EP0731382A1 - Procédé pour la traitement d'un matériau photographique - Google Patents
Procédé pour la traitement d'un matériau photographique Download PDFInfo
- Publication number
- EP0731382A1 EP0731382A1 EP96200135A EP96200135A EP0731382A1 EP 0731382 A1 EP0731382 A1 EP 0731382A1 EP 96200135 A EP96200135 A EP 96200135A EP 96200135 A EP96200135 A EP 96200135A EP 0731382 A1 EP0731382 A1 EP 0731382A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- substituted
- unsubstituted
- developer
- silver halide
- ring
- 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.)
- Withdrawn
Links
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 84
- 239000004332 silver Substances 0.000 title claims abstract description 84
- -1 silver halide Chemical class 0.000 title claims abstract description 74
- 239000000463 material Substances 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 title claims abstract description 50
- 238000012545 processing Methods 0.000 title claims abstract description 23
- 239000000839 emulsion Substances 0.000 claims abstract description 32
- 150000001875 compounds Chemical class 0.000 claims abstract description 28
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 23
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 125000004430 oxygen atom Chemical group O* 0.000 claims abstract description 16
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 11
- 150000001450 anions Chemical class 0.000 claims abstract description 7
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 6
- 125000003118 aryl group Chemical group 0.000 claims abstract description 6
- 125000006615 aromatic heterocyclic group Chemical group 0.000 claims abstract description 5
- 239000008139 complexing agent Substances 0.000 claims abstract description 5
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract description 4
- 229910052751 metal Inorganic materials 0.000 claims abstract description 4
- 239000002184 metal Substances 0.000 claims abstract description 4
- 125000006353 oxyethylene group Chemical group 0.000 claims abstract description 4
- 239000002243 precursor Substances 0.000 claims abstract description 4
- 125000001424 substituent group Chemical group 0.000 claims abstract description 4
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 3
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- 125000000304 alkynyl group Chemical group 0.000 claims abstract description 3
- 125000003710 aryl alkyl group Chemical group 0.000 claims abstract description 3
- 125000004429 atom Chemical group 0.000 claims abstract description 3
- 125000004181 carboxyalkyl group Chemical group 0.000 claims abstract description 3
- 125000000392 cycloalkenyl group Chemical group 0.000 claims abstract description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 3
- 125000000623 heterocyclic group Chemical group 0.000 claims abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 3
- 239000001257 hydrogen Substances 0.000 claims abstract description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract description 3
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims abstract description 3
- 150000003567 thiocyanates Chemical class 0.000 claims abstract description 3
- 239000013078 crystal Substances 0.000 claims description 19
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 claims description 4
- 229910021653 sulphate ion Inorganic materials 0.000 claims description 3
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N 1H-imidazole Chemical compound C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 claims description 2
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 claims description 2
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 claims description 2
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 claims description 2
- 229910001513 alkali metal bromide Inorganic materials 0.000 claims description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 2
- IPZJQDSFZGZEOY-UHFFFAOYSA-N dimethylmethylene Chemical compound C[C]C IPZJQDSFZGZEOY-UHFFFAOYSA-N 0.000 claims description 2
- 229930195712 glutamate Natural products 0.000 claims description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 claims 1
- 150000003842 bromide salts Chemical class 0.000 claims 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 34
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 31
- 229910021607 Silver chloride Inorganic materials 0.000 description 20
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 20
- 108010010803 Gelatin Proteins 0.000 description 18
- 229920000159 gelatin Polymers 0.000 description 18
- 239000008273 gelatin Substances 0.000 description 18
- 235000019322 gelatine Nutrition 0.000 description 18
