US3770448A - Lightsensitive photographic material - Google Patents
Lightsensitive photographic material Download PDFInfo
- Publication number
- US3770448A US3770448A US00137604A US3770448DA US3770448A US 3770448 A US3770448 A US 3770448A US 00137604 A US00137604 A US 00137604A US 3770448D A US3770448D A US 3770448DA US 3770448 A US3770448 A US 3770448A
- Authority
- US
- United States
- Prior art keywords
- silver
- lightsensitive
- compound
- silver salt
- salt
- 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 - Lifetime
Links
- 239000000463 material Substances 0.000 title abstract description 20
- 229910052709 silver Inorganic materials 0.000 claims abstract description 28
- 239000004332 silver Substances 0.000 claims abstract description 28
- 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 claims abstract description 27
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 20
- -1 silver halide Chemical class 0.000 claims description 41
- 239000000203 mixture Substances 0.000 claims description 25
- 150000003839 salts Chemical class 0.000 claims description 18
- AQRYNYUOKMNDDV-UHFFFAOYSA-M silver behenate Chemical group [Ag+].CCCCCCCCCCCCCCCCCCCCCC([O-])=O AQRYNYUOKMNDDV-UHFFFAOYSA-M 0.000 claims description 6
- 150000007933 aliphatic carboxylic acids Chemical group 0.000 claims description 4
- 238000011065 in-situ storage Methods 0.000 claims description 3
- 150000004668 long chain fatty acids Chemical class 0.000 claims description 2
- 229940100890 silver compound Drugs 0.000 claims description 2
- 150000003379 silver compounds Chemical class 0.000 claims description 2
- 125000000101 thioether group Chemical group 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 abstract description 12
- 238000010438 heat treatment Methods 0.000 abstract description 6
- XBYRMPXUBGMOJC-UHFFFAOYSA-N 1,2-dihydropyrazol-3-one Chemical class OC=1C=CNN=1 XBYRMPXUBGMOJC-UHFFFAOYSA-N 0.000 abstract description 4
- 238000001035 drying Methods 0.000 abstract description 3
- 150000002736 metal compounds Chemical class 0.000 abstract description 3
- 239000010410 layer Substances 0.000 description 30
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- 239000003638 chemical reducing agent Substances 0.000 description 18
- 238000000034 method Methods 0.000 description 14
- 150000003378 silver Chemical class 0.000 description 14
- 125000004432 carbon atom Chemical group C* 0.000 description 13
- 239000007800 oxidant agent Substances 0.000 description 12
- 125000001931 aliphatic group Chemical group 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 229910052736 halogen Inorganic materials 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 8
- 238000006479 redox reaction Methods 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 125000003118 aryl group Chemical group 0.000 description 7
- 238000005266 casting Methods 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 7
- 125000003545 alkoxy group Chemical group 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 6
- 125000000753 cycloalkyl group Chemical group 0.000 description 6
- 150000002367 halogens Chemical class 0.000 description 6
- 150000007524 organic acids Chemical class 0.000 description 6
- 229920006395 saturated elastomer Polymers 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 5
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 5
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 5
- 229940093915 gynecological organic acid Drugs 0.000 description 5
- 125000000623 heterocyclic group Chemical group 0.000 description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 5
- 235000005985 organic acids Nutrition 0.000 description 5
- IJAPPYDYQCXOEF-UHFFFAOYSA-N phthalazin-1(2H)-one Chemical compound C1=CC=C2C(=O)NN=CC2=C1 IJAPPYDYQCXOEF-UHFFFAOYSA-N 0.000 description 5
- 235000021357 Behenic acid Nutrition 0.000 description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 125000002252 acyl group Chemical group 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- 229940116226 behenic acid Drugs 0.000 description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 4
- 229910052794 bromium Inorganic materials 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- PYRKKGOKRMZEIT-UHFFFAOYSA-N 2-[6-(2-cyclopropylethoxy)-9-(2-hydroxy-2-methylpropyl)-1h-phenanthro[9,10-d]imidazol-2-yl]-5-fluorobenzene-1,3-dicarbonitrile Chemical compound C1=C2C3=CC(CC(C)(O)C)=CC=C3C=3NC(C=4C(=CC(F)=CC=4C#N)C#N)=NC=3C2=CC=C1OCCC1CC1 PYRKKGOKRMZEIT-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 229920002301 cellulose acetate Polymers 0.000 description 3
- 229940125773 compound 10 Drugs 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- ZLVXBBHTMQJRSX-VMGNSXQWSA-N jdtic Chemical compound C1([C@]2(C)CCN(C[C@@H]2C)C[C@H](C(C)C)NC(=O)[C@@H]2NCC3=CC(O)=CC=C3C2)=CC=CC(O)=C1 ZLVXBBHTMQJRSX-VMGNSXQWSA-N 0.000 description 3
- 230000001376 precipitating effect Effects 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- 229910001864 baryta Inorganic materials 0.000 description 2
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 229920002678 cellulose Chemical class 0.000 description 2
- 239000001913 cellulose Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229940125898 compound 5 Drugs 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical class [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000006303 photolysis reaction Methods 0.000 description 2
- 230000015843 photosynthesis, light reaction Effects 0.000 description 2
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- JEXVQSWXXUJEMA-UHFFFAOYSA-N pyrazol-3-one Chemical group O=C1C=CN=N1 JEXVQSWXXUJEMA-UHFFFAOYSA-N 0.000 description 2
- NDGRWYRVNANFNB-UHFFFAOYSA-N pyrazolidin-3-one Chemical class O=C1CCNN1 NDGRWYRVNANFNB-UHFFFAOYSA-N 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- ABJSOROVZZKJGI-OCYUSGCXSA-N (1r,2r,4r)-2-(4-bromophenyl)-n-[(4-chlorophenyl)-(2-fluoropyridin-4-yl)methyl]-4-morpholin-4-ylcyclohexane-1-carboxamide Chemical compound C1=NC(F)=CC(C(NC(=O)[C@H]2[C@@H](C[C@@H](CC2)N2CCOCC2)C=2C=CC(Br)=CC=2)C=2C=CC(Cl)=CC=2)=C1 ABJSOROVZZKJGI-OCYUSGCXSA-N 0.000 description 1
- SZUVGFMDDVSKSI-WIFOCOSTSA-N (1s,2s,3s,5r)-1-(carboxymethyl)-3,5-bis[(4-phenoxyphenyl)methyl-propylcarbamoyl]cyclopentane-1,2-dicarboxylic acid Chemical compound O=C([C@@H]1[C@@H]([C@](CC(O)=O)([C@H](C(=O)N(CCC)CC=2C=CC(OC=3C=CC=CC=3)=CC=2)C1)C(O)=O)C(O)=O)N(CCC)CC(C=C1)=CC=C1OC1=CC=CC=C1 SZUVGFMDDVSKSI-WIFOCOSTSA-N 0.000 description 1
- IUSARDYWEPUTPN-OZBXUNDUSA-N (2r)-n-[(2s,3r)-4-[[(4s)-6-(2,2-dimethylpropyl)spiro[3,4-dihydropyrano[2,3-b]pyridine-2,1'-cyclobutane]-4-yl]amino]-3-hydroxy-1-[3-(1,3-thiazol-2-yl)phenyl]butan-2-yl]-2-methoxypropanamide Chemical compound C([C@H](NC(=O)[C@@H](C)OC)[C@H](O)CN[C@@H]1C2=CC(CC(C)(C)C)=CN=C2OC2(CCC2)C1)C(C=1)=CC=CC=1C1=NC=CS1 IUSARDYWEPUTPN-OZBXUNDUSA-N 0.000 description 1
- STBLNCCBQMHSRC-BATDWUPUSA-N (2s)-n-[(3s,4s)-5-acetyl-7-cyano-4-methyl-1-[(2-methylnaphthalen-1-yl)methyl]-2-oxo-3,4-dihydro-1,5-benzodiazepin-3-yl]-2-(methylamino)propanamide Chemical compound O=C1[C@@H](NC(=O)[C@H](C)NC)[C@H](C)N(C(C)=O)C2=CC(C#N)=CC=C2N1CC1=C(C)C=CC2=CC=CC=C12 STBLNCCBQMHSRC-BATDWUPUSA-N 0.000 description 1
