mol% of iodide ions and up to 1 mol% of iodide ions. This is an emulsion containing silver halide crystals.
【００２４】本発明により使用する塩化銀、塩臭化銀又
は塩臭沃化銀乳剤の製造のため、通常のライム処理又は
酸処理したゼラチンを使用できる。かかるゼラチン種の
製造は、例えば Academic Press １９７７年発行、A.
G. Ward 及び A. Courts編集、The Science and T
echnolgy of Gelatin の２９５〜２９６頁に記載され
ている。ゼラチンは又 Bull. Soc. Sci. Phot. Japan、
Ｎｏ．１６、３０頁（１９６６年）に記載されている如
く酵素処理もできる。For the production of the silver chloride, silver chlorobromide or silver chlorobromoiodide emulsion used in the present invention, conventional lime-treated or acid-treated gelatin can be used. The production of such gelatin species is described, for example, in Academic Press 1977, A.
Edited by G. Ward and A. Courts, The Science and T
echnolgy of Gelatin at pages 295-296. Gelatin is also available from Bull. Soc. Sci. Phot. Japan,
No. Enzymatic treatment can also be performed as described on pages 16 and 30 (1966).
【００２５】ハロゲン化銀粒子の形成前又は形成中、ゼ
ラチン濃度は分散媒中で約０．０５〜５．０重量％で保
つ。追加のゼラチンは乳剤製造の後の段階、例えば洗浄
後に加える。ゼラチン対ハロゲン化銀比は０．３〜１．
２の範囲である。本発明との関連において沈澱は原則的
に一つの二重ジェット工程で行うことができるが、核形
成工程及び少なくとも一つの生長工程の順序で行うこと
もできる。Before or during the formation of the silver halide grains, the gelatin concentration is maintained at about 0.05 to 5.0% by weight in the dispersion medium. Additional gelatin is added at a later stage of emulsion preparation, for example, after washing. The gelatin to silver halide ratio is 0.3-1.
2 range. In the context of the present invention, the precipitation can in principle be carried out in one double jet step, but also in the order of a nucleation step and at least one growth step.
【００２６】沈澱する全ハロゲン化銀の好ましくは０．
５〜５．０％を、好ましくは銀塩及びハロゲン化物塩の
ほぼ等分子添加からなる前記核形成工程中に加える。残
余の銀塩及びハロゲン化物塩は続く一つ以上の二重ジェ
ット生長工程中に加える。沈澱の異なる工程は物理熟成
工程によって変えることができる。生長工程中、銀塩及
びハロゲン化物塩溶液の増大する流速、例えば直線的に
増大する流速を確立するのが好ましい。終了時の代表的
流速は、生長工程の開始時より約３〜１０倍大である。
これらの流速は例えば磁気バルブで監視できる。ハロゲ
ン化銀結晶の全容量にわたって、ハロゲン化銀の不均質
又は均質分布を使用できる。後者の場合においては、ハ
ロゲン化物溶液の組成は全沈澱中変化させないままでお
く。本発明の範囲内では、臭素イオンの２５モル％以下
の量及び沃素イオンの１モル％以下の量を、ハロゲン化
銀結晶中に均質に形成させるとよい。Preferably, the total amount of silver halide to be precipitated is 0.1.
5 to 5.0% is added during the nucleation step, which preferably consists of approximately equal molecular additions of silver and halide salts. Residual silver and halide salts are added during one or more subsequent double jet growth steps. The different steps of precipitation can be varied by the physical ripening step. During the growth process, it is preferred to establish an increasing flow rate of the silver salt and halide salt solution, for example, a linearly increasing flow rate. Typical flow rates at the end are about 3-10 times greater than at the beginning of the growth process.
These flow rates can be monitored, for example, with a magnetic valve. A heterogeneous or homogeneous distribution of silver halide over the entire volume of the silver halide crystal can be used. In the latter case, the composition of the halide solution is left unchanged during the entire precipitation. Within the scope of the present invention, an amount of up to 25 mol% of bromide ions and an amount of up to 1 mol% of iodide ions may be homogeneously formed in the silver halide crystals.
【００２７】沈澱後均質ハロゲン化銀結晶分布を得るた
め、沈澱の異なる段階の開始前及び段階中、ｐＡｇは、
核形成工程中は１０５〜８５ｍＶの間で、好ましくは生
長工程中で９０〜６５ｍＶで保ち、ｐＨは５．２〜５．
８、好ましくは５．６〜５．８で保つ。In order to obtain a homogeneous silver halide crystal distribution after precipitation, before and during the different stages of precipitation, the pAg is
Maintain between 105-85 mV during the nucleation step, preferably between 90-65 mV during the growth step, and maintain the pH between 5.2-5.
8, preferably 5.6 to 5.8.
【００２８】通常の沈澱条件を用いたとき、塩素を多く
含むハロゲン化銀乳剤粒子は、（１００）結晶面を有す
る立方晶形態を示す。これは他の結晶形態、例えば八面
体、斜方十二面体又は平板状塩化銀結晶（これらはいわ
ゆる生長変性剤又は晶癖変性剤の使用を必要とする）よ
りも良好な現像特性を提供する。本発明により使用する
塩化銀、塩臭化銀又は塩臭沃化銀は０．１０〜０．４０
μｍの平均粒度を有するのが好ましい。When using ordinary precipitation conditions, silver halide emulsion grains rich in chlorine exhibit a cubic morphology having a (100) crystal plane . This provides better development properties than other crystal forms such as octahedral, rhombohedral or tabular silver chloride crystals, which require the use of so-called growth or habit modifiers. . The silver chloride, silver chlorobromide or silver chlorobromoiodide used in the present invention is 0.10 to 0.40.
It preferably has an average particle size of μm.
【００２９】一度粒子がそれらの究極的な大きさ及び形
に達したなら、乳剤は、粒子形成及び粒子生長の副生成
物を除去するため一般に洗浄する。過剰の可溶性塩を除
去するため、洗浄は、洗浄中変化できるが、ポリスチレ
ンスルホン酸の如き凝集剤の使用をする３．７〜３．０
の間にあるｐＨ値で適用する。乳剤はいわゆる限外濾過
とも称される半透膜によるダイア濾過によって洗浄でき
る。従って被覆工程前、中又は後での被覆組成物の安定
性を損うことのある重合体凝集剤の使用は必要ない。か
かる方法は例えば Research Disclosure Vol. １０２
（１９７２年１０月）、Item １０２０８、 Research
Disclosure Vol. １３１（３月）、Item １３１２
２、及びＵＳ−Ｐ４３３４０１２に記載されている。好
ましくは限外濾過の開始時に、何ら調整段階なしで、先
行する沈澱の終了時と同じレベルでｐＨ及びｐＡｇが保
たれるので、ｐＨ及びｐＡｇ調整はない。Once the grains have reached their ultimate size and shape, the emulsions are generally washed to remove grain formation and grain growth by-products. Washing can be varied during the wash to remove excess soluble salts, but the use of a flocculant such as polystyrene sulfonic acid 3.7-3.0.
Apply at a pH value between The emulsion can be washed by diafiltration through a semipermeable membrane, also called ultrafiltration . Thus, it is not necessary to use a polymeric flocculant which may impair the stability of the coating composition before, during or after the coating step. Such a method is described, for example, in Research Disclosure Vol.
(October 1972), Item 10208, Research
Disclosure Vol. 131 (March), Item 1312
2, and U.S. Pat. No. 4,334,012. There is no pH and pAg adjustment, preferably at the beginning of the ultrafiltration, without any adjustment steps, as the pH and pAg are maintained at the same levels as at the end of the preceding precipitation.
【００３０】本発明によれば、乳剤は酸凝固性ゼラチン
誘導体又はアニオン重合体化合物を用いる酸凝固法によ
り、又はシリカ媒体中で沈澱が生じたときにはシリカと
水素架橋を形成しうる一定の重合体（ヨーロッパ特許出
願公開ＥＰ−Ａ ０５１７９６１に記載されている如く
シリカ粒子と凝固しうる凝集体を形成しうるに充分な量
で）により洗浄するのが好ましい。According to the present invention, the emulsion is prepared by acid coagulation using an acid-coagulable gelatin derivative or an anionic polymer compound, or a polymer capable of forming hydrogen bridges with silica when precipitation occurs in a silica medium. Preferably , it is washed with silica particles (in an amount sufficient to form coagulateable aggregates with the silica particles, as described in EP-A 0 517 961 ).