- 235000011852 gelatine desserts Nutrition 0.000 description 18
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 15
- 229910001961 silver nitrate Inorganic materials 0.000 description 14
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 8
- 239000011780 sodium chloride Substances 0.000 description 8
- 229960005070 ascorbic acid Drugs 0.000 description 7
- 239000011668 ascorbic acid Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 230000002829 reductive effect Effects 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 235000010323 ascorbic acid Nutrition 0.000 description 6
- 230000003595 spectral effect Effects 0.000 description 6
- 239000004094 surface-active agent Substances 0.000 description 6
- 239000002612 dispersion medium Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 230000005070 ripening Effects 0.000 description 5
- 231100000489 sensitizer Toxicity 0.000 description 5
- GGZHVNZHFYCSEV-UHFFFAOYSA-N 1-Phenyl-5-mercaptotetrazole Chemical class SC1=NN=NN1C1=CC=CC=C1 GGZHVNZHFYCSEV-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 230000008929 regeneration Effects 0.000 description 4
- 238000011069 regeneration method Methods 0.000 description 4
- 230000035945 sensitivity Effects 0.000 description 4
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical compound OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 description 4
- GFFGJBXGBJISGV-UHFFFAOYSA-N Adenine Chemical compound NC1=NC=NC2=C1N=CN2 GFFGJBXGBJISGV-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000002180 anti-stress Effects 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000002609 medium Substances 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 230000001737 promoting effect Effects 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 235000011149 sulphuric acid Nutrition 0.000 description 3
- 239000001117 sulphuric acid Substances 0.000 description 3
- JLAMDELLBBZOOX-UHFFFAOYSA-N 3h-1,3,4-thiadiazole-2-thione Chemical class SC1=NN=CS1 JLAMDELLBBZOOX-UHFFFAOYSA-N 0.000 description 2
- 229930024421 Adenine Natural products 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 210000000988 bone and bone Anatomy 0.000 description 2
- 238000010668 complexation reaction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 2
- XBDZRROTFKRVES-UHFFFAOYSA-N 2,3-dihydroxy-4,4,5,5-tetramethylcyclopent-2-en-1-one Chemical compound CC1(C)C(O)=C(O)C(=O)C1(C)C XBDZRROTFKRVES-UHFFFAOYSA-N 0.000 description 1
- CYEJMVLDXAUOPN-UHFFFAOYSA-N 2-dodecylphenol Chemical compound CCCCCCCCCCCCC1=CC=CC=C1O CYEJMVLDXAUOPN-UHFFFAOYSA-N 0.000 description 1
- ZFIQGRISGKSVAG-UHFFFAOYSA-N 4-methylaminophenol Chemical compound CNC1=CC=C(O)C=C1 ZFIQGRISGKSVAG-UHFFFAOYSA-N 0.000 description 1
- FCSKOFQQCWLGMV-UHFFFAOYSA-N 5-{5-[2-chloro-4-(4,5-dihydro-1,3-oxazol-2-yl)phenoxy]pentyl}-3-methylisoxazole Chemical compound O1N=C(C)C=C1CCCCCOC1=CC=C(C=2OCCN=2)C=C1Cl FCSKOFQQCWLGMV-UHFFFAOYSA-N 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- FKLJPTJMIBLJAV-UHFFFAOYSA-N Compound IV Chemical compound O1N=C(C)C=C1CCCCCCCOC1=CC=C(C=2OCCN=2)C=C1 FKLJPTJMIBLJAV-UHFFFAOYSA-N 0.000 description 1
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical class N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 description 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 1
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 1
- 150000000996 L-ascorbic acids Chemical class 0.000 description 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-M Methanesulfonate Chemical compound CS([O-])(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-M 0.000 description 1
- IWPZUNZVUVXGPW-UHFFFAOYSA-N OS(=O)=S.Cc1ccccc1 Chemical compound OS(=O)=S.Cc1ccccc1 IWPZUNZVUVXGPW-UHFFFAOYSA-N 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 239000004141 Sodium laurylsulphate Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 229960000643 adenine Drugs 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 235000006708 antioxidants Nutrition 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
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- NLFBCYMMUAKCPC-KQQUZDAGSA-N ethyl (e)-3-[3-amino-2-cyano-1-[(e)-3-ethoxy-3-oxoprop-1-enyl]sulfanyl-3-oxoprop-1-enyl]sulfanylprop-2-enoate Chemical compound CCOC(=O)\C=C\SC(=C(C#N)C(N)=O)S\C=C\C(=O)OCC NLFBCYMMUAKCPC-KQQUZDAGSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 150000002344 gold compounds Chemical class 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 238000009659 non-destructive testing Methods 0.000 description 1
- 150000004989 p-phenylenediamines Chemical class 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- CMCWWLVWPDLCRM-UHFFFAOYSA-N phenidone Chemical compound N1C(=O)CCN1C1=CC=CC=C1 CMCWWLVWPDLCRM-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000001397 quillaja saponaria molina bark Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 229930182490 saponin Natural products 0.000 description 1