- HUWSZNZAROKDRZ-RRLWZMAJSA-N (3r,4r)-3-azaniumyl-5-[[(2s,3r)-1-[(2s)-2,3-dicarboxypyrrolidin-1-yl]-3-methyl-1-oxopentan-2-yl]amino]-5-oxo-4-sulfanylpentane-1-sulfonate Chemical compound OS(=O)(=O)CC[C@@H](N)[C@@H](S)C(=O)N[C@@H]([C@H](C)CC)C(=O)N1CCC(C(O)=O)[C@H]1C(O)=O HUWSZNZAROKDRZ-RRLWZMAJSA-N 0.000 description 1
- MPDDTAJMJCESGV-CTUHWIOQSA-M (3r,5r)-7-[2-(4-fluorophenyl)-5-[methyl-[(1r)-1-phenylethyl]carbamoyl]-4-propan-2-ylpyrazol-3-yl]-3,5-dihydroxyheptanoate Chemical compound C1([C@@H](C)N(C)C(=O)C2=NN(C(CC[C@@H](O)C[C@@H](O)CC([O-])=O)=C2C(C)C)C=2C=CC(F)=CC=2)=CC=CC=C1 MPDDTAJMJCESGV-CTUHWIOQSA-M 0.000 description 1
- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical compound C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 description 1
- KQZLRWGGWXJPOS-NLFPWZOASA-N 1-[(1R)-1-(2,4-dichlorophenyl)ethyl]-6-[(4S,5R)-4-[(2S)-2-(hydroxymethyl)pyrrolidin-1-yl]-5-methylcyclohexen-1-yl]pyrazolo[3,4-b]pyrazine-3-carbonitrile Chemical compound ClC1=C(C=CC(=C1)Cl)[C@@H](C)N1N=C(C=2C1=NC(=CN=2)C1=CC[C@@H]([C@@H](C1)C)N1[C@@H](CCC1)CO)C#N KQZLRWGGWXJPOS-NLFPWZOASA-N 0.000 description 1
- UNILWMWFPHPYOR-KXEYIPSPSA-M 1-[6-[2-[3-[3-[3-[2-[2-[3-[[2-[2-[[(2r)-1-[[2-[[(2r)-1-[3-[2-[2-[3-[[2-(2-amino-2-oxoethoxy)acetyl]amino]propoxy]ethoxy]ethoxy]propylamino]-3-hydroxy-1-oxopropan-2-yl]amino]-2-oxoethyl]amino]-3-[(2r)-2,3-di(hexadecanoyloxy)propyl]sulfanyl-1-oxopropan-2-yl Chemical compound O=C1C(SCCC(=O)NCCCOCCOCCOCCCNC(=O)COCC(=O)N[C@@H](CSC[C@@H](COC(=O)CCCCCCCCCCCCCCC)OC(=O)CCCCCCCCCCCCCCC)C(=O)NCC(=O)N[C@H](CO)C(=O)NCCCOCCOCCOCCCNC(=O)COCC(N)=O)CC(=O)N1CCNC(=O)CCCCCN\1C2=CC=C(S([O-])(=O)=O)C=C2CC/1=C/C=C/C=C/C1=[N+](CC)C2=CC=C(S([O-])(=O)=O)C=C2C1 UNILWMWFPHPYOR-KXEYIPSPSA-M 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- OTDZDMSLXORVOV-UHFFFAOYSA-N 2-(hydroxyiminomethyl)-4-nitrophenol silver Chemical compound [Ag].ON=CC1=CC([N+]([O-])=O)=CC=C1O OTDZDMSLXORVOV-UHFFFAOYSA-N 0.000 description 1
- FMKGJQHNYMWDFJ-CVEARBPZSA-N 2-[[4-(2,2-difluoropropoxy)pyrimidin-5-yl]methylamino]-4-[[(1R,4S)-4-hydroxy-3,3-dimethylcyclohexyl]amino]pyrimidine-5-carbonitrile Chemical compound FC(COC1=NC=NC=C1CNC1=NC=C(C(=N1)N[C@H]1CC([C@H](CC1)O)(C)C)C#N)(C)F FMKGJQHNYMWDFJ-CVEARBPZSA-N 0.000 description 1
- TVTJUIAKQFIXCE-HUKYDQBMSA-N 2-amino-9-[(2R,3S,4S,5R)-4-fluoro-3-hydroxy-5-(hydroxymethyl)oxolan-2-yl]-7-prop-2-ynyl-1H-purine-6,8-dione Chemical compound NC=1NC(C=2N(C(N(C=2N=1)[C@@H]1O[C@@H]([C@H]([C@H]1O)F)CO)=O)CC#C)=O TVTJUIAKQFIXCE-HUKYDQBMSA-N 0.000 description 1
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical class NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 1
- LDLCZOVUSADOIV-UHFFFAOYSA-N 2-bromoethanol Chemical compound OCCBr LDLCZOVUSADOIV-UHFFFAOYSA-N 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- BOTGCZBEERTTDQ-UHFFFAOYSA-N 4-Methoxy-1-naphthol Chemical compound C1=CC=C2C(OC)=CC=C(O)C2=C1 BOTGCZBEERTTDQ-UHFFFAOYSA-N 0.000 description 1
- KXIXZZRUFWKXKM-UHFFFAOYSA-N 4-chloro-2-(hydroxyiminomethyl)phenol silver Chemical compound [Ag].ON=CC1=CC(Cl)=CC=C1O KXIXZZRUFWKXKM-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
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- KCBAMQOKOLXLOX-BSZYMOERSA-N CC1=C(SC=N1)C2=CC=C(C=C2)[C@H](C)NC(=O)[C@@H]3C[C@H](CN3C(=O)[C@H](C(C)(C)C)NC(=O)CCCCCCCCCCNCCCONC(=O)C4=C(C(=C(C=C4)F)F)NC5=C(C=C(C=C5)I)F)O Chemical compound CC1=C(SC=N1)C2=CC=C(C=C2)[C@H](C)NC(=O)[C@@H]3C[C@H](CN3C(=O)[C@H](C(C)(C)C)NC(=O)CCCCCCCCCCNCCCONC(=O)C4=C(C(=C(C=C4)F)F)NC5=C(C=C(C=C5)I)F)O KCBAMQOKOLXLOX-BSZYMOERSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
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- LVDRREOUMKACNJ-BKMJKUGQSA-N N-[(2R,3S)-2-(4-chlorophenyl)-1-(1,4-dimethyl-2-oxoquinolin-7-yl)-6-oxopiperidin-3-yl]-2-methylpropane-1-sulfonamide Chemical compound CC(C)CS(=O)(=O)N[C@H]1CCC(=O)N([C@@H]1c1ccc(Cl)cc1)c1ccc2c(C)cc(=O)n(C)c2c1 LVDRREOUMKACNJ-BKMJKUGQSA-N 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 206010034960 Photophobia Diseases 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- LJOOWESTVASNOG-UFJKPHDISA-N [(1s,3r,4ar,7s,8s,8as)-3-hydroxy-8-[2-[(4r)-4-hydroxy-6-oxooxan-2-yl]ethyl]-7-methyl-1,2,3,4,4a,7,8,8a-octahydronaphthalen-1-yl] (2s)-2-methylbutanoate Chemical compound C([C@H]1[C@@H](C)C=C[C@H]2C[C@@H](O)C[C@@H]([C@H]12)OC(=O)[C@@H](C)CC)CC1C[C@@H](O)CC(=O)O1 LJOOWESTVASNOG-UFJKPHDISA-N 0.000 description 1
- NZHXEWZGTQSYJM-UHFFFAOYSA-N [bromo(diphenyl)methyl]benzene Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)(Br)C1=CC=CC=C1 NZHXEWZGTQSYJM-UHFFFAOYSA-N 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 229940051880 analgesics and antipyretics pyrazolones Drugs 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910001622 calcium bromide Inorganic materials 0.000 description 1
- WGEFECGEFUFIQW-UHFFFAOYSA-L calcium dibromide Chemical compound [Ca+2].[Br-].[Br-] WGEFECGEFUFIQW-UHFFFAOYSA-L 0.000 description 1
- 229930008380 camphor Natural products 0.000 description 1
- 229920006218 cellulose propionate Polymers 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229940126543 compound 14 Drugs 0.000 description 1
- 229940125833 compound 23 Drugs 0.000 description 1
- 229940125851 compound 27 Drugs 0.000 description 1
- 229940127204 compound 29 Drugs 0.000 description 1
- 229940125877 compound 31 Drugs 0.000 description 1
- 229940125878 compound 36 Drugs 0.000 description 1
- 229940125807 compound 37 Drugs 0.000 description 1
- 229940127113 compound 57 Drugs 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- OPTDDWCXQQYKGU-UHFFFAOYSA-N diphenyldichloromethane Chemical compound C=1C=CC=CC=1C(Cl)(Cl)C1=CC=CC=C1 OPTDDWCXQQYKGU-UHFFFAOYSA-N 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical class [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Chemical class 0.000 description 1
- 239000010931 gold Chemical class 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 150000002443 hydroxylamines Chemical class 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 208000013469 light sensitivity Diseases 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002730 mercury Chemical class 0.000 description 1
- BRMYZIKAHFEUFJ-UHFFFAOYSA-L mercury diacetate Chemical compound CC(=O)O[Hg]OC(C)=O BRMYZIKAHFEUFJ-UHFFFAOYSA-L 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000004780 naphthols Chemical class 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000002896 organic halogen compounds Chemical class 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 150000004986 phenylenediamines Chemical class 0.000 description 1
- XKJCHHZQLQNZHY-UHFFFAOYSA-N phthalimide Chemical compound C1=CC=C2C(=O)NC(=O)C2=C1 XKJCHHZQLQNZHY-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 125000005936 piperidyl group Chemical group 0.000 description 1
- 229920000191 poly(N-vinyl pyrrolidone) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 150000003219 pyrazolines Chemical class 0.000 description 1