【００３１】酸凝固性ゼラチン誘導体を用いる凝固法は
例えばＵＳ−Ｐ２６１４９２８、ＵＳ−Ｐ２６１４９２
９及びＵＳ−Ｐ２７２８６６２に記載されている。酸凝
固性ゼラチン誘導体はゼラチンと、有機カルボン酸もし
くはスルホン酸クロライド、カルボン酸無水物、芳香族
イソシアネート又は１，４−ジケトンとの反応生成物で
ある。これらの酸凝固性ゼラチン誘導体の使用は、一般
に全体に酸凝固しうる性質を与えるに充分な割合で酸凝
固性ゼラチン誘導体を加えたゼラチンの水性溶液中で又
は酸凝固性ゼラチン誘導体の水性溶液中でハロゲン化銀
粒子を沈澱させることを含む。或いはゼラチン誘導体は
通常のゼラチン中での乳化段階後に、及び酸性条件下凝
固性を与えるに充分な量で加えられるならば物理熟成段
階後でさえも加えることができる。本発明により使用す
るのに好適な酸凝固性ゼラチン誘導体の例は例えば前述
した米国特許中に見出すことができる。特に好適なのは
フタロイルゼラチン及びＮ−フェニルカルバモイルゼラ
チンである。Coagulation methods using acid-coagulable gelatin derivatives are described, for example, in US Pat. No. 2,614,928, US Pat.
9 and U.S. Pat. No. 2,728,662. Acid-coagulable gelatin derivatives are reaction products of gelatin with organic carboxylic acids or sulfonic acid chlorides, carboxylic anhydrides, aromatic isocyanates or 1,4-diketones. The use of these acid-coagulable gelatin derivatives is generally carried out in an aqueous solution of gelatin to which the acid-coagulable gelatin derivative is added in a ratio sufficient to give the whole acid-coagulable properties or in an aqueous solution of the acid-coagulable gelatin derivative. Precipitation of the silver halide grains. Alternatively, the gelatin derivative can be added after the emulsification step in conventional gelatin, and even after the physical ripening step if added in an amount sufficient to provide coagulation under acidic conditions. Examples of acid-coagulable gelatin derivatives suitable for use according to the invention can be found, for example, in the aforementioned US patents. Particularly preferred are phthaloyl gelatin and N-phenylcarbamoyl gelatin.
【００３２】形成された凝集塊は、好適な手段で液体か
ら除去できる。例えば上澄液を傾瀉するか又はサイホン
で除去する。そして凝集塊を一回又は数回洗う。The agglomerates formed can be removed from the liquid by any suitable means . For example, the supernatant is decanted or siphoned off . The agglomerates are then washed once or several times.
【００３３】凝集塊の洗浄は単なる冷水で洗浄すること
によって行いうる。しかしながら、第一回の洗浄水は、
凝結点のｐＨまで水のｐＨを下げるため酸性にするのが
好ましい。例えば前述したドイツ特許公開（ＤＯＳ）Ｎ
ｏ．２３３７１７２に記載されている如く酸凝固性ゼラ
チン誘導体を使用したときでさえも洗浄水にアニオン重
合体例えばポリスチレンスルホン酸を加えることができ
る。或いは洗浄は、凝集塊を少量のアルカリ例えば水酸
化ナトリウムもしくはアンモニウムを用い高温で水中で
再分散し、凝結点までｐＨを低下させるため酸を加えて
再凝固し、続いて上澄液を除去して行うことができる。
この再分散及び再凝固法は必要に応じて何回も繰返すこ
とができる。The washing of the agglomerates can be carried out simply by washing with cold water. However, the first wash water is
It is preferred to make the water acidic to lower the pH of the water to the freezing point pH. For example, the aforementioned German Patent Publication (DOS) N
o. Even when using acid-coagulable gelatin derivatives as described in 2337172, anionic polymers such as polystyrene sulfonic acid can be added to the wash water. Alternatively, washing may be performed by redispersing the agglomerate in water using a small amount of alkali such as sodium or ammonium hydroxide at an elevated temperature, adding an acid to lower the pH to the freezing point, and resolidifying, followed by removing the supernatant. Can be done.
This redispersion and resolidification process can be repeated as many times as necessary.
【００３４】洗浄操作後、凝集塊は、必要量の水、ゼラ
チン及び必要ならばアルカリを用い、凝集塊の完全再分
散を行うために必要な時間、好ましくは３５〜７０℃の
範囲の温度で処理して、続いて完成及び被覆操作に好適
な写真乳剤を形成するために再分散させる。After the washing operation, the agglomerates are removed using the required amount of water, gelatin and, if necessary, alkali, for the time necessary for complete redispersion of the agglomerates, preferably at a temperature in the range from 35 to 70 ° C. Processing and subsequent redispersion to form a photographic emulsion suitable for completion and coating operations.
【００３５】使用するのが好ましい通常のゼラチンに代
えて又はそれに加えて、再分散のため他の既知の写真親
水性コロイド、例えば前述した如きゼラチン誘導体、ア
ルブミン、寒天、アルギン酸ナトリウム、加水分解した
セルロースエステル、ポリビニルアルコール、親水性ポ
リビニル共重合体、コロイドシリカ等も使用できる。Instead of, or in addition to, normal gelatin, which is preferably used, other known photographic hydrophilic colloids for redispersion, such as gelatin derivatives as described above, albumin, agar, sodium alginate, hydrolyzed cellulose Esters, polyvinyl alcohol, hydrophilic polyvinyl copolymers, colloidal silica and the like can also be used.
【００３６】感光性臭沃化銀及び塩化銀含有乳剤は、硫
黄及び金増感剤で別々に化学的に増感する。これは、例
えば P. Glafkides の Chimie et Physique Photogr
aphique 、G. F. Duffin の Photographic Emulsion
Chemistry、V. L. Zelikman等の Making and Coatin
g Photographic Emulsion 、及び Akademische Verl
agsgesellschaft １９６８年発行、H. Frieser 編、Di
e Grundlagen derPhotographischen Prozesse mit
Silberhalogeniden に記載されている。前記文献に記載
されている如く、硫黄増感は、少量の硫黄を含有する化
合物例えばチオサルフェート、チオシアネート、チオ尿
素、亜硫酸塩、メルカプト化合物、及びローダミンの存
在下に熟成を行うことによって行うことができる。金増
感は金化合物によって生ずる。更に少量のＩｒ，Ｒｈ，
Ｒｕ，Ｐｂ，Ｃｄ，Ｈｇ，Ｔｌ，Ｐｄ又はＰｔの化合物
を使用できる。乳剤は更に還元剤例えばＧＢ−Ａ７８９
８２３に記載されている如き錫化合物、アミン、ヒドラ
ジン誘導体、ホルムアミジン−スルフィン酸及びシラン
化合物によって増感できる。The photosensitive silver bromoiodide and silver chloride containing emulsions are separately chemically sensitized with sulfur and gold sensitizers. This is for example the Chimie et Physique Photogr of P. Glafkides.
aphique, GF Duffin's Photographic Emulsion
Making and Coatin by Chemistry, VL Zelikman, etc.
g Photographic Emulsion and Akademische Verl
agsgesellschaft 1968, H. Frieser, Di
e Grundlagen derPhotographischen Prozesse mit
It is described in Silberhalogeniden. As described in the literature, sulfur sensitization can be performed by ripening in the presence of a compound containing a small amount of sulfur such as thiosulfate, thiocyanate, thiourea, sulfite, mercapto compound, and rhodamine. it can. Gold sensitization is caused by gold compounds. A small amount of Ir, Rh,
Compounds of Ru, Pb, Cd, Hg, Tl, Pd or Pt can be used. The emulsion may further comprise a reducing agent such as GB-A789
No. 823, sensitized by a tin compound, an amine, a hydrazine derivative, formamidine-sulfinic acid and a silane compound.
【００３７】化学熟成後、臭沃化銀結晶及び塩化銀含有
乳剤は、７０／３０〜９８／２で変化する重量比量で被
覆溶液を含有する容器に別々に加えることができる。After chemical ripening, the silver bromoiodide crystals and the silver chloride-containing emulsion can be added separately to the container containing the coating solution in a weight ratio varying from 70/30 to 98/2.