- 150000007949 saponins Chemical class 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003019 stabilising effect Effects 0.000 description 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000003536 tetrazoles Chemical class 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 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
- G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
- G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
- G03C5/29—Development processes or agents therefor
- G03C5/305—Additives other than developers
-
- 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
- G03C1/0051—Tabular grain emulsions
- G03C1/0053—Tabular grain emulsions with high content of silver chloride
-
- 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
- G03C2200/00—Details
- G03C2200/01—100 crystal face
-
- 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
- G03C2200/00—Details
- G03C2200/03—111 crystal face
-
- 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
- G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
- G03C5/29—Development processes or agents therefor
- G03C5/30—Developers
Definitions
- the present invention relates a method of processing an exposed photographic silver halide material coated from hydrophilic layers comprising thin tabular emulsion crystals rich in chloride.
- silver deposit can be attributed to the presence in conventional developers of silver halide complexing agents like, e.g., sulphite and thiocyanate ions, which make silver ions still more soluble.
- silver halide complexing agents like, e.g., sulphite and thiocyanate ions, which make silver ions still more soluble.
- the complex ions formed are effectively reduced to metallic silver nuclei. Growth of said nearly invisible fine nuclei leads to the formation of said silver deposit.
- the silver halide emulsions utilized in high-contrast room-light-handleable elements are slow speed emulsions.
- the desired slow speed is achieved by the use of small grain sizes and by the doping of the silver halide grains with appropriate doping agents that control photographic speed.
- sparingly soluble and non-reducible silver salts as, e.g., 5,5'-bis-1,2,4-triazolin-3-thiones or derivatives of 1,3,4-thiadiazole-2-thiols as described, e.g. in BE-P 606,550 and GB-P 1,120,963, 2-mercapto-1,3,4-thiadiazoles described in US-P 3,212,892.
- emulsion layer may contain auxiliary coating agents such as saponin, sodium lauryl sulphate, dodecylphenol polyethylene oxide ether and hexadecyltrimethyl ammonium bromide.
- EP-Specification 0 223 883 a method has been described which comprises the treating of a silver halide photographic material with an aqueous alkaline liquid in the presence of (i) a developing agent, (ii) a heterocyclic mercapto compound including an aliphatic group of at least 3 carbon atoms and (iii) a surface active agent, characterised in that said surface active agent is an anionic alkylphenoxy polyalkyleneoxy phosphate ester surfactant.
- EP-A 0 620 484 reduction of the so-called "pi-line" defect, especially for processed materials for non-destructive testing purposes, has been described.
- Such materials should comprise at least one vinyl sulphone compound as a hardening agent and at least one polyoxyalkylene compound as a surfactant in at least one of its hydrophilic layers.
- a processing method comprising a developing step wherein the developer comprises as a surfactant at least one anionic alkylphenoxy and/or alkoxy polyalkyleneoxy phosphate ester, sulphate ester, alkyl carboxylic, sulphonic or phosphonic acid and/or a salt thereof a remarkable improvement has been obtained.
- a similar result has been obtained as disclosed in EP-A's 0 621 506 and 0 620 483.
- silver chloride is the more soluble silver halide salt, and therefor especially suitable in rapid processing applications, the problem of sludge formation by processing light-sensitive silver halide materials comprising such grains is more pronounced.
- the said thin tabular grains with their large surfaces are desired, e.g., as they allow the adsorption of high amounts of spectral sensitiser(s), leading to strong absorption of incident radiation. As a result a high sensitivity can be expected. Furthermore, as scattering of incident radiation throughout parallel twin planes is reduced, sharpness of the processed material is expected to be better. And last but not least the covering power of thin tabular grains comprised in coated layers of forehardened materials is not reduced in the processing of the said materials.