- 125000002755 pyrazolinyl group Chemical group 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 231100000489 sensitizer Toxicity 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- LTYHQUJGIQUHMS-UHFFFAOYSA-M silver;hexadecanoate Chemical compound [Ag+].CCCCCCCCCCCCCCCC([O-])=O LTYHQUJGIQUHMS-UHFFFAOYSA-M 0.000 description 1
- ORYURPRSXLUCSS-UHFFFAOYSA-M silver;octadecanoate Chemical compound [Ag+].CCCCCCCCCCCCCCCCCC([O-])=O ORYURPRSXLUCSS-UHFFFAOYSA-M 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- CVYDEWKUJFCYJO-UHFFFAOYSA-M sodium;docosanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCCCCCC([O-])=O CVYDEWKUJFCYJO-UHFFFAOYSA-M 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- RKSOPLXZQNSWAS-UHFFFAOYSA-N tert-butyl bromide Chemical compound CC(C)(C)Br RKSOPLXZQNSWAS-UHFFFAOYSA-N 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/494—Silver salt compositions other than silver halide emulsions; Photothermographic systems ; Thermographic systems using noble metal compounds
- G03C1/498—Photothermographic systems, e.g. dry silver
- G03C1/49827—Reducing agents
Definitions
- This invention relates to a single-layer or multi-layer lightsensitive recording material containing an oxidising agent, a reducing agent and a lightsensitive compound whose photolytic products initiate a redox reaction between the oxidising agent and reducing agent on subsequent heating.
- a photographic material which contains an oxidising agent, a reducing agent and a relatively small quantity of a lightsensitive substance whose photolytic products found at the light-struck areas initiate a redox reaction.
- Organic silver salts are used as the oxidising agents and aminophenols, hydroxylamines, pyrazolidones or phenols as the reducing agent.
- Suitable lightsensitive
- the compounds include heavy metal salts which, on exposure, form nuclei of the free metal. More particularly, the lightsensitive compounds are light-sensitive silver salts, for example silver halides, which on exposure undergo photolysis to form silver. The redox reaction is initiated by these photolytic heavy metal nuclei.
- a photographic recording material for, the production of dry copies which contains a silver salt that is substantially non-sensitive to light as oxidising agent, a reducing agent and a lightsensitive heavy metal compound which on exposure photolytically forms metal nuclei through which a redox reaction is initiated under the effect of heat, the reducing agent used being a compound of the pyrazolin-S-one series which is able to reduce the non-lightsensitive silver salt at a temperature of from 60 to 160 C. in the presence of photolytically formedheavy-metal nuclei.
- Particularly suitable reducing agents include pyrazolin-5-one compounds ofthe kind which contain at least one hydrogen atom or a 4-aminophenylamino group in the 4-position of the pyrazoline ring. It is preferred to use pyrazoline derivatives of the following formula B4 TIT-31 in which R represents (1) hydrogen, (2) a saturated or olefinically unsaturated aliphatic group having up to 18 C- atoms, preferably up to five C-atoms, which can optionally be substituted, for example by phenyl, as in the ably up to five C-atoms, by halogen such as fluorine,
- R represents (1 hydrogen, (2) a saturated or olefinically unsaturated aliphatic group having up to 18 carbon atoms, in which case the aliphatic group can contain further substituents, for example phenyl, as in the case of a benzyl or phenylethyl group, halogen such as fluorine, alkoxycarbonyl, hydroxyl or alkoxy, (3) aryl, especially a group of the phenyl series in which case the aryl ring can be substituted, for example by alkyl or alkoxy with preferably up-to five C-atoms', by halogen such as chlorine or bromine, by hydroxyl, by nitro or by acyl, (4) a heterocyclic group, especially a ring of the pyridine, furan or thiophene, series, (5) a cycloalkyl group, such as cyclohexyl or cyclopentyl, (6) an alkoxycarbonyl group with up to l
- R represents (1) hydrogen, (2) a saturated or olefin ically unsaturated aliphatic group having up to 18 C- atoms, preferably with up to five C-atoms, which can be substituted, for example by phenyl as in the case of benzyl or phenylethyl groups, with halogen such as chlorine or bromine, by nitrile, by alkoxy, by amino groups which in turn can be substituted, for example by alkyl, phenyl, substituted phenyl for example dialkylaminophenyl or sulfophenyl, by carbamoyl, alkoxycarbonyl, piperidyl or the like, (3) aryl, especially a group of the phenyl series which can in turn be substituted,
- alkyl or alkoxy with preferably up to five C-atoms for example by alkyl or alkoxy with preferably up to five C-atoms, (4) amino, which can be substituted for example by acyl, especially those of aliphatic carboxylic acids with up to 18 C-atoms or benzoyl, (5) alkoxy with preferably up to five C-atoms like the aforementioned aliphatic group, and which can contain further substituents, (6) halogen, for example, chlorine or bromine, (7) cycloalkyl such as cyclopentyl, or (8) carbamoyl, and when R represents hydrogen R can also represent an alkylene chain between two pyrazolone rings of the above formula; and
- pyrazolin-5-one derivatives used in accordance with the present invention can be obtained by known methods. Suitable methods are described, for example, in the monograph by RH. Wiley and P. Wiley Pyrazolones, pyrazolidones and Derivatives 1964) (Interscience Publishers, New York) and in German Pat. specification No. 1,155,675.
- suitable oxidising agents for the image-producing redox system include silver salts of organic acids which show little or no lightsensitivity under the conditions of the process.
- silver sacchan'de silver 5- chlorosalicylaldoxime, silver 5-nitrosalicylaldoxime or preferably a silver salt of a long-chain fatty acid with up to about 30 C-atoms, for example silver stearate, silver palmitate or silver behenate, or the silver salts of aliphatic carboxylic acidscontaining a-thioether group described in US. Pat. No. 3,330,663.
- non-lightsensitive silver salt used as oxidising agent and the pyrazolin-5-one used as reducing agent are generally employed in a molar ratio of from 1:1, to
- Inorganic or organic salts of silver, mercury or gold are examples of suitable lightsensitive heavy metal salts which on exposure form metal nuclei able to initiate the image-producing redox reaction.
- Heavy metals of Sub-Group lb of the Periodic System of elements, especially silver salts, are preferred. Of these silver salts, silver halides'are especially suitable.
- the light sensitive heavy metal salt most suitable for the particular redox system employed can be found by a few laborating tests.
- an aqueous suspension of the metal salt can be mixed with the components of the redox system, in which case no changes should occur in darkness. If this mixture is exposed to UV-radiation, it should become colored relatively quickly. If this is observed, the. heavy metal salt is suitable for use with the'redox system.