【００３８】本発明によれば、写真材料の製造中もしく
は貯蔵中又はその写真処理中に写真特性を安定化するた
め又はかぶりの形成を防止するための化合物を補助的に
加えることができる。かかる安定剤の例には、複素環式
窒素含有安定化化合物例えばベンゾチアゾリウム塩、ニ
トロイミダゾール、ニトロベンズイミダゾール、クロロ
ベンズイミダゾール、ブロモベンズイミダゾール、メル
カプトチアゾール、メルカプトベンゾチアゾール、メル
カプトベンズイミダゾール、メルカプトチアジアゾー
ル、アミノトリアゾール、ベンゾトリアゾール（好まし
くは５−メチルベンゾトリアゾール）、ニトロベンゾト
リアゾール、メルカプトテトラゾール、特に１−フェニ
ル−５−メルカプトテトラゾール、メルカプトピリミジ
ン、メルカプトトリアジン、ベンゾチアゾリン−２−チ
オン、オキサゾリン−チオン、トリアザインデン、テト
ラザインデン、及びペンタザインデン、特に Z. Wiss.
Phot. ４７巻（１９５２年）、２〜５８頁に記載された
もの、トリアゾロピリミジン例えばＧＢ−Ａ１２０３７
５７、ＧＢ−Ａ１２０９１４６、特願昭５０−３９５３
７、及びＧＢ−Ａ１５００２７８に記載されたもの、及
び他の化合物例えばベンゼンチオスルホン酸、ベンゼン
チオスルフィン酸、ベンゼンチオスルホン酸アミド、及
び他の二硫化誘導体があり、これらは唯一の安定剤とし
て加えたときには不満足な結果を与える。従って前述し
た安定剤の群に属する他の安定剤と組合せる。他方水銀
塩及びかぶり防止化合物として使用できる他の金属塩例
えば Research Disclosure Ｎｏ．１７６４３（１９７
８年）、VI章に記載されたカドミウム塩及び関連化合物
は、環境汚染の理由から避けるべきである。According to the present invention, compounds can be added to stabilize photographic properties or prevent fogging during the manufacture or storage of the photographic material or during its photographic processing. Examples of such stabilizers include heterocyclic nitrogen-containing stabilizing compounds such as benzothiazolium salts, nitroimidazole, nitrobenzimidazole, chlorobenzimidazole, bromobenzimidazole, mercaptothiazole, mercaptobenzothiazole, mercaptobenzimidazole, mercapto Thiadiazole, aminotriazole, benzotriazole (preferably 5-methylbenzotriazole), nitrobenzotriazole, mercaptotetrazole, especially 1-phenyl-5-mercaptotetrazole, mercaptopyrimidine, mercaptotriazine, benzothiazoline-2-thione, oxazoline-thione , Triazaindene, tetrazaindene, and pentazaindene, especially Z. Wiss.
Phot. 47 (1952), pp. 2-58, triazolopyrimidines such as GB-A12037.
57, GB-A1209146, Japanese Patent Application No. 50-3953
And other compounds such as benzenethiosulfonic acid, benzenethiosulfinic acid, benzenethiosulfonic acid amide, and other disulfide derivatives, which are added as sole stabilizers. Gives unsatisfactory results . Thus, they are combined with other stabilizers belonging to the group of stabilizers mentioned above. On the other hand, mercury salts and other metal salts which can be used as antifogging compounds, for example Research Disclosure No. 17643 (197
8 years), cadmium salts and related compounds described in Chapter VI should be avoided for reasons of environmental pollution.
【００３９】本発明による写真材料のハロゲン化銀乳剤
層中でのゼラチン対ハロゲン化銀（硝酸銀として表示す
る）の比は０．３〜１．２、好ましくは０．６〜１．１
の間に含まれる。The ratio of gelatin to silver halide (expressed as silver nitrate) in the silver halide emulsion layer of the photographic material according to the present invention is from 0.3 to 1.2, preferably from 0.6 to 1.1.
Included between.
【００４０】本発明による写真材料のゼラチン結合剤
は、適切な硬化剤例えばエポキシド系のもの、エチレン
イミン系のもの、ビニルスルホン系のもの例えば１，３
−ビニルスルホニル−２−プロパノールもしくはジ−
（ビニルスルホニル）−メタン、アルデヒド例えばホル
ムアルデヒド、グリオキサール、及びグルタルアルデヒ
ド、Ｎ−メチロール化合物例えばジメチロール尿素及び
メチロールジメチルヒダントイン、ジオキサン誘導体例
えば２，３−ジヒドロキシ−ジオキサン、活性ビニル化
合物例えば１，３，５−トリアクリロイル−ヘキサヒド
ロ−ｓ−トリアジン、活性ハロゲン化合物例えば２，４
−ジクロロ−６−ヒドロキシ−ｓ−トリアジン、及びム
コハロゲン酸例えばムコクロル酸及びムコフエノキシク
ロル酸で硬化できる。これらの硬化剤は単独で又は組合
せて使用できる。結合剤は又ＵＳ−Ｐ４０６３９５２に
記載されている如き急速硬化剤例えばカルバモイルピリ
ジニウム塩、及びヨーロッパ特許出願公開ＥＰ−Ａ ０
４０８１４３に記載されている如きオニウム化合物で硬
化することができる。The gelatin binder of the photographic material according to the present invention may be a suitable hardener such as an epoxide type, an ethyleneimine type or a vinyl sulfone type such as 1,3.
-Vinylsulfonyl-2-propanol or di-
(Vinylsulfonyl) -methane, aldehydes such as formaldehyde, glyoxal and glutaraldehyde, N-methylol compounds such as dimethylolurea and methyloldimethylhydantoin, dioxane derivatives such as 2,3-dihydroxy-dioxane, active vinyl compounds such as 1,3,5- Triacryloyl-hexahydro-s-triazine, an active halogen compound such as 2,4
-Dichloro-6-hydroxy-s-triazine, and can be cured with mucohalic acids such as mucochloric acid and mucophenoxycyclolic acid. These curing agents can be used alone or in combination. Binders are also fast-curing agents such as carbamoylpyridinium salts as described in US Pat. No. 4,063,952, and EP-A 0 0
It can be cured with an onium compound as described in US Pat .
【００４１】硬化は、写真材料が処理サイクルの終り
で、乾燥直前に洗浄されるとき、ゼラチン１ｇについて
多くても２．５ｇの水が吸収される程にする。これは後
述する実施例から明らかになるであろう。Curing is such that at the end of the processing cycle, at most 2.5 g of water per gram of gelatin is absorbed when the photographic material is washed immediately before drying . This will become clear from the embodiments described below.
【００４２】考慮に入れる写真材料は更に写真乳剤層及
び／又は少なくとも一つの他の親水性コロイド層層中に
種々の界面活性剤を含有できる。好ましい界面活性剤は
過弗素化アルキル基を含有する化合物である。The photographic materials to be considered can further contain various surfactants in the photographic emulsion layer and / or at least one other hydrophilic colloid layer. Preferred surfactants are compounds containing a perfluorinated alkyl group.
【００４３】写真材料は更に各種の他の添加剤例えば写
真材料の寸法安定性を改良する化合物、紫外線吸収剤、
間隔剤及び可塑剤を含有できる。The photographic material may further comprise various other additives, such as compounds which improve the dimensional stability of the photographic material, UV absorbers,
Spacing agents and plasticizers can be included.
【００４４】本発明の写真材料は更に各種の界面活性剤
を写真乳剤層又は少なくとも一つの他の親水性コロイド
層中に含有できる。好適な界面活性剤には、サポニン、
アルキレンオキサイド例えばポリエチレングリコール、
ポリエチレングリコール／ポリプロピレングリコール縮
合生成物、ポリエチレングリコールアルキルエーテル又
はポリエチレングリコールアルキルアリールエーテル、
ポリエチレングリコールエステル、ポリエチレングリコ
ールソルビタンエステル、ポリアルキレングリコールア
ルキルアミン又はアルキルアミド、シリコーン−ポリエ
チレンオキサイド付加物、グリシドール誘導体、多価ア
ルコールの脂肪酸エステル及びサッカライドのアルキル
エステルの如き非イオン界面活性剤；カルボキシ、スル
ホ、ホスホ、硫酸もしくはリン酸エステル基の如き酸基
を含有するアニオン界面活性剤；アミノ酸、アミノアル
キルスルホン酸、アミルアルキルサルフェート又はホス
フェート、アルキルベタイン及びアミン−Ｎ−オキサイ
ドの如き両性界面活性剤；及びアルキルアミン塩、脂肪
族、芳香族もしくは複素環式族四級アンモニウム塩、脂
肪族もしくは複素環式環含有ホスホニウムもしくはスル
ホニウム塩の如きカチオン界面活性剤を含む。かかる界
面活性剤は種々の目的のため、例えば被覆助剤として、
帯電防止化合物として、滑性を改良する化合物として、
分散乳化を容易にする化合物として、接着を防止又は低
下する化合物として、及び写真特性例えば高コントラス
ト、増感及び現像促進を改良する化合物として使用でき
る。The photographic material of the present invention can further contain various surfactants in the photographic emulsion layer or at least one other hydrophilic colloid layer. Suitable surfactants include saponins,
Alkylene oxides such as polyethylene glycol,
Polyethylene glycol / polypropylene glycol condensation products, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers,
Nonionic surfactants such as polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkylamines or alkylamides, silicone-polyethylene oxide adducts, glycidol derivatives, fatty acid esters of polyhydric alcohols and alkyl esters of saccharides; carboxy, sulfo Anionic surfactants containing an acid group such as a phospho, sulfate or phosphate group; amphoteric surfactants such as amino acids, aminoalkyl sulfonic acids, amylalkyl sulfates or phosphates, alkyl betaines and amine-N-oxides; Alkylamine salts, aliphatic, aromatic or heterocyclic quaternary ammonium salts, such as aliphatic or heterocyclic ring-containing phosphonium or sulfonium salts Including thione surfactant. Such surfactants can be used for various purposes, for example, as coating aids.