- an exposed silver halide photographic material comprising at least one coated hydrophilic silver halide emulsion layer comprising tabular grains rich in chlqride, bounded by [100] or [111] major faces, characterised by the steps of developing, followed by fixing, rinsing and drying the said material, wherein developing proceeds in a developer, comprising hydroquinone in an amount from 0 to 30 g per litre, an auxiliary developer, as silver halide complexing agents alkali metal sulphite salts in an amount from 1 to 50 g per litre, at least 1 g of a compound corresponding to the formula (I), a precursor thereof, a derivative thereof and/or a metal salt thereof wherein
- the said heterocyclic aromatic ring is a pyridine, a pyrimidine, an imidazol, a benzimidazol, a thiazol, a benzothiazol or a derivative thereof.
- at least R or one of the ring substituents represents at least 3 oxyethylene units.
- anions are required to neutralise the total electrical charge of these N-heterocyclic aromatic onium compounds.
- Preferred anions are sulphonate anions, like methylsulphonate and the like, toluyl sulphonate, carbamate, benzoate, glutamate, perchlorate, sulphate etc.
- the said anions are p-toluyl sulphonate.
- This formula corresponds with (iso)ascorbic acid, which is, together with 1-ascorbic acid, a preferred form of formula (I).
- the compound(s) according to formula (I) preferably is(are) present in the developer solution in an amount comprised between 1 g and 50 g per litre.
- reducing precursor compounds have, e.g., been described in WO's 94/3834 and 94/16362, which are both incorporated herein by reference.
- ascorbic acid is not merely used in the developer as an antioxidant as, e.g., described in WO 93/12463, in JP-A's 4428673 and 55149936, in GB 1,266,533 and in US-P's 3,865,591; 4,756,997 and 4,839,259 and in the literature as, e.g., J. Am. Chem. Soc., 60 (1938), p. 99 and p. 2084; 61 (1939), p. 442; 64 (1942), p. 1561, 65 (1943), p. 1489; 66 (1944), p. 700 and 104 (1982), p. 6273.
- the developer liquid may contain any combination of hydroquinone as a developing agent and auxiliary developer known for use in the development of exposed photographic silver halide, but the absence of hydroquinone is not excluded.
- auxiliary developing compounds may be utilized p-methylaminophenol, a 1-phenyl-3-pyrazolidine-1-one, p-phenylenediamine derivatives and the like. Amounts of hydroquinone are lower than 30 g per litre and more preferably lower than 20 g per litre.
- auxiliary developer Preferred amounts of auxiliary developer are present in a concentration range of up to 10 mmoles per litre of developer, said auxiliary developer being preferably a 1-phenyl-3-pyrazolidine-1-one compound, well-known as a "phenidone" compound.
- the developer further comprises silver complexing compound(s) such as alkali metal sulphites, bisulphites, metasulphites or metabisulphites, but preferably it contains an alkali metal sulphite salt, and more preferably sodium sulphite, in an amount of less than 50, and more preferably in an amount of less than 40 g per litre of developer.
- the developer solution can be alkalised with alkaline metal hydroxides, phosphates, borates, carbonates and the like.
- the developer liquid or activator liquid may contain still other ingredients, e.g., metal complexing agents, an anti-fogging agent, e.g., alkali metal bromide, in amounts ranging from 0.01 to 0.4 moles per litre, a benzotriazole, a benzothiazole, a tetrazole, e.g., up to 0.06 g per liter of 1-phenyl-5-mercapto-tetrazole, solvents improving the dissolution of the developing agents, e.g., alcohols, polyethylene glycols and esters thereof and alkanolamines, surface active agents, development retarding or activating compounds, e.g., quaternary ammonium salts, and gelatin hardening agents, e.g., dialdehyde compounds such as glutardialdehyde.
- polyethylene glycols having a low molecular weight in the range from 200 to 400 is preferred.