- the lightsensitive heavy metal salt is preferably used in relatively small quantities of from about 0.05 to 0.2 percent by weight, based on the weight of the oxidising agent. This proportion of photosensitive salt is sufficient for mostsystems. In exceptional instances, this percentage can of course be increased or reduced.
- the lightsensitive heavy metal salt for example the silver halide
- the lightsensitive heavy metal salt should be present in such small quantities that the photolytically formed heavy metal nuclei can initiate the redox reaction, although the concentration of the silver halide should be so low that the metal nuclei formed cause little or no discoloration of the photographic material.
- the silver halide can be added to the casting solution for the layer containing the components for the redox reaction or alternatively can be prepared in situ in the casting solution, i.e., by precipitating the silver halide in the mixture.
- the silver ions for the precipitated silver halide can be provided substantially by the nonlight-sensitive silver salt.
- the non-lightsensitive silver salts present as oxidising agents can be prepared in known manner by precipitating silver salt solutions, for
- the silver halides can be produced from the nonlight-sensitive silver salts in various different ways.
- the surface of the non-lightsensitive silver salts can be treated with vapours of hydrohalic acids, for example hydrochloric acid, hydrobromic acid or hydriodic acid.
- the quantity of silver halide formed at the surface can be kept within the required limits by adjusting the concentration of-the hydrogen halide in the vapour phase, and the treatment time.
- the non-lightsensitive silver salts of the organic acids can, of course, also be treated with a solution containing halogen ions, such as chloride ions, bromide ions or iodide ions.
- halogen ions such as chloride ions, bromide ions or iodide ions.
- the halogen ions can be provided by the hydrohalic acids themselves or by their salts, especially their ammonium 'or alkali metal salts.
- non-lightsensitive silver salts are reacted with the compounds yielding halogen ions preferably in the form of their suspensions in a volatile non-aqueous liquid. It is also possible, however, to react the dry salts with hydrohalic acid vapours for example.
- hydrohalic acids and their salts for example the already mentioned alkali metal salts and ammonium salts, alkaline earth metal salts or other metal salts, for example zinc salts and mercury salts
- ionisable organic halogen compounds for example triphenylinethyl chloride, triphenylmethyl bromide, 2-bromo-2-methylpropane, Z-bromobutyric acid, 2-bromoethanol or benzophenone dichloride.
- Formation of the lightsensitive silver halides from the non-lightsensitive silver salts of the organic acids is preferredfor the production of the materials according to the present invention. This enhances the ability of the silverhalides to form, on photolysis, silver nuclei which are particularly active in initiating the redox reaction.
- binders include organic polymers, such as copolymers of vinyl chloride and vinyl acetate or of butadiene and styrene, polyethylene, polyamides, polyisobutylene, polyvinyl chloride, polyvinylidene chloride, polyvinyl pyrrolidone, polystyrene, chlorinated rubber, polyvinyl butyral, polymers or acrylic acid or methacrylic acid esters or copolymers of derivatives of acrylic acid and methacrylic acid, and cellulose derivatives such as nitrocellulose, cellulose acetate, cellulose propionates or mixtures thereof such as cellulose acetobutyrates.
- organic polymers such as copolymers of vinyl chloride and vinyl acetate or of butadiene and styrene, polyethylene, polyamides, polyisobutylene, polyvinyl chloride, polyvinylidene chloride, polyvinyl pyrrolidone, polystyrene, chlorinated rubber
- the lightsensitive layer can be a selfsupporting layer, it is preferably applied to a suitable layer support.
- the layer support must be stable at the processing temperature of from 60 to 200 C.
- suitable supports include sheets or films of paper, cellulose acetate, polyethylene terephthalate, textile fabrics, metal foils or glass. 1n the case of paper supports, they can comprise the usual auxiliary layers such as baryta layers, polyethylene layers, etc.
- the concentration of the reducing agent and of the oxidising agent in the layer can be varied within wide limits.
- weight ratios between the components of the redox system and the binder of from 4:1 4to about 1:1 have provded to be adequate.
- the thickness of the lightsensitive layer can also be adapted to suit the requirements of the particular reproduction process. In general, layer thicknesses of from S to 100 microns are sufficient for normal requirements.
- the layer supports preferably have the usual thickness of from about 0.1 to 0.8 mm.
- the lightsensitive layers can also be optically sensitised by the addition of dyes.
- Preferred sensitisers include those compounds of the kind that are also normally used for optically sensitising conventional silver halide emulsion layers, i.e., cyanine dyes, merocyanines, oxonoles or thiocyanines of various kinds, for example those described in the book by EM. Hamer entitled The Cyanine Dyes and Related Compounds, 1964.
- the usual white pigments for example silicon dioxide, and toners such as for example phthalazone, phthalazone derivatives, or phthalimide, can be added to the photosensitive layers.
- the photographic materials according to the invention can be processed in known manner.
- Image-wise exposure is carried out with the light sources commonly used in the photographic art, for example. mercury lamps, quartz-iodine lamps or ordinary incandescent lamps.
- the type of light source used will depend upon the spectral sensitivity of the heavy metal salt used. When silver halides are used, as is preferably the case, ordinary incandescent lamps are sufficient.
- the exposure time amounts to a few seconds.
- the exposed material is then uniformly heated at a temperature of from about 60 to 160 C.
- the time and the temperature required for heat treatment will be governed by the type of redox system used. Times of from 3 to 80 seconds are generally sufficient. As a rule, a dark brown to black image is obtained and can be immediately used.
- EXAMPLE 1 Lightsensitive material An equimolar mixture of silver behenate and behenic acid is prepared by precipitating silver nitrate with a solution of sodium behenate and behenic acid in alcohol and water. The precipitate is carefully washed and dried.
- the suspension for the preparation of the layer is prepared by treating'the mixture indicated below for 12 hours in a ball mill:
- the above mixture is applied to a paper support in a concentration of 100 g/m and dried at room temperature.
- the lightsensitive layer is exposed through a transparent original.
- a 750 watt UV-lamp is used as the light source.
- the exposure time is 2 seconds, the distance from the light source 5 cm. This is followed by heating for 5 seconds at a temperature of C.
- the application is such that the applied layer contains from 0.3 to 0.4 g/m of silver in the form of the silver salt.
- the top casting is then applied to the dried sub-casting.
- the reducing agent is applied in a quantity of from 0.5 to 1.5 g/m.
- the reducing agents can be added to the sublayer suspension and ground with this suspension in a ball mill for about 30 minutes, for example:
- the lightsensitive material is exposed for 3 to 30 seconds with tungsten lamps, depending upon their intensity and upon the required gradation, and developed by heating.
- the developing time ranges from 3 to 80 seconds depending upon the temperature, which can be in the range from 60 to 160 C. and the apparatus used.
- Suitable developing apparatus include heatable presses, drying cylinders, rollers, the apparatus described in Belgian Pat. No. 628,174 and in French Pat. Nos. 1,512,332; 1,416,752 or 1,419,101, and conventional commercial apparatus.
- the layer side of the material can be developed under heat in contact with a polyester film.
- Brown, brown-black to neutral-black images on a white to yellow background are obtained upon heating depending upon the reducing substance used and the processing conditions.
- a photographic composition containing in layer form a substantially non-lightsensitive silver salt as an oxidizing agent and a reducing agent in a combination substantially latent under ambient conditions and a light-sensitive heavy metal compound which photolytically forms metal nuclei that upon heating of the composition initiate into reaction the oxidizing agent and the reducing agent to produce a visible change
- the improvement comprises the reducing agent is a pyrazolin-S-one of the following formula:
- R represents hydrogen, a saturated or olefinically unsaturated aliphatic group having up to 18 carbons, aryl, a heterocyclic group or cycloalkyl;
- R represents hydrogenQa saturated or olefinically unsaturated aliphatic group having up to 18 carbons, aryl, a heterocyclic group, an amino group, cycloalkyl, alkoxycarbonyl having up to 18 C- atoms, hydroxyl, a carbamic acid ester group or a carbamoyl group;
- R represents hydrogen, a saturated or olefinically unsaturated aliphatic group having up to 18 carbons, aryl, alkoxy, halogen, cycloalkyl, or carbamoyl;
- R represents hydrogen or a 4-aminophenylamino group; and R and R together can represent the ring members required to complete a fiveor sixmembered ring.
- composition of claim 1, wherein the photosensitive heavy metal salt is a silver halide.