As an antistatic compound, as a compound that improves lubrication,
They can be used as compounds that facilitate dispersion emulsification, as compounds that prevent or reduce adhesion, and as compounds that improve photographic properties such as high contrast, sensitization and development acceleration.
【００４５】現像促進は種々の化合物、好ましくは例え
ばＵＳ−Ｐ３０３８８０５、ＵＳ−Ｐ４０３８０７５、
ＵＳ−Ｐ４２９２４００に記載されているものの如く、
少なくとも４００の分子量を有するポリアルキレン誘導
体により達成できる。The development is accelerated by various compounds, preferably, for example, US Pat. No. 3,038,805, US Pat.
As described in US-P 4,292,400,
This can be achieved with a polyalkylene derivative having a molecular weight of at least 400.
【００４６】本発明の写真材料は更に他の添加剤例えば
写真材料の寸法安定性を改良する化合物、紫外線吸収
剤、間隔剤、硬化剤、可塑剤、帯電防止剤等を含有でき
る。The photographic material of the present invention may further contain other additives such as a compound for improving the dimensional stability of the photographic material, an ultraviolet absorber, a spacing agent, a curing agent, a plasticizer, an antistatic agent and the like.
【００４７】写真の寸法安定性を改良するのに好適な添
加剤には、例えば水溶性又は殆ど可溶性でない合成重合
体例えばアルキル（メタ）アクリレート、アルコキシ
（メタ）アクリレート、グリシジル（メタ）アクリレー
ト、（メタ）アクリルアミド、ビニルエステル、アクリ
ロニトリル、オレフィン、及びスチレンの重合体、又は
前記のものとアクリル酸、メタクリル酸、α，β−不飽
和ジカルボン酸、ヒドロキシアルキル（メタ）アクリレ
ート、スルホアルキル（メタ）アクリレート及びスチレ
ンスルホン酸との共重合体がある。Additives suitable for improving the dimensional stability of photographs include, for example, water-soluble or poorly soluble synthetic polymers such as alkyl (meth) acrylates, alkoxy (meth) acrylates, glycidyl (meth) acrylates, ( (Meth) acrylamide, vinyl ester, acrylonitrile, olefin, and polymer of styrene or the above and acrylic acid, methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth) acrylate, sulfoalkyl (meth) acrylate And styrene sulfonic acid.
【００４８】好適な紫外線吸収剤には例えばＵＳ−Ｐ３
５３３７９４に記載された如きアリール置換ベンゾトリ
アゾール化合物、ＵＳ−Ｐ３３１４７９４及びＵＳ−Ｐ
３３５２６８１に記載された如き４−チアゾリドン化合
物、ＪＰ−Ａ４６−２７８４に記載された如きベンゾフ
エノン化合物、ＵＳ−Ｐ３７０５８０５及びＵＳ−Ｐ３
７０７３７５に記載された如きシンナム酸エステル、Ｕ
Ｓ−Ｐ４０４５２２９に記載された如きブタジエン化合
物、及びＵＳ−Ｐ３７００４５５に記載された如きベン
ゾキサゾール化合物がある。Suitable UV absorbers include, for example, US-P3
Aryl-substituted benzotriazole compounds as described in US Pat. No. 5,337,794, US Pat.
4-thiazolidone compounds as described in US Pat. No. 3,352,681, benzophenone compounds as described in JP-A46-2784, US Pat. No. 3,705,805 and US-P3
Cinnamates as described in 707375, U
There are butadiene compounds as described in S-P 4045229 and benzoxazole compounds as described in U.S. Pat. No. 3,700,455.
【００４９】一般に間隔剤の平均粒度は０．２〜１０μ
ｍの間に含まれる。間隔剤はアルカリに可溶性又は不溶
性であることができる。アルカリ不溶性間隔剤は通常永
久的に写真材料中に残る。一方アルカリ可溶性間隔剤は
通常アルカリ性処理浴中でそこから除去される。好適な
間隔剤は例えばポリメチルメタクリレート、アクリル酸
とメチルメタクリレートの共重合体、及びヒドロキシプ
ロピルメチルセルロースヘキサヒドロフタレートから作
ることができる。他の好適な間隔剤はＵＳ−Ｐ４６１４
７０８に記載されている。Generally, the average particle size of the spacing agent is 0.2 to 10 μm.
m. Spacing agents can be soluble or insoluble in alkali. The alkali-insoluble spacing agent usually remains permanently in the photographic material . Alkali-soluble spacing agents, on the other hand, are usually removed therefrom in an alkaline treatment bath. Suitable spacing agents can be made, for example, from polymethyl methacrylate, copolymers of acrylic acid and methyl methacrylate, and hydroxypropyl methylcellulose hexahydrophthalate. Another suitable spacing agent is U.S. Pat.
708.
【００５０】写真材料は、例えば材料の被覆、処理及び
他の取扱い中に、静電放電を避けるため帯電防止層を含
有できる。かかる帯電防止層は１種以上の帯電防止剤の
最外被覆もしくは層、又はフィルム支持体もしくは他の
支持体に直接付与し、バリヤーもしくはゼラチン層で上
塗被覆された被覆であることができる。かかる層で使用
するのに好適な帯電防止化合物には例えば五酸化バナジ
ンゾル、酸化錫ゾル又はポリエチレンオキサイド等の如
き導電性重合体がある。Photographic materials can contain an antistatic layer to avoid electrostatic discharge, for example during coating, processing and other handling of the material. Such an antistatic layer can be an outermost coating or layer of one or more antistatic agents, or a coating applied directly to a film or other support and overcoated with a barrier or gelatin layer. Suitable antistatic compounds for use in such a layer include conductive polymers such as, for example, vanadium pentoxide sol, tin oxide sol or polyethylene oxide.
【００５１】本発明による写真材料は、フィルム支持体
の両側に乳剤層を有する二重材料であるのが好ましい。
両乳剤層は応力防止（保護）最上層で上塗被覆する。工
業用放射線写真のため、ハロゲン化銀乳剤層は、一側
で、１ｍ2 について銀５〜１５ｇの間に相当するハロゲ
ン化銀の量を含有するのが好ましい。The photographic material according to the present invention is preferably a dual material having an emulsion layer on both sides of a film support.
Both emulsion layers are overcoated with an antistress (protection) top layer. For industrial radiography, the silver halide emulsion layer preferably contains, on one side, an amount of silver halide corresponding to between 5 and 15 g of silver per m 2 .
【００５２】本発明による写真材料の支持体は透明樹
脂、好ましくは青着色ポリエステル支持体例えばポリエ
チレンテレフタレート支持体であることができる。かか
る有機樹脂フィルムの厚さは約１７５μｍであるのが好
ましい。支持体には、乳剤層と前記支持体の間に良好な
接着性をもたせるため、両側に下塗層を設ける。The support of the photographic material according to the present invention can be a transparent resin, preferably a blue-colored polyester support such as a polyethylene terephthalate support. The thickness of such an organic resin film is preferably about 175 μm. The support is provided with an undercoat layer on both sides to provide good adhesion between the emulsion layer and the support.
【００５３】写真材料はＸ線放射線源により像に従って
露光する。そのエネルギーはｋＶで表わし、特定用途に
よって決る。他の代表的な放射線源には放射性６０Ｃｏ
源がある。散乱する放射線の効果を減ずるため、金属ス
クリーン、通常鉛スクリーンを写真フィルムと組合せて
使用する。その外に二次電子の発生が感度を増強させ
る。The photographic material is image-wise exposed by an X-ray radiation source . The energy is expressed in kV and depends on the specific application. Other representative sources include radioactive 60 Co.