- values of the pH of the developer solution are preferably in the range from 9.0 to 12.5, more preferably in the range of 9.5 to 12.0 and still more preferably from 9.5 to 11.0. Even at those relatively "lower” pH values, if compared with more frequently used alkaline pH values of 12.0 and more, the required sensitometry is still attained, which means that a developer having a composition according to this invention offers enough reactivity to get the required sensitivity for a material that is processed therein within a reasonable processing time.
- the present invention thus includes a method for developing, by means of the developer according to this invention, of any type of photographic silver halide emulsion layer material, e.g., a graphic art, micrographic and an X-ray recording material, after image-wise exposing the said material by means of suitable radiation sources, adapted to each application in particular, and immersing it into the developer the composition of which has been described hereinbefore, with the proviso that the said material comprises at least one coated hydrophilic silver halide emulsion layer containing tabular silver halide grains rich in chloride.
- any type of photographic silver halide emulsion layer material e.g., a graphic art, micrographic and an X-ray recording material
- tabular silver halide grains rich in chloride, coated in hydrophilic layers of materials to be processed according to the method of this invention are bounded by [100] or [111] major faces.
- Tabular silver halide grains rich in chloride, bounded by [100] major faces and/or the preparation method thereof and/or materials in which said grains are incorporated have been described in, e.g., US-P's 5,264,337; 5,275,930; 5,292,632; 5,310,635; 5,314,798; 5,320,938; in the published EP-A's 0 534 395, 0 569 971, 0 584 815, 0 584 644, 0 617 325, 0 618 492 and 0 653 669, which is incorporated herein by reference.
- Tabular silver halide grains rich in chloride, bounded by [111] major faces and/or the preparation method thereof and/or materials in which said grains are incorporated have been described in, e.g., US-P's 4,399,215; 4,400,463; 4,804,621; 5,061,617; 5,176,991; 5,176,992; 5,178,997; 5,178,998; 5,183,732; 5,185,239; 5,217,858; 5,221,602; 5,264,337; 5,272,052; 5,275,930; 5,286,621; 5,292,632; 5,298,385; 5,298,387; 5,298,388; 5,310,644; 5,320,938; 5,356,764; in the published EP-A's 0 481 133, 0 503 700, 0 532 801, 0 533 189, 0 647 877 and 0 678 772, which are incorporated herein by reference.
- the said tabular silver halide grains rich in chloride comprised in silver halide photographic materials to be processed according to the method of this invention preferably have an average thickness over the total crystal population of less than 0.5 ⁇ m, more preferably of less than 0.3 ⁇ m and still more preferably from 0.05 ⁇ m to 0.2 ⁇ m.
- an average aspect ratio defined as the ratio, calculated from the measurements of the equivalent diameter of a circle having the same surface area as the different individual grains, and its thickness, is preferably higher than 2:1; more preferably higher than 5:1 and still more preferably higher than 8:1, up to a ratio of about 100:1.
- Silver halide emulsions incorporated in at least one photosensitive layer in a suitable layer arrangement of the said materials processed by the method according to this invention are composed of preferred amounts of chloride, in mole %, of at least 50 %, more preferably at least 70 % and even more preferably at least 90 %, up to 100 %.
- Other halides present are bromide, in amounts from 0 up to 50 mole% and iodide in amounts from 0 up to 2 mole %.
- processing steps according to the present invention are advantageously applied in automatic processing equipment, preferably containing conveyer rollers as described, e.g., in US-P 3,025,779 and 3,545,971, in a time from 5 to 45 seconds at a temperature from 25 to 40°C.
- concentration of the derivatives corresponding to formula (I) and the pH are maintained at a constant value by replenishment with unoxidised developing agent, thereby adding a concentrated alkali hydroxide solution under controlled constant redox potential as has been illustrated in EP-A 0 552 511, which is incorporated herein by reference.
- This invention allows the use of low regeneration amounts for the developer used in the developing step according to the method of this invention, having a composition wherein minimum regeneration amounts of developing solution from 50 to 250 ml/m 2 of photographic material are possible and even more preferred from 50 to 150 ml/m 2 .