- composition of claim 3 wherein the heavy metal salt is present in a quantity of from 0.05 to 0.2 percent by weight, based on the weight of the nonlightsensitive silver salt.
- composition of claim 1, wherein the non-lightsensitive silver salt is a silver salt of along-chain fatty acid.
- composition of claim 1, wherein the non-lightsensitive silver salt is silver behenate.
- composition of claim 1 wherein the non-lightsensitive silver salt is a silver salt of an aliphatic carboxylic acid substituted by a thioether group.
- composition of claim 1 in which the silver halide compound is a silver salt formed in situ.
- composition of claim 1 in which the silver halide compound is a silver salt formed on the surface of the non-lightsensitive silver compound.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
Abstract
Photographic images are obtained by a dry process by imagewise exposing and then heating a light-sensitive material containing a substantially non-lightsensitive silver salt, a compound of the pyrazolin-5-on series capable of reducing the silver salt at a temperature of between 60* and 160* C in the presence of photolytically formed heavy metal nuclei and a light-sensitive silver or other heavy metal compound capable of forming such nuclei upon exposure to light.
Description
United States Patent I 11 1 Poot et al. I Nov. 6, 1973 54] LIGHTSENSITIVE PHOTOGRAPHIC 3,149,990 9/1964 c6165 96/ll4.l MATERIAL 3,457,075 11/1969 Morgan 96/1141 3,531,286 9/1970 Renfrew 96/1 14.1
Inventors: Albert Lucien Poot; Frans Clement Heugebaert, both of Kontich; Eric Maria Brinckman, Mortsel, all of Belgium; Anita Von Kiinig, Leverkusen; l-lelmut Kampfer, Cologne, both of Germany Assignee: Afga-Gevaert Aktiengesellschaft,
Leverkusen, Germany Filed: Apr. 26, 1971 Appl. No.: 137,604
Foreign Application Priority Data Apr. 29, 1970 Germany P 20 20 939.6
US. Cl. 96/1l4.l, 96/66 R, 96/66 T lnt. Cl G03c 1/02, G030 5/30 Field of Search 96/1 14.1, 66 HD,
96/66 T, 48 HD References Cited UNITED STATES PATENTS 7/1969 Sorenson 96/1l4.l
OTHER PUBLICATIONS Handbook of Photography, ed. by Henney et al., I939, ed. pp. 329-333.
Primary Examiner-Norman G. Torchin Assistant ExaminerM. F. Kelley Att0meyConnolly and Hutz 57 ABSTRACT 8 Claims, No Drawings This invention relates to a single-layer or multi-layer lightsensitive recording material containing an oxidising agent, a reducing agent and a lightsensitive compound whose photolytic products initiate a redox reaction between the oxidising agent and reducing agent on subsequent heating.
In conventional photographic recording processes, photographic materials containing lightsensitive silver halide/gelatin emulsion layers are exposed to light and subsequently treated with a developer solution, and the resulting developed image is finally fixed in a fixing bath.
This conventional recording process has previously been modified in several different ways in order to avoid the use of aqueous treatment baths. The object of all such efforts has been to modify the known process in such a way that a recording of adequate quality is obtained in a dry process, optionally employing heat, with as few process steps as possible.'
According to a known process there is used a photographic material which contains an oxidising agent, a reducing agent and a relatively small quantity of a lightsensitive substance whose photolytic products found at the light-struck areas initiate a redox reaction. Organic silver salts are used as the oxidising agents and aminophenols, hydroxylamines, pyrazolidones or phenols as the reducing agent. Phenylene diamine or etherified naphthols, for example 4-methoxy-1-naphthol, have also been used for this purpose. Suitable lightsensitive,
compounds include heavy metal salts which, on exposure, form nuclei of the free metal. More particularly, the lightsensitive compounds are light-sensitive silver salts, for example silver halides, which on exposure undergo photolysis to form silver. The redox reaction is initiated by these photolytic heavy metal nuclei.
As a result of these conventional processes, it is possible to produce photographic images of satisfactory quality under dry conditions. One serious disadvantage of the materials used in this process, however, is their relatively poor shelf life, which is attributable in particular to the sensitivity of the reducing agents to oxidation by atmospheric oxygen. In order to provide a shelf .45
life that is satisfactory for practical requirements, it is thus necessary to take additional measures to protect the reducing agents against the effect of atmospheric oxygen. In most instances, this is done by adding antioxidants. It is among the objects of this invention to provide photographic processes and materials therefor, by which it-is possible to obtain high-quality photographic images under dry conditions.
A photographic recording material for, the production of dry copies has now been found which contains a silver salt that is substantially non-sensitive to light as oxidising agent, a reducing agent and a lightsensitive heavy metal compound which on exposure photolytically forms metal nuclei through which a redox reaction is initiated under the effect of heat, the reducing agent used being a compound of the pyrazolin-S-one series which is able to reduce the non-lightsensitive silver salt at a temperature of from 60 to 160 C. in the presence of photolytically formedheavy-metal nuclei.
Particularly suitable reducing agents include pyrazolin-5-one compounds ofthe kind which contain at least one hydrogen atom or a 4-aminophenylamino group in the 4-position of the pyrazoline ring. It is preferred to use pyrazoline derivatives of the following formula B4 TIT-31 in which R represents (1) hydrogen, (2) a saturated or olefinically unsaturated aliphatic group having up to 18 C- atoms, preferably up to five C-atoms, which can optionally be substituted, for example by phenyl, as in the ably up to five C-atoms, by halogen such as fluorine,
chlorine or bromine, by nitro, by amino, by substituted amino groups, for example alkylated or acylated, especially acyl groups derived from aliphatic carboxylic acids, or by phenoxyor alkoxycarbonyl groups, (4) a heterocyclic group, for example a ring of the furan or pyridine series, or a condensed heterocyclic ring obtained therefrom by anellation of an aromatic ring system, or (5) a cycloalkyl group, such as cyclohexyl or cyclopentyl;
R represents (1 hydrogen, (2) a saturated or olefinically unsaturated aliphatic group having up to 18 carbon atoms, in which case the aliphatic group can contain further substituents, for example phenyl, as in the case of a benzyl or phenylethyl group, halogen such as fluorine, alkoxycarbonyl, hydroxyl or alkoxy, (3) aryl, especially a group of the phenyl series in which case the aryl ring can be substituted, for example by alkyl or alkoxy with preferably up-to five C-atoms', by halogen such as chlorine or bromine, by hydroxyl, by nitro or by acyl, (4) a heterocyclic group, especially a ring of the pyridine, furan or thiophene, series, (5) a cycloalkyl group, such as cyclohexyl or cyclopentyl, (6) an alkoxycarbonyl group with up to l8 C-atoms preferably up to five C-atoms 7) a hydroxyl group which can be etherified, especially with aliphatic radicals with up to 18 C- atoms, (8) an amino group which can be substituted, for example by alkyl-or acyl groups, especially those derived from aliphatic c'arboxylic acids with up to 18. C-atoms or with benzoyl, (9) a carbamic acidester group, especially with aliphatic ester groups with up to 18 carbon atoms or (10) a carbamoyl group. R represents (1) hydrogen, (2) a saturated or olefin ically unsaturated aliphatic group having up to 18 C- atoms, preferably with up to five C-atoms, which can be substituted, for example by phenyl as in the case of benzyl or phenylethyl groups, with halogen such as chlorine or bromine, by nitrile, by alkoxy, by amino groups which in turn can be substituted, for example by alkyl, phenyl, substituted phenyl for example dialkylaminophenyl or sulfophenyl, by carbamoyl, alkoxycarbonyl, piperidyl or the like, (3) aryl, especially a group of the phenyl series which can in turn be substituted,
for example by alkyl or alkoxy with preferably up to five C-atoms, (4) amino, which can be substituted for example by acyl, especially those of aliphatic carboxylic acids with up to 18 C-atoms or benzoyl, (5) alkoxy with preferably up to five C-atoms like the aforementioned aliphatic group, and which can contain further substituents, (6) halogen, for example, chlorine or bromine, (7) cycloalkyl such as cyclopentyl, or (8) carbamoyl, and when R represents hydrogen R can also represent an alkylene chain between two pyrazolone rings of the above formula; and
CII3 Num bnr 1 R2 R3 R 4 3 (kHz-F CH; CHzn-C'H3 N l L N (Jo-H5 C 0H5 The pyrazolin-5-one derivatives used in accordance with the present invention can be obtained by known methods. Suitable methods are described, for example, in the monograph by RH. Wiley and P. Wiley Pyrazolones, pyrazolidones and Derivatives 1964) (Interscience Publishers, New York) and in German Pat. specification No. 1,155,675.