There is a source. Metal screens, usually lead screens, are used in combination with photographic film to reduce the effects of scattered radiation. In addition, the generation of secondary electrons enhances the sensitivity.
【００５４】処理のため、実施例で明らかに示す如く、
処理溶液の自動補給のための装置を設けた自動操作装置
を使用するのが好ましい。For processing, as clearly shown in the examples,
It is preferable to use an automatic operating device provided with a device for automatic replenishment of the processing solution.
【００５５】本発明による現像溶液は、次の処理溶液へ
の交差による液体溶積の減少に対してばかりでなく、現
像剤分子の酸化によるｐＨ変化に対しても補給しなけれ
ばならない。これは規則的な時間間隔基準で、又は処理
したフィルムの量の基準で又は両者の組合せで行うこと
ができる。現像工程に続いて洗浄工程、定着溶液及び他
の洗浄又は安定化工程をすることができる。最後に最後
の洗浄工程後に写真材料を乾燥する。この処理後得られ
る如き材料の吸収スペクトルのそれ以上の微細な同調
は、支持体の両側での下塗層、乳剤層又は最上層に好適
な非移行性染料を添加することによって得ることができ
る。青着色染料が本発明の範囲内で特に推奨される。The developer solution according to the present invention must be replenished not only for the reduction of liquid deposition due to crossover to the next processing solution, but also for pH changes due to oxidation of the developer molecules. This can be done on a regular time interval basis, or on the basis of the amount of film processed, or a combination of both. The development step may be followed by a washing step, a fixing solution and other washing or stabilizing steps. Finally, the photographic material is dried after the last washing step. Further fine tuning of the absorption spectrum of the material as obtained after this treatment can be obtained by adding suitable non-migratory dyes to the subbing layer, emulsion layer or top layer on both sides of the support. . Blue coloring dyes are particularly recommended within the scope of the present invention.
【００５６】下記実施例は更に本発明を完全に示すであ
ろう。The following examples will further illustrate the invention.
【００５７】実施例 １乳剤Ａ 下記の方法で９９モル％の臭化銀及び１モル％の沃化銀
を含有するゼラチン臭沃化銀Ｘ線乳剤を作った。ゼラチ
ンの３重量％水溶液１５５０ｍｌを含有する反応容器に
４５℃でメチオニン１１ｇを含有する水性溶液を加え
た。前記反応容器に、烈しい撹拌条件下に、臭化カリウ
ムの水性１．５モル溶液２０００ｍｌ及び硝酸銀の水性
１．５モル溶液２０００ｍｌを、８６ｍｌ／分の一定速
度で導入した。沈澱中ｐＡｇは、銀／飽和カロメル参照
電極を参照して＋２０ｍＶの E.M.F. に相当する値に調
整しかつ維持した。この方法で０．１９μｍの結晶直径
を有する均質レギュラーハロゲン化銀粒子を得た。Example 1 Emulsion A A gelatin silver bromoiodide X-ray emulsion containing 99 mol% of silver bromide and 1 mol% of silver iodide was prepared by the following method. An aqueous solution containing 11 g of methionine was added at 45 ° C. to a reaction vessel containing 1550 ml of a 3% by weight aqueous solution of gelatin. Under vigorous stirring conditions, 2000 ml of an aqueous 1.5 molar solution of potassium bromide and 2000 ml of an aqueous 1.5 molar solution of silver nitrate were introduced into the reaction vessel at a constant rate of 86 ml / min. During precipitation, the pAg was adjusted and maintained at a value corresponding to an EMF of +20 mV with reference to a silver / saturated calomel reference electrode. In this way, homogeneous regular silver halide grains having a crystal diameter of 0.19 μm were obtained.
【００５８】沈澱工程の終りに、反応容器中の乳剤のｐ
Ｈを硫酸で３．５に調整した後、凝集剤として作用する
ポリスチレンスルホン酸を加えて凝結させた。前記ハロ
ゲン化銀乳剤の急速沈降後、上澄液を傾瀉した。前記凝
集体から水溶性塩を除去するため、制御した撹拌条件下
に１１℃の脱イオン水を加え、続いて更に沈降させ、傾
瀉した。この洗浄法を、乳剤が充分に脱塩されるまで繰
返した。その後凝集塊を、０．４のゼラチン対硝酸銀の
比を得るのに充分な量のゼラチンを加えた後水中に４５
℃で再分散した。銀／飽和カロメル電極を参照してｐＨ
値を６．５に、ｐＡｇ値を＋７０ｍＶの値に調整した。At the end of the precipitation step, the p of the emulsion in the reaction vessel
After H was adjusted to 3.5 with sulfuric acid, polystyrene sulfonic acid acting as a flocculant was added for coagulation. After rapid precipitation of the silver halide emulsion, the supernatant was decanted. To remove water-soluble salts from the aggregates, deionized water at 11 ° C. was added under controlled stirring conditions, followed by further sedimentation and decantation. This washing procedure was repeated until the emulsion was sufficiently desalted. The agglomerates are then added to the water after adding a sufficient amount of gelatin to obtain a gelatin to silver nitrate ratio of 0.4.
Redispersed at ° C. PH with reference to silver / saturated calomel electrode
The value was adjusted to 6.5 and the pAg value was adjusted to +70 mV.
【００５９】前記乳剤の化学増感は、なお受容しうるか
ぶりレベルに対して、最高感度に達する点まで、硫黄及
び金増感剤を加え、５０℃で熟成して行った。Chemical sensitization of the emulsion was carried out by adding sulfur and gold sensitizers and ripening at 50 ° C. to the point where the maximum sensitivity was reached for still acceptable fog levels.
【００６０】乳剤Ｂ 下記の方法で、９０モル％の塩化銀及び１０モル％の臭
化銀を含有するゼラチン塩臭化銀乳剤を作った。ハロゲ
ン化銀は、４０℃でゼラチンの水溶液中で、前述した組
成を得るため、正しい混合物の形での塩化物及び臭化物
塩の水性溶液及び硝酸銀の水性溶液を二重ジェット法を
使用して加えて沈澱させた。ハロゲン化銀結晶は、０．
１６μｍの所望粒度に達するまで通常の方法で物理的に
熟成し、スチレンスルホン酸を加えて前記ハロゲン化銀
乳剤の凝結によって前記物理熟成工程を停止し、乳剤の
ｐＨを３．０まで酸性にした。乳剤Ａに対するのと同様
に続いて洗浄をし、その後ゼラチンを加えて、硝酸銀と
して表示したハロゲン化銀に対するゼラチンの重量比
０．５を得た。乳剤を硫黄及び金増感剤を加えて化学的
に増感し、続いて、感度とかぶりの間に最良の関係が得
られるまで４５℃で熟成した。ハロゲン化銀結晶は０．
１６μｍの平均直径を有していた。 Emulsion B A gelatin silver chlorobromide emulsion containing 90 mol% of silver chloride and 10 mol% of silver bromide was prepared in the following manner. Silver halide is added at 40 ° C. in an aqueous solution of gelatin by using a double jet method with an aqueous solution of chloride and bromide salts and an aqueous solution of silver nitrate in the correct mixture to obtain the composition described above. And precipitated. The silver halide crystal has a content of 0.1 mm.
Physically ripened in the usual manner until the desired grain size of 16 μm was reached, the physical ripening step was stopped by the addition of styrene sulfonic acid and coagulation of the silver halide emulsion, and the pH of the emulsion was acidified to 3.0. . Following washing as for Emulsion A , gelatin was then added to give a weight ratio of gelatin to silver halide expressed as silver nitrate of 0.5. The emulsion was chemically sensitized by the addition of sulfur and gold sensitizers and subsequently ripened at 45 ° C until the best relationship between speed and fog was obtained. Silver halide crystals
It had an average diameter of 16 μm.
【００６１】乳剤Ｃ 乳剤Ｂと同じ方法で、８３．６モル％の塩化銀、１６モ
ル％の臭化銀及び０．４モル％の沃化銀を含有する乳剤
Ｃを作った。前記乳剤のハロゲン化銀結晶は０．３μｍ
の平均直径を有していた。 Emulsion C Emulsion C containing 83.6 mol% silver chloride, 16 mol% silver bromide and 0.4 mol% silver iodide was prepared in the same manner as Emulsion B. The silver halide crystal of the emulsion is 0.3 μm
Average diameter.