- Photosensitive silver halide emulsion layer(s) present in silver halide photographic materials processed by the method according to this invention may be of any type or composition used in silver halide photography, provided that at least one layer comprises at least one thin tabular silver halide emulsion rich in chloride bounded by [100] or [111] major faces and may be present in whatever a layer arrangement used in the art of photography.
- So black-and-white silver halide films intended to be used for contact exposures form an important class of photographic films. These so-called contact films are used for proper reproduction on one hand and for dry dot-etching on the other hand. In modern pre-press graphic arts these contact materials are designed to be usable for several minutes under roomlight conditions, meaning light containing substantially no UV-light.
- the method for determining the silver deposit makes use of the GEVASET 437N automatic processor, trademarked product from Agfa-Gevaert, which has a tank volume of only 1 litre per tank.
- the temperature and the processing velocity are made variable. As there is only one roller before entering and after leaving every bath, there is no danger to disturb the outlook of the film surface.
- the agitation of the developer is reduced to a negligable extent and the developer tank is followed by two fixation tanks and one rinsing tank, both having a content of 1 litre.
- the film is immersed into the developer tank for 46 seconds at a temperature of 30°C. The developer is not regenerated.
- the washing procedure was performed in a discontinous way, adding 3 1 of demineralised water, containing up to 8 mmole of sodium chloride pro liter, until pAg was reaching a value of about 7.3.
- the emulsion was peptised and was chemically ripened to an optimal fog-sensitivity relationship at 52°C, pAg having a value of about 6.95.
- Chemical ripening agents besides gold (in an amount of 0.019 mmole) and sulphur (tetramethyl thiodithiocarboxylic acid diamide in an amount of 0.061 mmole), were toluene thiosulphonic acid and iodide ions, both being predigestion agents in amounts of 0.02 and 8.6 mmoles respectively.
- a photographic material was prepared having on a subbed polyester base a gelatinous silver halide emulsion of which the silver halide consists for 99.7 % of silver chloride having an average grain size of 0.55 ⁇ m the preparation of which has been described above.
- said emulsion was spectrally sensitised with two spectral sensitisers, corresponding to the following formulae (see compound III and compound IV):
- spectral sensitisers were added consecutively in an amount of 0.1 mmole and 0.3 mmole per mole of silver nitrate respectively.
- the emulsion was further stabilised with 0.22 mmole of compound (V) and 0.68 mmole of compound (VI) per mole of silver nitrate.
- a coated amount of silver expressed as the equivalent amount of silver nitrate of 3.8 g per square meter and a gelatin to silver chloride (expressed in equivalent amount of silver nitrate) ratio of 0.35 was provided with a gelatin covering layer (anti-stress layer) of 1.30 g of gelatin per m2 on both sides of a polyethylene terephtalate film support having a thickness of 175 ⁇ m.
- a nucleation step was performed by introducing solution A and solution B1 simultaneously in dispersion medium C both at a flow rate of 30 ml/min during 30 seconds. After a physical ripening time of 15 min during which the temperature was raised to 70 °C and 97.5 g of gelatin and 1500 ml of water were added and the mixture was stirred for an additional 5 minutes.
- a growth step was performed by introducing by a double jet during 66 minutes solution A starting at a flow rate of 7.5 ml/min and linearly increasing the flow rate to an end value of 37.5 ml/min, and solution B1 at an increasing flow rate as to maintain a constant mV-value, measured by a silver electrode versus a saturated calomel electrode (S.C.E.), of +92 mV.
- the pH value of the said dispersing medium was adjusted to a value of 3.0 with sulphuric acid, and after the addition of 55.5 ml of polystyrene sulphonic acid the obtained flocculate was decanted and washed three times with an amount of 6 1 of demineralised water in order to remove the soluble salts present.
- Tabular silver chloride crystals having [111] major phase and a sphere equivalent average diameter of 1.20 ⁇ m were obtained, with an average thickness of 0.37 ⁇ m and thus an average aspect ratio of 3.3.