As already mentioned, suitable oxidising agents for the image-producing redox system include silver salts of organic acids which show little or no lightsensitivity under the conditions of the process. Reference is made for example to silver sacchan'de, silver 5- chlorosalicylaldoxime, silver 5-nitrosalicylaldoxime or preferably a silver salt of a long-chain fatty acid with up to about 30 C-atoms, for example silver stearate, silver palmitate or silver behenate, or the silver salts of aliphatic carboxylic acidscontaining a-thioether group described in US. Pat. No. 3,330,663.
The non-lightsensitive silver salt used as oxidising agent and the pyrazolin-5-one used as reducing agent are generally employed in a molar ratio of from 1:1, to
Inorganic or organic salts of silver, mercury or gold are examples of suitable lightsensitive heavy metal salts which on exposure form metal nuclei able to initiate the image-producing redox reaction. Heavy metals of Sub-Group lb of the Periodic System of elements, especially silver salts, are preferred. Of these silver salts, silver halides'are especially suitable.
The light sensitive heavy metal salt most suitable for the particular redox system employed can be found by a few laborating tests. For example, an aqueous suspension of the metal salt can be mixed with the components of the redox system, in which case no changes should occur in darkness. If this mixture is exposed to UV-radiation, it should become colored relatively quickly. If this is observed, the. heavy metal salt is suitable for use with the'redox system. The lightsensitive heavy metal salt is preferably used in relatively small quantities of from about 0.05 to 0.2 percent by weight, based on the weight of the oxidising agent. This proportion of photosensitive salt is sufficient for mostsystems. In exceptional instances, this percentage can of course be increased or reduced.
The lightsensitive heavy metal salt, for example the silver halide, should be present in such small quantities that the photolytically formed heavy metal nuclei can initiate the redox reaction, although the concentration of the silver halide should be so low that the metal nuclei formed cause little or no discoloration of the photographic material.
The silver halide can be added to the casting solution for the layer containing the components for the redox reaction or alternatively can be prepared in situ in the casting solution, i.e., by precipitating the silver halide in the mixture. In this case, the silver ions for the precipitated silver halide can be provided substantially by the nonlight-sensitive silver salt.
Just like the silver halide, the non-lightsensitive silver salts present as oxidising agents can be prepared in known manner by precipitating silver salt solutions, for
example silver nitrate, with the alkali metal salts of the organic acids. The free acid can of course also be present during precipitation. In order, however, to produce layers as transparent as possible, it is of advantage for the excess of free acid to be extremely limited,"or e'ven for stoichiometric quantities of the organic acid and of the silver salt to be used. Q
The silver halides can be produced from the nonlight-sensitive silver salts in various different ways. For example, the surface of the non-lightsensitive silver salts can be treated with vapours of hydrohalic acids, for example hydrochloric acid, hydrobromic acid or hydriodic acid. The quantity of silver halide formed at the surface can be kept within the required limits by adjusting the concentration of-the hydrogen halide in the vapour phase, and the treatment time. i
The non-lightsensitive silver salts of the organic acids can, of course, also be treated with a solution containing halogen ions, such as chloride ions, bromide ions or iodide ions. The halogen ions can be provided by the hydrohalic acids themselves or by their salts, especially their ammonium 'or alkali metal salts.
The non-lightsensitive silver salts are reacted with the compounds yielding halogen ions preferably in the form of their suspensions in a volatile non-aqueous liquid. It is also possible, however, to react the dry salts with hydrohalic acid vapours for example.
In addition to hydrohalic acids and their salts, for example the already mentioned alkali metal salts and ammonium salts, alkaline earth metal salts or other metal salts, for example zinc salts and mercury salts, it is also possible to use ionisable organic halogen compounds, for example triphenylinethyl chloride, triphenylmethyl bromide, 2-bromo-2-methylpropane, Z-bromobutyric acid, 2-bromoethanol or benzophenone dichloride.
Formation of the lightsensitive silver halides from the non-lightsensitive silver salts of the organic acids is preferredfor the production of the materials according to the present invention. This enhances the ability of the silverhalides to form, on photolysis, silver nuclei which are particularly active in initiating the redox reaction.
Although separate preparation of the silver halides and subsequent mixing with the non-lightsensitive silver salts also leads to useful materials, the photolytic heavy metal nuclei formed from mixtures of this kind are generally not so effective.
To prepare the material according to the present invention, the components of the redox system and'the I lightsensitive heavy metal are used together with a suitable binder. Preferred binders include organic polymers, such as copolymers of vinyl chloride and vinyl acetate or of butadiene and styrene, polyethylene, polyamides, polyisobutylene, polyvinyl chloride, polyvinylidene chloride, polyvinyl pyrrolidone, polystyrene, chlorinated rubber, polyvinyl butyral, polymers or acrylic acid or methacrylic acid esters or copolymers of derivatives of acrylic acid and methacrylic acid, and cellulose derivatives such as nitrocellulose, cellulose acetate, cellulose propionates or mixtures thereof such as cellulose acetobutyrates.
Although the lightsensitive layer can be a selfsupporting layer, it is preferably applied to a suitable layer support. The layer support must be stable at the processing temperature of from 60 to 200 C. Examples of suitable supports include sheets or films of paper, cellulose acetate, polyethylene terephthalate, textile fabrics, metal foils or glass. 1n the case of paper supports, they can comprise the usual auxiliary layers such as baryta layers, polyethylene layers, etc.
The concentration of the reducing agent and of the oxidising agent in the layer can be varied within wide limits.
In general, weight ratios between the components of the redox system and the binder of from 4:1 4to about 1:1 have provded to be adequate.
The thickness of the lightsensitive layer can also be adapted to suit the requirements of the particular reproduction process. In general, layer thicknesses of from S to 100 microns are sufficient for normal requirements. The layer supports preferably have the usual thickness of from about 0.1 to 0.8 mm.
The lightsensitive layers can also be optically sensitised by the addition of dyes. Preferred sensitisers include those compounds of the kind that are also normally used for optically sensitising conventional silver halide emulsion layers, i.e., cyanine dyes, merocyanines, oxonoles or thiocyanines of various kinds, for example those described in the book by EM. Hamer entitled The Cyanine Dyes and Related Compounds, 1964.
The usual white pigments, for example silicon dioxide, and toners such as for example phthalazone, phthalazone derivatives, or phthalimide, can be added to the photosensitive layers.
The photographic materials according to the invention can be processed in known manner. Image-wise exposure is carried out with the light sources commonly used in the photographic art, for example. mercury lamps, quartz-iodine lamps or ordinary incandescent lamps. The type of light source used will depend upon the spectral sensitivity of the heavy metal salt used. When silver halides are used, as is preferably the case, ordinary incandescent lamps are sufficient. The exposure time amounts to a few seconds.
The exposed material is then uniformly heated at a temperature of from about 60 to 160 C. The time and the temperature required for heat treatment will be governed by the type of redox system used. Times of from 3 to 80 seconds are generally sufficient. As a rule, a dark brown to black image is obtained and can be immediately used.
In the procedure described above, negative copies of the original are, of course, obtained. Positive copies can be obtained by a transfer process. In this case, pyrazolin-S-one compounds which can be transferred under the influence of heat are used in the lightsensitive layer. After the lightsensitive material has been exposed to form an image, it is heated in contact with an image receiving layer. The image-receiving layer contains reagents which undergo a color-producing reaction with the pyrazolin-S-one derivative transferred from the unexposed areas. For example, the same nonlightsensitive silver salts of organic acids which are normally present in the lightsensitive layer can be used for this purpose.
EXAMPLE 1 Lightsensitive material: An equimolar mixture of silver behenate and behenic acid is prepared by precipitating silver nitrate with a solution of sodium behenate and behenic acid in alcohol and water. The precipitate is carefully washed and dried.