【００６２】フィルム１１（比較例） 比較例として、このフィルムは、厚さ１７５μｍを有す
る青色ポリエチレンテレフタレート支持体の両側を乳剤
Ａで被覆した。両側でハロゲン化銀乳剤結晶及びゼラチ
ンは、１ｍ2 について硝酸銀として表示した１０．５ｇ
の量及び８．９ｇの量でそれぞれ支持体上に被覆した。
被覆前に安定剤５−メチル−７−ヒドロキシ−５−トリ
アゾロ−〔１．５−ａ〕−ピリミジン及び１−フェニル
−５−メルカプトテトラゾールを乳剤に加えた。両乳剤
層は１ｍ2 についてゼラチン１．４ｇの保護層で被覆
し、ジ−（ビニル−スルホニル）−メタンで硬化した。 Film 11 (Comparative Example) As a comparative example, this film was coated on both sides of a blue polyethylene terephthalate support having a thickness of 175 μm with emulsion A. 10.5 g of silver halide emulsion crystals and gelatin on both sides, expressed as silver nitrate per m 2
And 8.9 g, respectively, on the support.
Prior to coating the stabilizers 5-methyl-7-hydroxy-5-triazolo- [1.5-a] -pyrimidine and 1-phenyl-5-mercaptotetrazole were added to the emulsion. Both emulsion layers were covered with a protective layer of gelatin 1.4g for 1 m 2, di - (vinyl - sulphonyl) - hardened methane.
【００６３】前記被覆し、乾燥したフィルムを、厚さ８
ｍｍの銀フィルターを用い、２３５ｋＶ放射線源を有す
るＩＳＯ ７００４により露光した。The coated and dried film was applied to a thickness of 8
Exposure was with a 700 mm silver filter using ISO 7004 with a 235 kV radiation source.
【００６４】露光した放射線写真フィルムを、８分間の
自動機械処理サイクルで現像し、定着し、洗浄し、乾燥
した。フィルムはアグファ・ゲヴエルトによって市販さ
れている Structurix ＮＤＴ−１機中を送行させ、市
場で入手しうるアグファ・ゲヴエルトＮＤＴ現像液Ｇ１
３５で２８℃で現像し、続いて市場で入手しうるアグフ
ァ・ゲヴエルトＧ３３５定着液を用いて定着した。The exposed radiographic film was developed, fixed, washed and dried in an automatic machine processing cycle of 8 minutes. The film was transported in a Structurix NDT-1 machine marketed by Agfa Gevaert, and a commercially available Agfa Gevaert NDT developer G1
Developed at 28.degree. C. at 35 and subsequently fixed using the commercially available Agfa-Gevaert G335 fixer.
【００６５】フィルム１２ フィルム１２は、乳剤Ａに対して硝酸銀として表示した
ハロゲン化銀の合計量９５重量％及び乳剤Ｂに対して５
重量％に相当する量で、乳剤Ａ及び乳剤Ｂの混合物で作
ったことが前記フィルム１１と異なるが、フィルム１１
と同じ方法で作った。硝酸銀、ゼラチン及び硬度の量は
フィルム１２及びフィルム１１に対して同じであった。 Film 12 Film 12 contained 95% by weight of total silver halide expressed as silver nitrate for Emulsion A and 5% for Emulsion B.
%, Except that it was made from a mixture of Emulsion A and Emulsion B in an amount corresponding to
Made in the same way as The amounts of silver nitrate, gelatin and hardness were the same for Film 12 and Film 11.
【００６６】フィルム１３ フィルム１３は、乳剤Ｂを乳剤Ｃで置換したことのみを
変えて、フィルム１２と同じ方法で被覆した。 Film 13 Film 13 was coated in the same manner as film 12, except that emulsion B was replaced by emulsion C.
【００６７】フィルム１１に対して記載した方法により
露光し、処理した後の感度測定結果を表Ｉに示す。表Ｉ
における感度Ｓについて示した値は、参照フィルム１１
に対する相当速度値であり、フィルム１１の速度に１０
０の値を与えた。かぶりＦは、青色支持体の濃度を含
む。コントラストＣは濃度１．５及び３．５の間の二点
を結ぶ曲線のセグメントの平均階調度である。像色調は
温黒又は褐黒から青黒まで変化しうる。非破壊試験のた
めには、青黒像色調が好ましい。フィルム試料における
像色調Ｉ．Ｔ．の視感比較を表Ｉに示す。良い像色調を
有する試料に対して最低の数を与える。Table 1 shows the results of the sensitivity measurement after the film 11 was exposed and processed according to the method described above. Table I
The values shown for the sensitivity S in the reference film 11
And the speed of the film 11 is 10
A value of 0 was given. Fog F contains the density of the blue support. Contrast C is the average gradient of a segment of a curve connecting two points between densities 1.5 and 3.5. The image tone can vary from warm black or brown black to blue black. For non-destructive testing, a blue-black image tone is preferred. I. Image tones in film samples T. Table I shows a comparison of the visual sensations. Give the lowest number for samples with good image tone.
【００６８】 表 Ｉ ───────────────────────────────── フィルム 乳 剤 Ｆ Ｓ Ｃ Ｉ．Ｔ． ───────────────────────────────── １１ Ａ ０．１３４ １００ ６．３４ ３ １２ Ａ＋Ｂ ０．１３９ １１２ ６．１３ １ １３ Ａ＋Ｃ ０．１４０ １１０ ６．２１ ２ ─────────────────────────────────Table I—Film emulsion FSC I. T. ───────────────────────────────── 11 A 0.134 100 6.34 3 12 A + B 0.139 112 6 .13 1 13 A + C 0.140 110 6.22 2}
【００６９】表Ｉに示した結果は、像色調を改良するた
めに、塩化銀又は塩臭化銀乳剤結晶の存在の重要性を示
している。The results, shown in Table I, demonstrate the importance of the presence of silver chloride or silver chlorobromide emulsion crystals to improve image tone.
【００７０】実施例 ２Embodiment 2
【００７１】フィルム２１ 乳剤Ａ及びＢの混合物を作り、実施例１のフィルム１２
に対するのと同じ方法で被覆した。硬化剤としてジ−
（ビニル−スルホニル）−メタンを使用した。 Film 21 A mixture of emulsions A and B was prepared and
Coated in the same way as for Di- as a curing agent
(Vinyl-sulfonyl) -methane was used.
【００７２】フィルム２２ フィルム２１に対するのと同じであった。但し、ジ−
（ビニル−スルホニル）−メタンの量の７５％のみを用
いた。 Film 22 was the same as for Film 21 . However,
Only 75% of the amount of (vinyl-sulfonyl) -methane was used.
【００７３】フィルム２３ フィルム２１に対するのと同じにした。但し、ジ−（ビ
ニル−スルホニル）−メタンの量の５０％のみを用い
た。 Film 23 The same as for Film 21 . However, only 50% of the amount of di- (vinyl-sulfonyl) -methane was used.
【００７４】フィルム２４ フィルム２１と同じフィルムであるが、乳剤をホルムア
ルデヒドで硬化した。 Film 24 This is the same film as Film 21, but the emulsion was cured with formaldehyde.
【００７５】フィルム２５ フィルム２４と同じフィルムであるが、ホルムアルデヒ
ドの量の６６％のみを使用した。 Film 25 The same film as film 24, but using only 66% of the amount of formaldehyde.
【００７６】硬化度は、処理の終りでの洗浄後で乾燥直
前のフィルムによって吸収された水の量（ｇ／ｍ2 ）で
表示する。表IIに示したデータは、表IIに追加して示し
た前記硬化度以外は、表Ｉで示したものに対応する。The degree of cure is expressed as the amount of water (g / m 2 ) absorbed by the film immediately after drying after washing at the end of the treatment. The data shown in Table II correspond to those shown in Table I, except for the degree of cure shown in Table II.
【００７７】 表 II ──────────────────────────────── フィルム 乳 剤 F S C I.T. H2O g/m2 ──────────────────────────────── 21 Ａ＋Ｂ 0.141 100 6.41 1 37.29 22 Ａ＋Ｂ 0.141 102 6.62 3 41.84 23 Ａ＋Ｂ 0.143 107 6.74 5 43.60 24 Ａ＋Ｂ 0.141 102 6.34 2 40.06 25 Ａ＋Ｂ 0.142 105 6.62 4 43.44 ────────────────────────────────Table II フ ィ ル ム Film emulsion FSC IT H 2 O g / m 2 ─ ─────────────────────────────── 21 A + B 0.141 100 6.41 1 37.29 22 A + B 0.141 102 6.62 3 41.84 23 A + B 0.143 107 6.74 5 43.60 24 A + B 0.141 102 6.34 2 40.06 25 A + B 0.142 105 6.62 4 43.44 ────────────────────────────────
【００７８】表IIに示した結果は、硬化度が像色調に重
要な効果を有することを示している：硬化度が大であれ
ばある程像色調は良好である。The results, shown in Table II, show that the degree of cure has a significant effect on image tone: the higher the degree of cure, the better the image tone.