- a photographic material was further prepared having on a subbed polyester base a gelatinous silver halide emulsion of which the silver halide consists for 100 % of tabular silver chloride, the preparation and emulsion crystal characteristics have been given hereinbefore.
- a coated amount of silver expressed as the equivalent amount of silver nitrate of 3.8 g per square meter and a gelatin to silver chloride (expressed in equivalent amount of silver nitrate) ratio of 0.35 was provided with a gelatin covering layer (anti-stress layer) of 1.30 g of gelatin per m2 on both sides of a polyethylene terephtalate film support having a thickness of 175 ⁇ m.
- the temperature of A and B1 was established at 40°C.
- a nucleation step was performed by introducing solution A and solution B1 simultaneously in dispersion medium C both at a flow rate of 60 ml/min during 30 seconds. After a physical ripening time of 20 min during which the temperature was raised to 70 °C. Then a growth step was performed by introducing by a double jet during 64 minutes and 40 seconds solution A starting at a flow rate of 5 ml/min and linearly increasing the flow rate to an end value of 25 ml/min, and solution B1 at an increasing flow rate as to maintain a constant mV-value, measured by a silver electrode versus a saturated calomel electrode (S.C.E.), of +135 mV.
- S.C.E. saturated calomel electrode
- the pH value of the said dispersing medium was adjusted to a value of 3.0 with sulphuric acid, and after the addition of 37 ml of polystyrene sulphonic acid the obtained flocculate was decanted and washed three times with an amount of 6 l of demineralised water in order to remove the soluble salts present.
- the thus obtained silver chloride tabular emulsion showed a [100]-major faces.
- the average circle equivalent diameter d EM , average thickness d, average aspect ratio AR were obtained from electron microscopic photographs. Respective values of 1.58 ⁇ m; 0.42 ⁇ m and 3.8:1 were measured.
- a coated amount of silver expressed as the equivalent amount of silver nitrate of 3.8 g per square meter and a gelatin to silver chloride (expressed in equivalent amount of silver nitrate) ratio of 0.35 was provided with a gelatin covering layer (anti-stress layer) of 1.30 g of gelatin per m2 on both sides of a polyethylene terephtalate film support having a thickness of 175 ⁇ m.
- compositions of the developers Type of dev. DEV1 DEV2 DEV3 DEV4 DEV5 pH ready-for-use 10.5 10.0 10.0 10.0 10.0 Hydroquinone (mole/l) 0.27 0.18 0.18 0.18 - 1-phenyl-4-methyl-3-pyrazolidine-1-one (mmole/l) 4.6 4.6 4.6 4.6 4.6 Br - (mmole/l) 33.6 21 21 21 21 SO 3 -- (mole/l) 0.57 0.19 0.19 0.19 0.19 0.19 CO 3-- (mole/l) 0.22 0.44 0.44 0.44 0.44 0.44 0.44 0.44 0.44 0.44 0.44 Polyglycol (ml/l) (M.W. ca.
- Table 1 amounts, in mg/l, of deposited silver determined by means of the method described hereinbefore in Exhausted Developer (ED), after 24 hours (in mg/l)(ED24), after 4 weeks present in the filtrate (mg/l)(ED4W) as well as the Total Deposit (mg/l) (TD) and the rest amount of Deposited Silver in the Filtrate (DSF) are given for material A (regular cubic AgCl) and for materials B and C (tabular AgCl crystals with [111] and [100] major faces respectively), in the developers DEV1, DEV2 and DEV5.
- Samples of the coating materials A, B and C were exposed according to the ANSI procedure 1043. After processing in the developers mentioned in Table 2 for developing times of 11 seconds at 33°C, the sensitometric properties of each material was measured.
- sensitometric results are matching those obtained with DEV1 and material A (as described in EP-A No. 94203085, filed October 24, 1994) containing cubic AgCl emulsion crystals as has been illustrated in Table 2 for [111]-tabular AgCl crystals and for [100]-tabular AgCl crystals.
- the same sensitometric values can be obtained by using a developer with ascorbic acid instead of hydroquinone.
- high covering power obtained with cubic crystals rich in chloride, described in the non-published EP-A is confirmed.