The suspension for the preparation of the layer is prepared by treating'the mixture indicated below for 12 hours in a ball mill:
240 ml of methanol v 125 ml of a 10 percent by weight solution of polyvinyl-n-butyral in methanol 20 ml of a 10 percent by weight solution of poly-N- vinyl-pyrrolidone in methanol 30 g of the equimolar mixture of silver behenate and behenic acid 10 ml of a 1 percent by weight solution of ammonium bromide in methanol 1.2 g of phthalazone 15 g of compound 10.
The above mixture is applied to a paper support in a concentration of 100 g/m and dried at room temperature.
Processing:
The lightsensitive layer is exposed through a transparent original. A 750 watt UV-lamp is used as the light source. The exposure time is 2 seconds, the distance from the light source 5 cm. This is followed by heating for 5 seconds at a temperature of C.
A black-brown negative image of the original is obtained. Similar results are obtained by using compounds 12, 33 or 34, for example, instead of compound 10.
EXAMPLE 2 Lightsensitive material: Sub-casting suspension: 1.8 g of the equimolar mixture of silver behenate and behenic acid 3 g of cellulose acetate 3 g of phthalazone 4.5 ml of calcium bromide solution (1 g dissolved inml of methanol) 5.7 ml of mercuric acetate solution (1 g 1 ml of glacial acetic acid dissolved in 100 ml of methanol) 3 ml of 1-methyl-3-allyl-5-[2-(3-ethylben'zoxazo1yliden-( 2 )-ethylidene]-2-thiohydantoin solution (0.01 g dissolved in 100 ml of chloroform) 0.15 g of silicon dioxide 55 g of acetone 1 g of 88:12 vinyl chloride/vinyl acetate copolymer dissolved in 20 g of butyl acetate Top-casting: 10 g of polyvinylbutyral 1.5 g of phthalazone 5 g of compound 44 100 ml of methanol The sub-casting suspension is ground in a ball mill for about 16 hours, applied to baryta paper and dried. The application is such that the applied layer contains from 0.3 to 0.4 g/m of silver in the form of the silver salt. The top casting is then applied to the dried sub-casting. The reducing agent is applied in a quantity of from 0.5 to 1.5 g/m.
Instead of compound 44 the following reducing agents can also be added to the top layer:
6 g of compound 5 6 g of compound 6 4 g of compound 8 5 g of compound 10 5 g of compound 13 g of compound 14 5 g of compound 23 5 g of compound 29 6 g of compound 31 4 g of compound 35 5 g of compound 36 4 g of compound 37 5 g of compound 40 5 g of compound 57 5 g of compound 60 Instead of being added to the top layer like compound 44, the reducing agents can be added to the sublayer suspension and ground with this suspension in a ball mill for about 30 minutes, for example:
6 g of compound 5 4 g of compound 27 4 g of compound 50 Processing:
The lightsensitive material is exposed for 3 to 30 seconds with tungsten lamps, depending upon their intensity and upon the required gradation, and developed by heating. The developing time ranges from 3 to 80 seconds depending upon the temperature, which can be in the range from 60 to 160 C. and the apparatus used. Suitable developing apparatus include heatable presses, drying cylinders, rollers, the apparatus described in Belgian Pat. No. 628,174 and in French Pat. Nos. 1,512,332; 1,416,752 or 1,419,101, and conventional commercial apparatus. In order to protect the layer and to produce a high-gloss image, the layer side of the material can be developed under heat in contact with a polyester film.
Brown, brown-black to neutral-black images on a white to yellow background are obtained upon heating depending upon the reducing substance used and the processing conditions.
We claim:
1. A photographic composition containing in layer form a substantially non-lightsensitive silver salt as an oxidizing agent and a reducing agent in a combination substantially latent under ambient conditions and a light-sensitive heavy metal compound which photolytically forms metal nuclei that upon heating of the composition initiate into reaction the oxidizing agent and the reducing agent to produce a visible change wherein the improvement comprises the reducing agent is a pyrazolin-S-one of the following formula:
in which R represents hydrogen, a saturated or olefinically unsaturated aliphatic group having up to 18 carbons, aryl, a heterocyclic group or cycloalkyl;
R represents hydrogenQa saturated or olefinically unsaturated aliphatic group having up to 18 carbons, aryl, a heterocyclic group, an amino group, cycloalkyl, alkoxycarbonyl having up to 18 C- atoms, hydroxyl, a carbamic acid ester group or a carbamoyl group;
R represents hydrogen, a saturated or olefinically unsaturated aliphatic group having up to 18 carbons, aryl, alkoxy, halogen, cycloalkyl, or carbamoyl;
R represents hydrogen or a 4-aminophenylamino group; and R and R together can represent the ring members required to complete a fiveor sixmembered ring.
2. The composition of claim 1, wherein the photosensitive heavy metal salt is a silver halide.
3. The composition of claim 1, wherein the heavy metal salt is present in a quantity of from 0.05 to 0.2 percent by weight, based on the weight of the nonlightsensitive silver salt.
4. The composition of claim 1, wherein the non-lightsensitive silver salt is a silver salt of along-chain fatty acid. a I
5. The composition of claim 1, wherein the non-lightsensitive silver salt is silver behenate.
6. The composition of claim 1, wherein the non-lightsensitive silver salt is a silver salt of an aliphatic carboxylic acid substituted by a thioether group.
7. The composition of claim 1 in which the silver halide compound is a silver salt formed in situ.
8. The composition of claim 1 in which the silver halide compound is a silver salt formed on the surface of the non-lightsensitive silver compound.
Claims (7)
- 2. The composition of claim 1, wherein the photosensitive heavy metal salt is a silver halide.
- 3. The composition of claim 1, wherein the heavy metal salt is present in a quantity of from 0.05 to 0.2 percent by weight, based on the weight of the non-lightsensitive silver salt.
- 4. The composition of claim 1, wherein the non-light-sensitive silver salt is a silver salt of a long-chain fatty acid.
- 5. The composition of claim 1, wherein the non-light-sensitive silver salt is silver behenate.
- 6. The composition of claim 1, wherein the non-light-sensitive silver salt is a silver salt of an aliphatic carboxylic acid substituted by a thioether group.
- 7. The composition of claim 1 in which the silver halide compound is a silver salt formed in situ.