【００７９】実施例 ３Embodiment 3
【００８０】フィルム３１ 乳剤Ａ及びＢの混合物を作り、実施例１のフィルム１２
と同じ方法で被覆した。硝酸銀として表示したハロゲン
化銀に対するゼラチンの重量比は０．８５であった。こ
の重量比以後「ＧＥＳＩ」と称する。 Film 31 A mixture of emulsions A and B was made and
Coated in the same manner. The weight ratio of gelatin to silver halide, expressed as silver nitrate, was 0.85. This weight ratio will be referred to as "GESI" hereinafter.
【００８１】フィルム３２ フィルム３１と同じであるが、硝酸銀として表示したハ
ロゲン化銀に対するゼラチンの重量比は０．９８であっ
た。 Film 32 Same as film 31, but the weight ratio of gelatin to silver halide expressed as silver nitrate was 0.98.
【００８２】フィルム３３ フィルム３１と同じであるが、硝酸銀として表示したハ
ロゲン化銀に対するゼラチンの重量比は１．１０であっ
た。 Film 33 Same as Film 31, but the weight ratio of gelatin to silver halide expressed as silver nitrate was 1.10.
【００８３】表III に、ＧＥＳＩと称するハロゲン化銀
に対するゼラチンの重量比のデータを加えて、表IIに示
したのと同じデータを集計した。ハロゲン化銀の量は、
硝酸銀の当量として表示する。The same data as shown in Table II was tabulated by adding to Table III data on the weight ratio of gelatin to silver halide, referred to as GESI. The amount of silver halide is
Expressed as the equivalent of silver nitrate.
【００８４】[0084]
【表１】 [Table 1]
【００８５】表III に示した結果は、硝酸銀として表示
したハロゲン化銀に対するゼラチンの比が像色調に著し
い効果を有することを示している。実施例３における場
合と同様に、ゼラチン１ｇについてそして１ｍ2 につい
ての水吸収の同じ量に対して、その比が小さくなればな
る程、良好な色調である。The results, shown in Table III, show that the ratio of gelatin to silver halide, expressed as silver nitrate, has a significant effect on image tone. As in Example 3, the lower the ratio for the same amount of water absorption for 1 g of gelatin and 1 m 2 , the better the shade.
【００８６】実施例 ４Embodiment 4
【００８７】フィルム４１ 乳剤Ａを作り、実施例１のフィルム１１に対するのと同
じ方法で被覆した。硬化剤としてジ−（ビニル−スルホ
ニル）−メタンを使用した。 Film 41 Emulsion A was made and coated in the same manner as for Film 11 of Example 1. Di- (vinyl-sulfonyl) -methane was used as a curing agent.
【００８８】フィルム４２ フィルム４２はフィルム４１に対するのと同じ方法で被
覆した。但し乳剤Ａ及び乳剤Ｂの混合物を、硝酸銀とし
て表示したハロゲン化銀の全量のそれぞれ９５重量％及
び５重量％の量で使用した。 Film 42 Film 42 was coated in the same manner as for Film 41 . However, the mixture of Emulsion A and Emulsion B was used in amounts of 95% and 5% by weight respectively of the total amount of silver halide expressed as silver nitrate.
【００８９】フィルム４３ フィルム４２と同じにしたが、乳剤Ａ及び乳剤Ｂは、硝
酸銀として表示したハロゲン化銀の全量のそれぞれ９０
重量％及び１０重量％の量で使用した。 Film 43 Same as Film 42 except that Emulsion A and Emulsion B contained 90% each of the total amount of silver halide expressed as silver nitrate.
% And 10% by weight.
【００９０】フィルム４４ フィルム４２と同じにしたが、乳剤Ａ及び乳剤Ｂは、そ
れぞれ８０重量％及び２０重量％の量で使用した。 Film 44 Same as Film 42, but Emulsion A and Emulsion B were used in amounts of 80% and 20% by weight, respectively.
【００９１】フィルム４５ フィルム４１と同じ被覆にしたが、BAYER AG の商標
名、CERESBLAU RR 、即ちソルベントブルー９７として
知られている青色染料（１，４−ビス−（２′，６′−
ジエチル−４′−メチル）−フェニルアミノ−アントラ
キノン）のゼラチン分散液を加えることが異なる。前記
青色染料は５６０ｍｇ／ｍ２ の合計量で被覆し、かつ
被覆直前に乳剤に加えた。 Film 45 had the same coating as film 41 but had a blue dye known as CERESBLAU RR, trade name of BAYER AG, ie Solvent Blue 97 (1,4-bis- (2 ', 6'-).
Diethyl-4'-methyl) -phenylamino-anthra
The difference is the addition of a gelatin dispersion of ( quinone) . The blue dye was coated in a total amount of 560 mg / m 2 and added to the emulsion just before coating.
【００９２】フィルム４６ フィルム４５と同じであるが、両側被覆し、１１２０ｍ
ｇ／ｍ2 の青色染料の被覆量とした。 Film 46 Same as film 45 but coated on both sides, 1120 m
g / m 2 of blue dye coverage.
【００９３】フィルム４７ フィルム４７はフィルム４２と同じ方法で作りかつ被覆
した。但し被覆直前に乳剤に１１２０ｍｇ／ｍ２ の量
でフィルム４５の青色染料の添加をしたことが異なる。 Film 47 Film 47 was made and coated in the same manner as Film 42 . The difference is that the blue dye of the film 45 was added in an amount of 1120 mg / m 2 to the emulsion immediately before coating.
【００９４】フィルム４８ フィルム４８はフィルム４３と同じ方法で作り、被覆し
た。但し、被覆直前に乳剤に１１２０ｍｇ／ｍ２ の量
でフィルム４５の青色染料の添加をしたことが異なる。 Film 48 Film 48 was made and coated in the same manner as film 43 . However, the difference is that the blue dye of the film 45 was added in an amount of 1120 mg / m 2 to the emulsion immediately before coating.
【００９５】フィルム４９ フィルム４９はフィルム４８と同じ方法で作り、被覆し
た。但し、フィルム４８について使用したジ−（ビニル
−スルホニル）−メタンの量の７５％のみの量を用いた
ことが異なる。 Film 49 Film 49 was made and coated in the same manner as film 48 . The difference is that only 75% of the amount of di- (vinyl-sulfonyl) -methane used for film 48 was used.
【００９６】フィルム５０ フィルム５０はフィルム４８と同じ方法で作り、被覆し
た。但し、硝酸銀として表示したハロゲン化銀に対する
ゼラチンの比を０．８５の代わりに１．１としたことが
異なる。 Film 50 Film 50 was made and coated in the same manner as film 48 . However, the difference is that the ratio of gelatin to silver halide expressed as silver nitrate was 1.1 instead of 0.85.
【００９７】表IVに、表III における如く結果を集計す
る。更に１ｍ2 についての青色染料CERESBLAU RR の
量及び加えた硬化剤の百分率を示す。混合物中の乳剤Ａ
及びＢの量の比も示す。Table IV summarizes the results as in Table III. In addition, the amount of blue dye CERESBLAU RR and the percentage of added curing agent per m 2 are shown. Emulsion A in mixture
And the ratio of the amounts of B and B are also shown.