- the covering power obtained for cubic crystals rich in chloride is always better than for [100] and [111] tabular grains rich in chloride, but the tendency is present that there is a relative increase in covering power, especially for the tabular [100] grains versus the cubic grains, if developing occurs in developers used in the method according to this invention.
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Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP96200135A EP0731382A1 (fr) | 1995-02-21 | 1996-01-19 | Procédé pour la traitement d'un matériau photographique |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP95200418 | 1995-02-21 | ||
| EP95200418 | 1995-02-21 | ||
| EP96200135A EP0731382A1 (fr) | 1995-02-21 | 1996-01-19 | Procédé pour la traitement d'un matériau photographique |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP0731382A1 true EP0731382A1 (fr) | 1996-09-11 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP96200135A Withdrawn EP0731382A1 (fr) | 1995-02-21 | 1996-01-19 | Procédé pour la traitement d'un matériau photographique |
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| Country | Link |
|---|---|
| EP (1) | EP0731382A1 (fr) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3512981A (en) * | 1968-02-05 | 1970-05-19 | Pako Corp | Stable photographic developers containing ascorbic acid |
| US3865591A (en) * | 1973-05-10 | 1975-02-11 | Delaware Photographic Products | General purpose developer |
| GB2109577A (en) * | 1981-11-12 | 1983-06-02 | Eastman Kodak Co | Radiation-sensitive photographic silver halide emulsion and process for preparing the same |
| EP0518352A1 (fr) * | 1991-06-13 | 1992-12-16 | Dainippon Ink And Chemicals, Inc. | Procédé pour former des images négatives à très haut contraste et matériau photographique à l'halogénure d'argent et développateur étant utilise pour ceux-ci |
| EP0538947A1 (fr) * | 1991-10-24 | 1993-04-28 | Agfa-Gevaert N.V. | Matériau photographique pour rayons X à l'halogénure d'argent, approprié pour traitement rapide |
| EP0580041A2 (fr) * | 1992-07-10 | 1994-01-26 | Fuji Photo Film Co., Ltd. | Composition pour développement et méthode de traitement d'un matériau photographique à l'halogénure d'argent |
| USH1294H (en) * | 1990-03-02 | 1994-03-01 | Fuji Photo Film Co., Ltd. | Silver halide photographic emulsion |
| US5384232A (en) * | 1991-12-02 | 1995-01-24 | E. I. Du Pont De Nemours And Company | Process for rapid access development of silver halide films using pyridinium as development accelerators |
-
1996
- 1996-01-19 EP EP96200135A patent/EP0731382A1/fr not_active Withdrawn
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3512981A (en) * | 1968-02-05 | 1970-05-19 | Pako Corp | Stable photographic developers containing ascorbic acid |
| US3865591A (en) * | 1973-05-10 | 1975-02-11 | Delaware Photographic Products | General purpose developer |
| GB2109577A (en) * | 1981-11-12 | 1983-06-02 | Eastman Kodak Co | Radiation-sensitive photographic silver halide emulsion and process for preparing the same |
| USH1294H (en) * | 1990-03-02 | 1994-03-01 | Fuji Photo Film Co., Ltd. | Silver halide photographic emulsion |
| EP0518352A1 (fr) * | 1991-06-13 | 1992-12-16 | Dainippon Ink And Chemicals, Inc. | Procédé pour former des images négatives à très haut contraste et matériau photographique à l'halogénure d'argent et développateur étant utilise pour ceux-ci |
| EP0538947A1 (fr) * | 1991-10-24 | 1993-04-28 | Agfa-Gevaert N.V. | Matériau photographique pour rayons X à l'halogénure d'argent, approprié pour traitement rapide |
| US5384232A (en) * | 1991-12-02 | 1995-01-24 | E. I. Du Pont De Nemours And Company | Process for rapid access development of silver halide films using pyridinium as development accelerators |
| EP0580041A2 (fr) * | 1992-07-10 | 1994-01-26 | Fuji Photo Film Co., Ltd. | Composition pour développement et méthode de traitement d'un matériau photographique à l'halogénure d'argent |
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