- 8. The composition of claim 1 in which the silver halide compound is a silver salt formed on the surface of the non-lightsensitive silver compound.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE2020939A DE2020939C3 (en) | 1970-04-29 | 1970-04-29 | Photographic recording material |
Publications (1)
Publication Number | Publication Date |
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US3770448A true US3770448A (en) | 1973-11-06 |
Family
ID=5769743
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US00137604A Expired - Lifetime US3770448A (en) | 1970-04-29 | 1971-04-26 | Lightsensitive photographic material |
Country Status (8)
Country | Link |
---|---|
US (1) | US3770448A (en) |
JP (1) | JPS5347688B1 (en) |
BE (1) | BE765923A (en) |
CA (1) | CA981514A (en) |
CH (1) | CH554002A (en) |
DE (1) | DE2020939C3 (en) |
FR (1) | FR2090961A5 (en) |
GB (1) | GB1324284A (en) |
Cited By (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3870523A (en) * | 1973-01-17 | 1975-03-11 | Fuji Photo Film Co Ltd | Heat developable photographic material containing azo dyes as sensitizers |
US3909271A (en) * | 1973-01-31 | 1975-09-30 | Fuji Photo Film Co Ltd | Heat developable photographic material containing sensitizers |
US3933507A (en) * | 1971-08-12 | 1976-01-20 | Agfa-Gevaert, A.G. | Photographic light-sensitive and heat developable material |
US4157289A (en) * | 1977-05-06 | 1979-06-05 | Fuji Photo Film Co., Ltd. | Process for preparing slightly soluble silver salt grains |
US4212937A (en) * | 1977-12-23 | 1980-07-15 | Asahi Kasei Kogyo Kabushiki Kaisha | Heat developable photosensitive materials |
US4268626A (en) * | 1978-08-28 | 1981-05-19 | Asahi Kasei Kogyo Kabushiki Kaisha | Dry image forming material |
US5409798A (en) * | 1991-08-30 | 1995-04-25 | Canon Kabushiki Kaisha | Plate blank, process for producing printing plate from plate blank, and printing method and apparatus using plate |
US5552409A (en) * | 1990-09-21 | 1996-09-03 | Rohm And Haas Company | Dihydropyridazinones, pyridazinones and related compounds as fungicides |
US5599648A (en) * | 1990-08-03 | 1997-02-04 | Canon Kabushiki Kaisha | Surface reforming method, process for production of printing plate, printing plate and printing process |
US5631254A (en) * | 1990-09-21 | 1997-05-20 | Rohm And Haas Company | Dihydropyridazinones, pyridazinones and related compounds as fungicides |
EP0802178A2 (en) | 1996-02-23 | 1997-10-22 | Fuji Photo Film Co., Ltd. | Schiff base quinone complexes and optical recording materials comprising the same |
FR2869905A1 (en) * | 2004-05-10 | 2005-11-11 | Sanofi Synthelabo | PROCESS FOR PREPARING ESTER OF 1,5-DIPHENYLPYRAZOLE CARBOXYLIC ACID |
US20060014111A1 (en) * | 2004-07-15 | 2006-01-19 | Konica Minolta Medical & Graphic, Inc. | Method of forming an image |
US20060088785A1 (en) * | 2004-10-22 | 2006-04-27 | Konica Minolta Medical & Graphic, Inc. | Silver salt photothermographic dry imaging material, thermal development method of the same, and thermal development apparatus for the same |
WO2007010777A1 (en) | 2005-07-20 | 2007-01-25 | Konica Minolta Medical & Graphic, Inc. | Method for image formation |
EP1953592A1 (en) | 2007-02-02 | 2008-08-06 | Konica Minolta Medical & Graphic, Inc. | Photothermographic material |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5129819B2 (en) * | 1972-03-27 | 1976-08-27 | ||
EP0227141A1 (en) * | 1985-11-26 | 1987-07-01 | Agfa-Gevaert N.V. | A process for the production of a photothermographic material |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US26719A (en) * | 1860-01-03 | Medicated pad | ||
US3149990A (en) * | 1962-01-19 | 1964-09-22 | Minnesota Mining & Mfg | Heat-sensitive copy-sheet |
US3457075A (en) * | 1964-04-27 | 1969-07-22 | Minnesota Mining & Mfg | Sensitized sheet containing an organic silver salt,a reducing agent and a catalytic proportion of silver halide |
US3531286A (en) * | 1966-10-31 | 1970-09-29 | Minnesota Mining & Mfg | Light-sensitive,heat developable copy-sheets for producing color images |
-
1970
- 1970-04-29 DE DE2020939A patent/DE2020939C3/en not_active Expired
-
1971
- 1971-04-19 BE BE765923A patent/BE765923A/en unknown
- 1971-04-23 CH CH594071A patent/CH554002A/en not_active IP Right Cessation
- 1971-04-23 CA CA111,154A patent/CA981514A/en not_active Expired
- 1971-04-26 US US00137604A patent/US3770448A/en not_active Expired - Lifetime
- 1971-04-26 GB GB1127271*[A patent/GB1324284A/en not_active Expired
- 1971-04-29 FR FR7115443A patent/FR2090961A5/fr not_active Expired
- 1971-04-30 JP JP2809171A patent/JPS5347688B1/ja active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US26719A (en) * | 1860-01-03 | Medicated pad | ||
US3149990A (en) * | 1962-01-19 | 1964-09-22 | Minnesota Mining & Mfg | Heat-sensitive copy-sheet |
US3457075A (en) * | 1964-04-27 | 1969-07-22 | Minnesota Mining & Mfg | Sensitized sheet containing an organic silver salt,a reducing agent and a catalytic proportion of silver halide |
US3531286A (en) * | 1966-10-31 | 1970-09-29 | Minnesota Mining & Mfg | Light-sensitive,heat developable copy-sheets for producing color images |
Non-Patent Citations (1)
Title |
---|
Handbook of Photography, ed. by Henney et al., 1939, ed. pp. 329 333. * |
Cited By (24)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3933507A (en) * | 1971-08-12 | 1976-01-20 | Agfa-Gevaert, A.G. | Photographic light-sensitive and heat developable material |
US3870523A (en) * | 1973-01-17 | 1975-03-11 | Fuji Photo Film Co Ltd | Heat developable photographic material containing azo dyes as sensitizers |
US3909271A (en) * | 1973-01-31 | 1975-09-30 | Fuji Photo Film Co Ltd | Heat developable photographic material containing sensitizers |
US4157289A (en) * | 1977-05-06 | 1979-06-05 | Fuji Photo Film Co., Ltd. | Process for preparing slightly soluble silver salt grains |
US4212937A (en) * | 1977-12-23 | 1980-07-15 | Asahi Kasei Kogyo Kabushiki Kaisha | Heat developable photosensitive materials |
US4268626A (en) * | 1978-08-28 | 1981-05-19 | Asahi Kasei Kogyo Kabushiki Kaisha | Dry image forming material |
US5599648A (en) * | 1990-08-03 | 1997-02-04 | Canon Kabushiki Kaisha | Surface reforming method, process for production of printing plate, printing plate and printing process |
US5728694A (en) * | 1990-09-21 | 1998-03-17 | Rohm And Haas Company | Dihydropyridazinones, pyridazinones and related compounds as fungicides |
US5552409A (en) * | 1990-09-21 | 1996-09-03 | Rohm And Haas Company | Dihydropyridazinones, pyridazinones and related compounds as fungicides |
US5631254A (en) * | 1990-09-21 | 1997-05-20 | Rohm And Haas Company | Dihydropyridazinones, pyridazinones and related compounds as fungicides |
US5753642A (en) * | 1990-09-21 | 1998-05-19 | Rohm And Haas Company | Dihydropyridazinones, pyridazinones and related compounds as fungicides |
US5726176A (en) * | 1990-09-21 | 1998-03-10 | Rohm And Haas Company | Dihydropyridazinones, pyridazinones and related compounds as fungicides |
US5726162A (en) * | 1990-09-21 | 1998-03-10 | Rohm And Haas Company | Dihydropyridazinones, pyridazinones and related compounds as fungicides |
US5728715A (en) * | 1990-09-21 | 1998-03-17 | Rohm And Haas Company | Dihydropyridazinones, pyridazinones and related compounds as fungicides |
US5728698A (en) * | 1990-09-21 | 1998-03-17 | Rohm And Haas Company | Dihydropyridazinones, pyridazinones and related compounds as fungicides |
US5409798A (en) * | 1991-08-30 | 1995-04-25 | Canon Kabushiki Kaisha | Plate blank, process for producing printing plate from plate blank, and printing method and apparatus using plate |
EP0802178A2 (en) | 1996-02-23 | 1997-10-22 | Fuji Photo Film Co., Ltd. | Schiff base quinone complexes and optical recording materials comprising the same |
FR2869905A1 (en) * | 2004-05-10 | 2005-11-11 | Sanofi Synthelabo | PROCESS FOR PREPARING ESTER OF 1,5-DIPHENYLPYRAZOLE CARBOXYLIC ACID |
US20060014111A1 (en) * | 2004-07-15 | 2006-01-19 | Konica Minolta Medical & Graphic, Inc. | Method of forming an image |
US7267934B2 (en) | 2004-07-15 | 2007-09-11 | Konica Minolta Medical & Graphic, Inc. | Method of forming an image |
US20060088785A1 (en) * | 2004-10-22 | 2006-04-27 | Konica Minolta Medical & Graphic, Inc. | Silver salt photothermographic dry imaging material, thermal development method of the same, and thermal development apparatus for the same |
US7220536B2 (en) | 2004-10-22 | 2007-05-22 | Konica Minolta Medical & Graphic, Inc. | Silver salt photothermographic dry imaging material, thermal development method of the same, and thermal development apparatus for the same |
WO2007010777A1 (en) | 2005-07-20 | 2007-01-25 | Konica Minolta Medical & Graphic, Inc. | Method for image formation |
EP1953592A1 (en) | 2007-02-02 | 2008-08-06 | Konica Minolta Medical & Graphic, Inc. | Photothermographic material |
Also Published As
Publication number | Publication date |
---|---|
FR2090961A5 (en) | 1972-01-14 |
JPS5347688B1 (en) | 1978-12-22 |
DE2020939A1 (en) | 1972-02-24 |
CH554002A (en) | 1974-09-13 |
DE2020939C3 (en) | 1978-11-02 |
CA981514A (en) | 1976-01-13 |
DE2020939B2 (en) | 1978-03-09 |
BE765923A (en) | 1971-10-19 |
GB1324284A (en) | 1973-07-25 |
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