【００９８】[0098]
【表２】 [Table 2]
【００９９】表IVに示した結果は、像色調を改良するた
め、臭沃化銀乳剤を部分的に置換して、塩化銀含有乳剤
の存在の重要性を明らかに示している。更にそればかり
でなく、非常に重要な改良を、塩化銀含有結晶及び青色
染料の同時添加によって得ることができる。この改良は
硬化度を増大させ、ゼラチン対ハロゲン化銀の比を下げ
ることによって増強される。これについての非常に明ら
かな例示は表IVのフィルム被覆Ｎｏ．４７及び４８によ
って与えられている。The results, shown in Table IV, clearly demonstrate the importance of the presence of silver chloride containing emulsions by partially substituting silver bromoiodide emulsions to improve image tone. Furthermore, very important improvements can be obtained by the simultaneous addition of silver chloride-containing crystals and a blue dye . This improvement is enhanced by increasing the degree of cure and lowering the gelatin to silver halide ratio. A very clear illustration of this is the film coating no. 47 and 48.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ Ｇ０３Ｃ 1/795 Ｇ０３Ｃ 1/795 (56)参考文献 特開 昭63−239434（ＪＰ，Ａ) 特開 昭64−73333（ＪＰ，Ａ) 特開 平３−156438（ＪＰ，Ａ) 特開 昭62−31846（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) G03C 1/035 G03C 1/00 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification symbol FI G03C 1/795 G03C 1/795 (56) References JP-A-63-239434 (JP, A) JP-A-64-73333 (JP) JP-A-3-156438 (JP, A) JP-A-62-31846 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) G03C 1/035 G03C 1/00
Claims (5)
少なくとも一つのハロゲン化銀乳剤層を含む工業用放射
線写真用写真ハロゲン化銀材料において、各ハロゲン化
銀乳剤層が、化学的に熟成した立方晶単分散臭沃化銀、
及び化学的に熟成した立方晶単分散塩化銀及び／又は塩
臭化銀及び／又は塩臭沃化銀乳剤結晶の混合物を含有す
ること、前記材料が、硝酸銀として表わしたハロゲン化
銀に対するゼラチンの重量比０．３〜１．２を有するこ
と、及び前記材料が処理サイクルの終りの洗浄後に、そ
れがゼラチン１ｇについて水２．５ｇ未満を吸収する程
度に硬化されていることを特徴とする写真ハロゲン化銀
材料。 1. A film support and industrial radiographic photographic silver halide material comprising at least one silver halide emulsion layer on one side or both sides thereof, each silver halide emulsion layer, was chemically ripened Cubic monodispersed silver bromoiodide,
And a mixture of chemically aged cubic monodisperse silver chloride and / or silver chlorobromide and / or silver chlorobromoiodide emulsion crystals , wherein said material has a halogenation expressed as silver nitrate.
Having a weight ratio of gelatin to silver of 0.3 to 1.2;
And after the material has been washed at the end of the processing cycle,
It absorbs less than 2.5 g of water per gram of gelatin
A photographic silver halide material characterized by being hardened every time .
剤結晶が、銀として表わして少なくとも８０重量％の量
で存在し、前記化学的に熟成した塩化銀及び／又は塩臭
化銀及び／又は塩臭沃化銀乳剤結晶が２０重量％以下の
量で存在することを特徴とする請求項１の写真ハロゲン
化銀材料。2. The chemically ripened monodispersed silver bromoiodide emulsion crystals are present in an amount of at least 80% by weight, expressed as silver, and wherein said chemically ripened silver chloride and / or silver chlorobromide is present. 2. The photographic silver halide material of claim 1 wherein the silver chlorobromoiodide emulsion crystals are present in an amount up to 20% by weight.
が０．１０〜０．３０μｍの結晶直径を有し、前記化学
的に熟成した塩化銀及び／又は塩臭化銀及び／又は塩臭
沃化銀乳剤結晶が、前記臭沃化銀乳剤よりも小さいか又
は大きさにおいて最大で３０％より大である結晶直径を
有することを特徴とする請求項１又は２の写真ハロゲン
化銀材料。3. The chemically ripened silver bromoiodide emulsion crystals have a crystal diameter of 0.10 to 0.30 μm, and the chemically ripened silver chloride and / or silver chlorobromide and / or 3. A photographic silver halide according to claim 1, wherein the silver chlorobromoiodide emulsion crystals have a crystal diameter smaller than or greater than 30% in size than the silver bromoiodide emulsion. material.
コロイド層中に、少なくとも１種の青着色非移行性染料
が存在することを特徴とする請求項１〜３の何れか１項
の写真材料。 Wherein the at least one hydrophilic colloid layer on the support, any one photograph of claims 1 to 3, characterized in that at least one blue-colored non-migratory dye is present material.
色染料が１２００ｍｇ／ｍ２ 以下の量で存在すること
を特徴とする請求項４の写真材料。 Wherein the support is a blue colored support, photographic material according to claim 4, wherein the blue colored dye is characterized by the presence in an amount of 1200 mg / m 2 or less.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP92200420 | 1992-02-14 | ||
| DE92200420.5 | 1992-02-14 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0611778A JPH0611778A (en) | 1994-01-21 |
| JP3150478B2 true JP3150478B2 (en) | 2001-03-26 |
Family
ID=8210423
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP04598693A Expired - Fee Related JP3150478B2 (en) | 1992-02-14 | 1993-02-09 | X-ray silver halide photographic material having suitable image tone and surface glare |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0555897B1 (en) |
| JP (1) | JP3150478B2 (en) |
| DE (1) | DE69318438T2 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0622668B1 (en) * | 1993-04-27 | 1999-03-03 | Agfa-Gevaert N.V. | Silver halide photographic material for industrial radiography suitable for various processing applications |
| EP0698817A1 (en) | 1994-08-22 | 1996-02-28 | Agfa-Gevaert N.V. | Assortment of silver halide photographic industrial X-ray films and method of processing said assortment |
| GB9603658D0 (en) * | 1996-02-21 | 1996-04-17 | Minnesota Mining & Mfg | Photographic materials with improved image tone |
| US20020106576A1 (en) * | 2000-12-06 | 2002-08-08 | Eastman Kodak Company | Radiation oncology treatment portal imaging film and method of use |
| US6582874B1 (en) | 2000-12-06 | 2003-06-24 | Eastman Kodak Company | Radiation oncology treatment portal imaging film and method of use |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57178235A (en) * | 1981-04-28 | 1982-11-02 | Konishiroku Photo Ind Co Ltd | Photographic sensitive silver halide material |
| CA1299424C (en) * | 1986-12-23 | 1992-04-28 | Donald R. Diehl | Radiographic element exhibiting reduced crossover |
-
1993
- 1993-01-20 DE DE1993618438 patent/DE69318438T2/en not_active Expired - Fee Related
- 1993-01-20 EP EP19930200139 patent/EP0555897B1/en not_active Expired - Lifetime
- 1993-02-09 JP JP04598693A patent/JP3150478B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| EP0555897A1 (en) | 1993-08-18 |
| EP0555897B1 (en) | 1998-05-13 |
| DE69318438D1 (en) | 1998-06-18 |
| JPH0611778A (en) | 1994-01-21 |
| DE69318438T2 (en) | 1998-11-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3190478B2 (en) | Method for producing tabular silver halide grains | |
| JPH05204068A (en) | Manufacture of photosensitive silver halogenide emulsion | |
| JP3150478B2 (en) | X-ray silver halide photographic material having suitable image tone and surface glare | |
| JPH06250305A (en) | Photosensitive photograph material of halogenated silver having reinforced image quality for quick processing in mammogram method | |
| JP3288849B2 (en) | X-ray film for silver halide photographic industry | |
| JPH0433019B2 (en) | ||
| JP3288852B2 (en) | Silver halide photographic materials for industrial radiography suitable for various processing applications | |
| JPH07191424A (en) | Manufacture of regular silver bromide or photosensitive emulsion of silver bromide and iodide and material containing above described emulsion | |
| JPH08334871A (en) | Silver halide photosensitive photographic screen film system with strengthened image quality for quickprocessing in mammography | |
| JPH06347955A (en) | Processing of x-ray film for halogenated silver photograph industry | |
| JP3030259B2 (en) | Method for reproducing electronically stored medical images on silver chloride rich photosensitive photographic materials for use as laser recording medical hard copy materials | |
| JPH0254534B2 (en) | ||
| JPH07128813A (en) | Processing of x-ray film for halogenated silver photograph industry | |
| JPS58111933A (en) | Prehardened photographic element | |
| US6528227B2 (en) | Film/screen system and image-forming system for use in direct X-ray applications | |
| JPH08101470A (en) | Combination of industrial x-ray film of silver halide photograph and processing method of said combination | |
| JP3138545B2 (en) | Photographic silver halide materials | |
| JPH06332125A (en) | Processing method of industrial x-ray film of prehardened silver halide photography | |
| JP2934607B2 (en) | Silver halide photographic material containing silver bromide or silver bromoiodide emulsion having triangular tabular grains | |
| EP1195641B1 (en) | Film/Screen system and image-forming system for use in direct X-ray applications | |
| JPH06250306A (en) | Photosensitive photograph material of halogenated silver for use as hard copy material for laser recording medical treatment and processing method thereof | |
| JPH10148899A (en) | Production of improved photographic planar emulsion rich in chloride | |
| JPH10104771A (en) | Silver halide photosensitive material coated with layer containing minimum amount of gelatin as binder material or not containing gelatin | |
| JPH10307353A (en) | Manufacture of (111) flat silver chloro(bromo)iodide salt | |
| JPH1184553A (en) | Multilayer silver halide photographic material and image forming method for industrial radiographic nondestructive test |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |