EP0600586B1 - Photothermographic elements - Google Patents
Photothermographic elements Download PDFInfo
- Publication number
- EP0600586B1 EP0600586B1 EP93307739A EP93307739A EP0600586B1 EP 0600586 B1 EP0600586 B1 EP 0600586B1 EP 93307739 A EP93307739 A EP 93307739A EP 93307739 A EP93307739 A EP 93307739A EP 0600586 B1 EP0600586 B1 EP 0600586B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- silver
- emulsion
- group
- pat
- compound
- 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
- 229910052709 silver Inorganic materials 0.000 claims description 108
- 239000004332 silver Substances 0.000 claims description 108
- -1 silver halide Chemical class 0.000 claims description 73
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 68
- 239000000839 emulsion Substances 0.000 claims description 44
- 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 description 38
- 150000001875 compounds Chemical class 0.000 claims description 33
- 239000003638 chemical reducing agent Substances 0.000 claims description 17
- 125000003118 aryl group Chemical group 0.000 claims description 11
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 239000011230 binding agent Substances 0.000 claims description 8
- 125000001072 heteroaryl group Chemical group 0.000 claims description 7
- 125000005647 linker group Chemical group 0.000 claims description 5
- 150000007524 organic acids Chemical class 0.000 claims description 5
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims description 4
- DIKBFYAXUHHXCS-OUBTZVSYSA-N tribromomethane Chemical group Br[13CH](Br)Br DIKBFYAXUHHXCS-OUBTZVSYSA-N 0.000 claims description 4
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 2
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims 1
- 239000010410 layer Substances 0.000 description 41
- 239000012948 isocyanate Substances 0.000 description 40
- 239000000975 dye Substances 0.000 description 32
- 150000002513 isocyanates Chemical class 0.000 description 26
- 239000000463 material Substances 0.000 description 22
- 230000032683 aging Effects 0.000 description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 238000000034 method Methods 0.000 description 14
- 150000003378 silver Chemical class 0.000 description 14
- 239000000243 solution Substances 0.000 description 12
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 150000003839 salts Chemical class 0.000 description 9
- 238000000576 coating method Methods 0.000 description 8
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 8
- AQRYNYUOKMNDDV-UHFFFAOYSA-M silver behenate Chemical compound [Ag+].CCCCCCCCCCCCCCCCCCCCCC([O-])=O AQRYNYUOKMNDDV-UHFFFAOYSA-M 0.000 description 8
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 7
- 239000004615 ingredient Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000000344 soap Substances 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000003384 imaging method Methods 0.000 description 6
- 239000003381 stabilizer Substances 0.000 description 6
- 125000001424 substituent group Chemical group 0.000 description 6
- 238000010276 construction Methods 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 229910052736 halogen Inorganic materials 0.000 description 5
- 150000002367 halogens Chemical class 0.000 description 5
- 230000001681 protective effect Effects 0.000 description 5
- 230000001235 sensitizing effect Effects 0.000 description 5
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 4
- 235000021357 Behenic acid Nutrition 0.000 description 4
- NVXLIZQNSVLKPO-UHFFFAOYSA-N Glucosereductone Chemical compound O=CC(O)C=O NVXLIZQNSVLKPO-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 238000007792 addition Methods 0.000 description 4
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 4
- 229940116226 behenic acid Drugs 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- AFOSIXZFDONLBT-UHFFFAOYSA-N divinyl sulfone Chemical compound C=CS(=O)(=O)C=C AFOSIXZFDONLBT-UHFFFAOYSA-N 0.000 description 4
- DZVCFNFOPIZQKX-LTHRDKTGSA-M merocyanine Chemical compound [Na+].O=C1N(CCCC)C(=O)N(CCCC)C(=O)C1=C\C=C\C=C/1N(CCCS([O-])(=O)=O)C2=CC=CC=C2O\1 DZVCFNFOPIZQKX-LTHRDKTGSA-M 0.000 description 4
- 229910052751 metal Chemical class 0.000 description 4
- 239000002184 metal Chemical class 0.000 description 4
- KFPBEVFQCXRYIR-UHFFFAOYSA-N n-(3,5-dichloro-4-hydroxyphenyl)benzenesulfonamide Chemical compound C1=C(Cl)C(O)=C(Cl)C=C1NS(=O)(=O)C1=CC=CC=C1 KFPBEVFQCXRYIR-UHFFFAOYSA-N 0.000 description 4
- IJAPPYDYQCXOEF-UHFFFAOYSA-N phthalazin-1(2H)-one Chemical class C1=CC=C2C(=O)NN=CC2=C1 IJAPPYDYQCXOEF-UHFFFAOYSA-N 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 229910001622 calcium bromide Inorganic materials 0.000 description 3
- WGEFECGEFUFIQW-UHFFFAOYSA-L calcium dibromide Chemical compound [Ca+2].[Br-].[Br-] WGEFECGEFUFIQW-UHFFFAOYSA-L 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 125000005442 diisocyanate group Chemical group 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002460 imidazoles Chemical class 0.000 description 3
- 229920006267 polyester film Polymers 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 3
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 3
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical class NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 2
- QWDQYHPOSSHSAW-UHFFFAOYSA-N 1-isocyanatooctadecane Chemical compound CCCCCCCCCCCCCCCCCCN=C=O QWDQYHPOSSHSAW-UHFFFAOYSA-N 0.000 description 2
- SULYEHHGGXARJS-UHFFFAOYSA-N 2',4'-dihydroxyacetophenone Chemical compound CC(=O)C1=CC=C(O)C=C1O SULYEHHGGXARJS-UHFFFAOYSA-N 0.000 description 2
- MOXDGMSQFFMNHA-UHFFFAOYSA-N 2-hydroxybenzenesulfonamide Chemical compound NS(=O)(=O)C1=CC=CC=C1O MOXDGMSQFFMNHA-UHFFFAOYSA-N 0.000 description 2
- CWJJAFQCTXFSTA-UHFFFAOYSA-N 4-methylphthalic acid Chemical compound CC1=CC=C(C(O)=O)C(C(O)=O)=C1 CWJJAFQCTXFSTA-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 241001061127 Thione Species 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 229960005070 ascorbic acid Drugs 0.000 description 2
- 235000010323 ascorbic acid Nutrition 0.000 description 2
- 239000011668 ascorbic acid Substances 0.000 description 2
- 239000000987 azo dye Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- 150000001565 benzotriazoles Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 229920002301 cellulose acetate Polymers 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- 125000001841 imino group Chemical group [H]N=* 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- PQNFLJBBNBOBRQ-UHFFFAOYSA-N indane Chemical compound C1=CC=C2CCCC2=C1 PQNFLJBBNBOBRQ-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- BQPIGGFYSBELGY-UHFFFAOYSA-N mercury(2+) Chemical class [Hg+2] BQPIGGFYSBELGY-UHFFFAOYSA-N 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000000123 paper Substances 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- AUHHYELHRWCWEZ-UHFFFAOYSA-N tetrachlorophthalic anhydride Chemical compound ClC1=C(Cl)C(Cl)=C2C(=O)OC(=O)C2=C1Cl AUHHYELHRWCWEZ-UHFFFAOYSA-N 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 150000003918 triazines Chemical class 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- OOCCDEMITAIZTP-QPJJXVBHSA-N (E)-cinnamyl alcohol Chemical compound OC\C=C\C1=CC=CC=C1 OOCCDEMITAIZTP-QPJJXVBHSA-N 0.000 description 1
- PPTXVXKCQZKFBN-UHFFFAOYSA-N (S)-(-)-1,1'-Bi-2-naphthol Chemical compound C1=CC=C2C(C3=C4C=CC=CC4=CC=C3O)=C(O)C=CC2=C1 PPTXVXKCQZKFBN-UHFFFAOYSA-N 0.000 description 1
- VDLWTJCSPSUGOA-UHFFFAOYSA-N 1,2,3,4-tetrahydronaphthalene-1-carboxylic acid Chemical class C1=CC=C2C(C(=O)O)CCCC2=C1 VDLWTJCSPSUGOA-UHFFFAOYSA-N 0.000 description 1
- 150000000178 1,2,4-triazoles Chemical class 0.000 description 1
- XBYRMPXUBGMOJC-UHFFFAOYSA-N 1,2-dihydropyrazol-3-one Chemical class OC=1C=CNN=1 XBYRMPXUBGMOJC-UHFFFAOYSA-N 0.000 description 1
- BIGYLAKFCGVRAN-UHFFFAOYSA-N 1,3,4-thiadiazolidine-2,5-dithione Chemical compound S=C1NNC(=S)S1 BIGYLAKFCGVRAN-UHFFFAOYSA-N 0.000 description 1
- QKOWXXDOHMJOMQ-UHFFFAOYSA-N 1,3,5-tris(6-isocyanatohexyl)biuret Chemical compound O=C=NCCCCCCNC(=O)N(CCCCCCN=C=O)C(=O)NCCCCCCN=C=O QKOWXXDOHMJOMQ-UHFFFAOYSA-N 0.000 description 1
- 150000005207 1,3-dihydroxybenzenes Chemical class 0.000 description 1
- UHKAJLSKXBADFT-UHFFFAOYSA-N 1,3-indandione Chemical class C1=CC=C2C(=O)CC(=O)C2=C1 UHKAJLSKXBADFT-UHFFFAOYSA-N 0.000 description 1
- ODIRBFFBCSTPTO-UHFFFAOYSA-N 1,3-selenazole Chemical class C1=C[se]C=N1 ODIRBFFBCSTPTO-UHFFFAOYSA-N 0.000 description 1
- ZOBPZXTWZATXDG-UHFFFAOYSA-N 1,3-thiazolidine-2,4-dione Chemical compound O=C1CSC(=O)N1 ZOBPZXTWZATXDG-UHFFFAOYSA-N 0.000 description 1
- YNGDWRXWKFWCJY-UHFFFAOYSA-N 1,4-Dihydropyridine Chemical class C1C=CNC=C1 YNGDWRXWKFWCJY-UHFFFAOYSA-N 0.000 description 1
- ZRHUHDUEXWHZMA-UHFFFAOYSA-N 1,4-dihydropyrazol-5-one Chemical class O=C1CC=NN1 ZRHUHDUEXWHZMA-UHFFFAOYSA-N 0.000 description 1
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 1
- PJDDFKGDNUTITH-UHFFFAOYSA-N 1,5-bis(2-chlorophenyl)-1,2,5,6-tetrahydro-[1,2,4]triazolo[1,2-a][1,2,4]triazole-3,7-dithione Chemical compound SC1=NC(C=2C(=CC=CC=2)Cl)N(C(=N2)S)N1C2C1=CC=CC=C1Cl PJDDFKGDNUTITH-UHFFFAOYSA-N 0.000 description 1
- LRGBKQAXMKYMHJ-UHFFFAOYSA-N 1,5-diphenyl-1,2,5,6-tetrahydro-[1,2,4]triazolo[1,2-a][1,2,4]triazole-3,7-dithione Chemical compound S=C1NC(C=2C=CC=CC=2)N(C(N2)=S)N1C2C1=CC=CC=C1 LRGBKQAXMKYMHJ-UHFFFAOYSA-N 0.000 description 1
- ZPANWZBSGMDWON-UHFFFAOYSA-N 1-[(2-hydroxynaphthalen-1-yl)methyl]naphthalen-2-ol Chemical compound C1=CC=C2C(CC3=C4C=CC=CC4=CC=C3O)=C(O)C=CC2=C1 ZPANWZBSGMDWON-UHFFFAOYSA-N 0.000 description 1
- NEPWWHQLHRGVQL-UHFFFAOYSA-N 1-n,4-n-dimethylbenzene-1,4-diamine;hydron;chloride Chemical compound Cl.CNC1=CC=C(NC)C=C1 NEPWWHQLHRGVQL-UHFFFAOYSA-N 0.000 description 1
- WFYLHMAYBQLBEM-UHFFFAOYSA-N 1-phenyl-1,2,4-triazolidine-3,5-dione Chemical compound O=C1NC(=O)NN1C1=CC=CC=C1 WFYLHMAYBQLBEM-UHFFFAOYSA-N 0.000 description 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- KJUGUADJHNHALS-UHFFFAOYSA-N 1H-tetrazole Substances C=1N=NNN=1 KJUGUADJHNHALS-UHFFFAOYSA-N 0.000 description 1
- AFBBKYQYNPNMAT-UHFFFAOYSA-N 1h-1,2,4-triazol-1-ium-3-thiolate Chemical compound SC=1N=CNN=1 AFBBKYQYNPNMAT-UHFFFAOYSA-N 0.000 description 1
- ZEQIWKHCJWRNTH-UHFFFAOYSA-N 1h-pyrimidine-2,4-dithione Chemical compound S=C1C=CNC(=S)N1 ZEQIWKHCJWRNTH-UHFFFAOYSA-N 0.000 description 1
- AVRPFRMDMNDIDH-UHFFFAOYSA-N 1h-quinazolin-2-one Chemical compound C1=CC=CC2=NC(O)=NC=C21 AVRPFRMDMNDIDH-UHFFFAOYSA-N 0.000 description 1
- HAZJTCQWIDBCCE-UHFFFAOYSA-N 1h-triazine-6-thione Chemical compound SC1=CC=NN=N1 HAZJTCQWIDBCCE-UHFFFAOYSA-N 0.000 description 1
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- KGLPWQKSKUVKMJ-UHFFFAOYSA-N 2,3-dihydrophthalazine-1,4-dione Chemical compound C1=CC=C2C(=O)NNC(=O)C2=C1 KGLPWQKSKUVKMJ-UHFFFAOYSA-N 0.000 description 1
- VZYDKJOUEPFKMW-UHFFFAOYSA-N 2,3-dihydroxybenzenesulfonic acid Chemical class OC1=CC=CC(S(O)(=O)=O)=C1O VZYDKJOUEPFKMW-UHFFFAOYSA-N 0.000 description 1
- ZXDDPOHVAMWLBH-UHFFFAOYSA-N 2,4-Dihydroxybenzophenone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 ZXDDPOHVAMWLBH-UHFFFAOYSA-N 0.000 description 1
- ZKEGGSPWBGCPNF-UHFFFAOYSA-N 2,5-dihydroxy-5-methyl-3-(piperidin-1-ylamino)cyclopent-2-en-1-one Chemical compound O=C1C(C)(O)CC(NN2CCCCC2)=C1O ZKEGGSPWBGCPNF-UHFFFAOYSA-N 0.000 description 1
- INQNLBFXQRNUCZ-UHFFFAOYSA-N 2,6-ditert-butyl-4-[(3,5-ditert-butyl-4-hydroxyphenyl)-phenylmethyl]phenol Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(C(C=2C=CC=CC=2)C=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 INQNLBFXQRNUCZ-UHFFFAOYSA-N 0.000 description 1
- QAQJMLQRFWZOBN-UHFFFAOYSA-N 2-(3,4-dihydroxy-5-oxo-2,5-dihydrofuran-2-yl)-2-hydroxyethyl hexadecanoate Chemical compound CCCCCCCCCCCCCCCC(=O)OCC(O)C1OC(=O)C(O)=C1O QAQJMLQRFWZOBN-UHFFFAOYSA-N 0.000 description 1
- FVQQWSSTYVBNST-UHFFFAOYSA-N 2-(4-methyl-2-sulfanylidene-1,3-thiazol-3-yl)acetic acid Chemical compound CC1=CSC(=S)N1CC(O)=O FVQQWSSTYVBNST-UHFFFAOYSA-N 0.000 description 1
- NREKJIIPVVKRNO-UHFFFAOYSA-N 2-(tribromomethylsulfonyl)-1,3-benzothiazole Chemical compound C1=CC=C2SC(S(=O)(=O)C(Br)(Br)Br)=NC2=C1 NREKJIIPVVKRNO-UHFFFAOYSA-N 0.000 description 1
- RSQZJBAYJAPBKJ-UHFFFAOYSA-N 2-[(dimethylamino)methyl]benzo[f]isoindole-1,3-dione Chemical compound C1=CC=C2C=C(C(N(CN(C)C)C3=O)=O)C3=CC2=C1 RSQZJBAYJAPBKJ-UHFFFAOYSA-N 0.000 description 1
- RPWDFMGIRPZGTI-UHFFFAOYSA-N 2-[1-(2-hydroxy-3,5-dimethylphenyl)-3,5,5-trimethylhexyl]-4,6-dimethylphenol Chemical compound C=1C(C)=CC(C)=C(O)C=1C(CC(C)CC(C)(C)C)C1=CC(C)=CC(C)=C1O RPWDFMGIRPZGTI-UHFFFAOYSA-N 0.000 description 1
- QRKJNCRCYBKANP-UHFFFAOYSA-N 2-amino-n-phenylacetamide Chemical compound NCC(=O)NC1=CC=CC=C1 QRKJNCRCYBKANP-UHFFFAOYSA-N 0.000 description 1
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 1
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- CZLCEPVHPYKDPJ-UHFFFAOYSA-N guanidine;2,2,2-trichloroacetic acid Chemical compound NC(N)=N.OC(=O)C(Cl)(Cl)Cl CZLCEPVHPYKDPJ-UHFFFAOYSA-N 0.000 description 1
- 229940093915 gynecological organic acid Drugs 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical class [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229940079865 intestinal antiinfectives imidazole derivative Drugs 0.000 description 1
- 229920000831 ionic polymer Polymers 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229940049918 linoleate Drugs 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- GPSDUZXPYCFOSQ-UHFFFAOYSA-M m-toluate Chemical compound CC1=CC=CC(C([O-])=O)=C1 GPSDUZXPYCFOSQ-UHFFFAOYSA-M 0.000 description 1
- FDZZZRQASAIRJF-UHFFFAOYSA-M malachite green Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](C)C)C=C1 FDZZZRQASAIRJF-UHFFFAOYSA-M 0.000 description 1
- 229940107698 malachite green Drugs 0.000 description 1
- CUONGYYJJVDODC-UHFFFAOYSA-N malononitrile Chemical class N#CCC#N CUONGYYJJVDODC-UHFFFAOYSA-N 0.000 description 1
- 239000006224 matting agent 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
- NGYIMTKLQULBOO-UHFFFAOYSA-L mercury dibromide Chemical compound Br[Hg]Br NGYIMTKLQULBOO-UHFFFAOYSA-L 0.000 description 1
- 238000005649 metathesis reaction Methods 0.000 description 1
- WREDNSAXDZCLCP-UHFFFAOYSA-N methanedithioic acid Chemical compound SC=S WREDNSAXDZCLCP-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- NSBNSZAXNUGWDJ-UHFFFAOYSA-O monopyridin-1-ium tribromide Chemical compound Br[Br-]Br.C1=CC=[NH+]C=C1 NSBNSZAXNUGWDJ-UHFFFAOYSA-O 0.000 description 1
- ZHFBNFIXRMDULI-UHFFFAOYSA-N n,n-bis(2-ethoxyethyl)hydroxylamine Chemical compound CCOCCN(O)CCOCC ZHFBNFIXRMDULI-UHFFFAOYSA-N 0.000 description 1
- WPGGNTDTBCRPCE-UHFFFAOYSA-N n-(1,3-benzothiazol-2-yl)-2-hydroxybutanamide Chemical compound C1=CC=C2SC(NC(=O)C(O)CC)=NC2=C1 WPGGNTDTBCRPCE-UHFFFAOYSA-N 0.000 description 1
- WHZPMLXZOSFAKY-UHFFFAOYSA-N n-(4-hydroxyphenyl)benzenesulfonamide Chemical compound C1=CC(O)=CC=C1NS(=O)(=O)C1=CC=CC=C1 WHZPMLXZOSFAKY-UHFFFAOYSA-N 0.000 description 1
- BWJFEONZAZSPSG-UHFFFAOYSA-N n-amino-n-(4-methylphenyl)formamide Chemical compound CC1=CC=C(N(N)C=O)C=C1 BWJFEONZAZSPSG-UHFFFAOYSA-N 0.000 description 1
- 239000000025 natural resin Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 125000004971 nitroalkyl group Chemical group 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000002916 oxazoles Chemical class 0.000 description 1
- 150000001475 oxazolidinediones Chemical class 0.000 description 1
- 150000002918 oxazolines Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- BHAAPTBBJKJZER-UHFFFAOYSA-N p-anisidine Chemical compound COC1=CC=C(N)C=C1 BHAAPTBBJKJZER-UHFFFAOYSA-N 0.000 description 1
- KLAKIAVEMQMVBT-UHFFFAOYSA-N p-hydroxy-phenacyl alcohol Natural products OCC(=O)C1=CC=C(O)C=C1 KLAKIAVEMQMVBT-UHFFFAOYSA-N 0.000 description 1
- AFAIELJLZYUNPW-UHFFFAOYSA-N pararosaniline free base Chemical compound C1=CC(N)=CC=C1C(C=1C=CC(N)=CC=1)=C1C=CC(=N)C=C1 AFAIELJLZYUNPW-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- CMCWWLVWPDLCRM-UHFFFAOYSA-N phenidone Chemical compound N1C(=O)CCN1C1=CC=CC=C1 CMCWWLVWPDLCRM-UHFFFAOYSA-N 0.000 description 1
- NFBAXHOPROOJAW-UHFFFAOYSA-N phenindione Chemical compound O=C1C2=CC=CC=C2C(=O)C1C1=CC=CC=C1 NFBAXHOPROOJAW-UHFFFAOYSA-N 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- LFSXCDWNBUNEEM-UHFFFAOYSA-N phthalazine Chemical compound C1=NN=CC2=CC=CC=C21 LFSXCDWNBUNEEM-UHFFFAOYSA-N 0.000 description 1
- 150000003022 phthalic acids 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
- 230000000704 physical effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920006289 polycarbonate film Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- JEXVQSWXXUJEMA-UHFFFAOYSA-N pyrazol-3-one Chemical class O=C1C=CN=N1 JEXVQSWXXUJEMA-UHFFFAOYSA-N 0.000 description 1
- 150000003217 pyrazoles Chemical class 0.000 description 1
- NDGRWYRVNANFNB-UHFFFAOYSA-N pyrazolidin-3-one Chemical class O=C1CCNN1 NDGRWYRVNANFNB-UHFFFAOYSA-N 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 150000003230 pyrimidines Chemical class 0.000 description 1
- 150000003236 pyrrolines Chemical class 0.000 description 1
- JWVCLYRUEFBMGU-UHFFFAOYSA-N quinazoline Chemical compound N1=CN=CC2=CC=CC=C21 JWVCLYRUEFBMGU-UHFFFAOYSA-N 0.000 description 1
- 150000008515 quinazolinediones Chemical class 0.000 description 1
- 239000012260 resinous material Substances 0.000 description 1
- KIWUVOGUEXMXSV-UHFFFAOYSA-N rhodanine Chemical class O=C1CSC(=S)N1 KIWUVOGUEXMXSV-UHFFFAOYSA-N 0.000 description 1
- 150000003283 rhodium Chemical class 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- MMRXYMKDBFSWJR-UHFFFAOYSA-K rhodium(3+);tribromide Chemical compound [Br-].[Br-].[Br-].[Rh+3] MMRXYMKDBFSWJR-UHFFFAOYSA-K 0.000 description 1
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 description 1
- 238000006748 scratching Methods 0.000 description 1
- 230000002393 scratching effect Effects 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- IZXSLAZMYLIILP-ODZAUARKSA-M silver (Z)-4-hydroxy-4-oxobut-2-enoate Chemical compound [Ag+].OC(=O)\C=C/C([O-])=O IZXSLAZMYLIILP-ODZAUARKSA-M 0.000 description 1
- NBYLLBXLDOPANK-UHFFFAOYSA-M silver 2-carboxyphenolate hydrate Chemical compound C1=CC=C(C(=C1)C(=O)O)[O-].O.[Ag+] NBYLLBXLDOPANK-UHFFFAOYSA-M 0.000 description 1
- 229940045105 silver iodide Drugs 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- YRSQDSCQMOUOKO-KVVVOXFISA-M silver;(z)-octadec-9-enoate Chemical compound [Ag+].CCCCCCCC\C=C/CCCCCCCC([O-])=O YRSQDSCQMOUOKO-KVVVOXFISA-M 0.000 description 1
- RUVFQTANUKYORF-UHFFFAOYSA-M silver;2,4-dichlorobenzoate Chemical compound [Ag+].[O-]C(=O)C1=CC=C(Cl)C=C1Cl RUVFQTANUKYORF-UHFFFAOYSA-M 0.000 description 1
- OEVSPXPUUSCCIH-UHFFFAOYSA-M silver;2-acetamidobenzoate Chemical compound [Ag+].CC(=O)NC1=CC=CC=C1C([O-])=O OEVSPXPUUSCCIH-UHFFFAOYSA-M 0.000 description 1
- JRTHUBNDKBQVKY-UHFFFAOYSA-M silver;2-methylbenzoate Chemical compound [Ag+].CC1=CC=CC=C1C([O-])=O JRTHUBNDKBQVKY-UHFFFAOYSA-M 0.000 description 1
- OXOZKDHFGLELEO-UHFFFAOYSA-M silver;3-carboxy-5-hydroxyphenolate Chemical compound [Ag+].OC1=CC(O)=CC(C([O-])=O)=C1 OXOZKDHFGLELEO-UHFFFAOYSA-M 0.000 description 1
- UCLXRBMHJWLGSO-UHFFFAOYSA-M silver;4-methylbenzoate Chemical compound [Ag+].CC1=CC=C(C([O-])=O)C=C1 UCLXRBMHJWLGSO-UHFFFAOYSA-M 0.000 description 1
- QHQMZVBSKDIZTK-UHFFFAOYSA-M silver;5-chloro-2h-benzotriazole-4-carboxylate Chemical compound [Ag+].[O-]C(=O)C1=C(Cl)C=CC2=NNN=C12 QHQMZVBSKDIZTK-UHFFFAOYSA-M 0.000 description 1
- CLDWGXZGFUNWKB-UHFFFAOYSA-M silver;benzoate Chemical compound [Ag+].[O-]C(=O)C1=CC=CC=C1 CLDWGXZGFUNWKB-UHFFFAOYSA-M 0.000 description 1
- JKOCEVIXVMBKJA-UHFFFAOYSA-M silver;butanoate Chemical compound [Ag+].CCCC([O-])=O JKOCEVIXVMBKJA-UHFFFAOYSA-M 0.000 description 1
- MNMYRUHURLPFQW-UHFFFAOYSA-M silver;dodecanoate Chemical compound [Ag+].CCCCCCCCCCCC([O-])=O MNMYRUHURLPFQW-UHFFFAOYSA-M 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
- OHGHHPYRRURLHR-UHFFFAOYSA-M silver;tetradecanoate Chemical compound [Ag+].CCCCCCCCCCCCCC([O-])=O OHGHHPYRRURLHR-UHFFFAOYSA-M 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229960002317 succinimide Drugs 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 1
- 150000003452 sulfinic acid derivatives Chemical class 0.000 description 1
- 125000004964 sulfoalkyl group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 150000003557 thiazoles Chemical class 0.000 description 1
- 150000001467 thiazolidinediones Chemical class 0.000 description 1
- 150000003549 thiazolines Chemical class 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- OTOHACXAQUCHJO-UHFFFAOYSA-H tripotassium;hexachlororhodium(3-) Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[K+].[K+].[K+].[Rh+3] OTOHACXAQUCHJO-UHFFFAOYSA-H 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000001018 xanthene dye Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 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
- G03C1/49836—Additives
- G03C1/49845—Active additives, e.g. toners, stabilisers, sensitisers
Definitions
- the invention relates to a photothermographic silver halide material and method for producing in such a material improved fog stability on shelf aging by a combination of an isocyanate and a halogenated compound.
- Silver halide photothermographic imaging materials often referred to as "dry silver" compositions because no liquid development is necessary to produce the final image, have been known in the art for many years. These imaging materials basically comprise a light insensitive, reducible silver source, a light sensitive material which generates silver when irradiated, and a reducing agent for the silver source.
- the light sensitive material is generally photographic silver halide which must be in catalytic proximity to the light insensitive silver source. Catalytic proximity is an intimate physical association of these two materials so that when silver specks or nuclei are generated by the irradiation or light exposure of the photographic silver halide, those nuclei are able to catalyze the reduction of the silver source by the reducing agent.
- silver is a catalyst for the reduction of silver ions and the silver-generating light sensitive silver halide catalyst progenitor may be placed into catalytic proximity with the silver source in a number of different fashions, such as partial metathesis of the silver source with a halogen-containing source (e.g., U.S. Pat. No. 3,457,075), coprecipitation of the silver halide and silver source material (e.g., U.S. Pat. No. 3,839,049), and any other method which intimately associates the silver halide and the silver source.
- a halogen-containing source e.g., U.S. Pat. No. 3,457,075
- coprecipitation of the silver halide and silver source material e.g., U.S. Pat. No. 3,839,049
- Photothermographic emulsions in a manner similar to photographic emulsions and other light sensitive systems, tend to suffer from fog. Fog is spurious image density which appears in unexposed areas of the element and is often reported in sensitometric results as Dmin.
- Traditionally, photothermographic materials have suffered from fog instability on shelf aging. The fog level rises steadily as the materials reach extended age such as one year at room temperature (ambient conditions). Adding to the difficulty of fog control on shelf aging is the fact that the developer is incorporated in the photothermographic element which is not the case in most silver halide photographic systems. The need for shelf life extenders in photothermographic elements is therefore considered to be very important.
- the fog level of freshly prepared photothermographic materials will be referred to as initial fog.
- Halogenated compounds have also been shown to be strong antifoggants and are described in U.S. Patents 4,546,075, 4,756,999, 4,452,885, 3,874,946 and 3,955,982.
- Halogen molecules or halogen molecules associated with a heteroatom ring are also useful antifoggants and are described in U.S. Patent No. 5,028,523.
- these compounds individually or in combination were not found to produce sufficient fog stability on shelf aging of the photothermographic element.
- Diisocyanates have been used to improve the physical properties of photothermographic materials. They will crosslink the resin or binder which toughens the layer and reduces or eliminates scratching during hot roll processing. Crosslinking by diisocyanates is described in U.S. Patent No. 4,281,060 and in combination with boric acid in U.S. Patent No. 4,558,003. These patents used diisocyanates to harden or crosslink the resin.
- a photothermographic emulsion comprising in one or two layers a silver salt of an organic acid, silver halide, a reducing agent for silver ion, and a binder, the silver salt of an organic acid and the silver halide being present in one layer, characterised in that the emulsion contains, as an antifoggant, the combination of 1) at least one compound having an isocyanate group, and 2) a halogenated antifoggant compound which has an aromatic or heteroaromatic group having at least one perhalogenated alkyl group thereon.
- the ability of the isocyanate to harden or crosslink is not critical to whether the isocyanate will act as a fog stabilizer on shelf aging.
- Octadecyl isocyanate which has only a single isocyanate group, cannot crosslink the resin but still improves the fog stability on shelf aging.
- the aryl ring may also carry substituents with examples of preferred substituents being selected from the class consisting of halogen (e.g. Br and Cl), hydroxy, amino, carboxy and alkoxy.
- halogen e.g. Br and Cl
- isocyanate compounds along with the manufacturer and class are set forth below.
- the examples include aliphatic, aromatic and polymeric isocyanates.
- the isocyanates are used in general amount of at least 0.0002 moles/mole of silver. Usually the range is between 0.002 and 2 moles of the compound per mole of silver and preferably between 0.003 and 0.3 moles of compound per mole of silver.
- Isocyanates improve the fog stability on shelf aging of photothermographic systems incorporating a halogenated antifoggant compound.
- the antifoggant preferably has at least one brominated alkyl group thereon, more preferably at least one tribromomethane group which may be directly attached to the aromatic or heteroaromatic group or bonded through a linking group, e.g. sulphonyl.
- the preferred antifoggant compounds are represented by the formula: Ar-(SO 2 ) y -CX 3 (II) in which:
- alkyl group includes for example ether groups (e.g., CH 3 -CH 2 -CH 2 -O-CH 2 -), haloalkyls, nitroalkyls, carboxyalkyls, hydroxyalkyls, sulfoalkyls while the term alkyl includes only hydrocarbons.
- ether groups e.g., CH 3 -CH 2 -CH 2 -O-CH 2 -
- haloalkyls e.g., CH 3 -CH 2 -CH 2 -O-CH 2 -
- haloalkyls e.g., haloalkyls, nitroalkyls, carboxyalkyls, hydroxyalkyls, sulfoalkyls while the term alkyl includes only hydrocarbons.
- Substituents which react with active ingredients, such as very strongly electrophilic or oxidizing substituents would of course be excluded as not being inert or harmless.
- the halogenated compounds used in the present invention are generally incorporated in the silver or topcoat layer in a content of 5 x 10 -4 mole to 0.5 mole preferably 5 x 10 -3 to 5 x 10 -2 mole, per mole of total silver.
- halogenated antifoggant compounds used in the present invention are listed below.
- the photothermographic dry silver emulsions of this invention may be constructed of one or more layers on a substrate.
- Single layer constructions must contain the silver source material, the silver halide, the developer and binder as well as optional additional materials such as toners, coating aids, and other adjuvants.
- Two-layer constructions must contain the silver source and silver halide in one emulsion layer (usually the layer adjacent to the substrate) and some of the other ingredients in the second layer or both layers, although two layer constructions comprising a single emulsion layer containing all the ingredients and a protective topcoat are envisioned.
- Multicolor photothermographic dry silver constructions may contain sets of these bilayers for each color, or they may contain all ingredients within a single layer as described in U.S. Pat. No.
- mercury (II) salts While not necessary for practice of the present invention, it may be advantageous to add mercury (II) salts to the emulsion layer(s) as an antifoggant.
- Preferred mercury (II) salts for this purpose are mercuric acetate and mercuric bromide.
- the light sensitive silver halide used in the present invention may typically be employed in a range of 0.75 to 25 mol percent and, preferably, from 2 to 20 mol percent of organic silver salt.
- the silver halide may be any photosensitive silver halide such as silver bromide, silver iodide, silver chloride, silver bromoiodide, silver chlorobromoiodide and silver chlorobromide.
- the silver halide may be in any form which is photosensitive including, but not limited to cubic, orthorhombic, tabular and tetrahedral, and may have epitaxial growth of crystals thereon.
- the silver halide used in the present invention may be employed without modification. However, it may be chemically sensitized with a chemical sensitizing agent such as a compound containing sulfur, selenium or tellurium, or a compound containing gold, platinum, palladium, rhodium or iridium, a reducing agent such as a tin halide, or a combination thereof.
- a chemical sensitizing agent such as a compound containing sulfur, selenium or tellurium, or a compound containing gold, platinum, palladium, rhodium or iridium, a reducing agent such as a tin halide, or a combination thereof.
- the silver halide may be added to the emulsion layer in any fashion which places it in catalytic proximity to the silver source.
- Silver halide and the organic silver salt which are separately formed or "preformed” in a binder can be mixed prior to use to prepare a coating solution, but it is also effective to blend both of them in a ball mill for a long period of time. Further, it is effective to use a process which comprises adding a halogen-containing compound in the organic silver salt prepared to partially convert the silver of the organic silver salt to silver halide.
- preformed silver halide emulsions of this invention can be unwashed or washed to remove soluble salts.
- the soluble salts can be removed by chill-setting and leaching or the emulsion can be coagulation washed, e.g., by the procedures described in U.S. Pat. Nos. 2,618,556; 2,614,928; 2,565,418; 3,241,969; and 2,489,341.
- the silver halide grains may have any crystalline habit including, but not limited to cubic, tetrahedral, orthorhombic, tabular, laminar and platelet.
- the organic silver salt may be any organic material which. contains a reducible source of silver ions.
- Silver salts of organic acids, particularly long chain (10 to 30 preferably 15 to 28 carbon atoms) fatty carboxylic acids are preferred.
- Complexes of organic or inorganic silver salts wherein the ligand has a gross stability constant between 4.0 and 10.0 are also desirable.
- the silver source material should preferably constitute from about 5 to 30 percent by weight of the imaging layer.
- the organic silver salt which can be used in the present invention is a silver salt which is comparatively stable to light, but forms a silver image when heated to 80°C or higher in the presence of an exposed photocatalyst (such as photographic silver halide) and a reducing agent.
- Preferred organic silver salts include silver salts of organic compounds having a carboxy group.
- Non-limiting examples thereof include silver salts of an aliphatic carboxylic acid and a silver salt of an aromatic carboxylic acid.
- Preferred examples of the silver salts of aliphatic carboxylic acids include silver behenate, silver stearate, silver oleate, silver laurate, silver caproate, silver myristate, silver palmitate, silver maleate, silver fumarate, silver tartrate, silver linoleate, silver butyrate and silver camphorate and mixtures thereof.
- Silver salts with a halogen atom or a hydroxyl on the aliphatic carboxylic acid can also be effectively used.
- Preferred examples of the silver salts of aromatic carboxylic acids and other carboxyl group-containing compounds include silver benzoate, a silver substituted benzoate such as silver 3,5-dihydroxybenzoate, silver o -methylbenzoate, silver m -methylbenzoate, silver p -methylbenzoate, silver 2,4-dichlorobenzoate, silver acetamidobenzoate, silver p -phenyl benzoate, silver gallate, silver tannate, silver phthalate, silver terephthalate, silver salicylate, silver phenylacetate, silver pyromellitate, a silver salt of 3-carboxymethyl-4-methyl-4-thiazoline-2-thione as described in U.S. Pat. No. 3,785,830, and silver salt of an aliphatic carboxylic acid containing a thioether group as described in U.S. Pat. No. 3,330,663.
- Silver salts of compounds containing mercapto or thione groups and derivatives thereof can also be used.
- Preferred examples of these compounds include a silver salt of 3-mercapto-4-phenyl-1,2,4-triazole, a silver salt of 2-mercaptobenzimidazole, a silver salt of 2-mercapto-5-aminothiadiazole, a silver salt of 2-(ethylglycolamido)benzothiazole, a silver salt of thioglycolic acid such as a silver salt of an S -alkyl thioglycolic acid (wherein the alkyl group has from 12 to 22 carbon atoms), a silver salt of a dithiocarboxylic acid such as a silver salt of dithioacetic acid, a silver salt of a thioamide, a silver salt of 5-carboxylic-1-methyl-2-phenyl-4-thiopyridine, a silver salt of mercaptotriazine, a silver salt of 2-mer
- a silver salt of 1,2,4-mercaptotriazole derivative such as a silver salt of 3-amino-5-benzylthio-1,2,4-triazole
- a silver salt of a thione compound such as a silver salt of 3-(2-carboxyethyl)-4-methyl-4-thiazoline-2-thione as disclosed in U.S. Pat. No. 3,301,678.
- a silver salt of a compound containing an imino group may be used.
- Preferred examples of these compounds include silver salts of benzotriazole and derivatives thereof, for example, silver salts of benzotriazoles such as silver methylbenzotriazolate, silver salt of halogen-substituted benzotriazoles, such as silver 5-chlorobenzotriazolate, silver salts of carboimidobenzotriazole, silver salt of 1,2,4-triazoles or 1- H -tetrazoles as described in U.S. Pat. No. 4,220,709, silver salts of imidazoles and imidazole derivatives.
- Various silver acetylide compounds can also be used, for instance, as described in U.S. Pat. Nos. 4,761,361 and 4,775,613.
- silver half soaps of which an equimolar blend of silver behenate and behenic acid, prepared by precipitation from aqueous solution of the sodium salt of commercial behenic acid and analyzing about 14.5 percent silver, represents a preferred example.
- Transparent sheet materials made on transparent film backing require a transparent coating and for this purpose the silver behenate full soap, containing not more than about four or five percent of free behenic acid and analyzing about 25.2 percent silver may be used.
- the light-sensitive silver halides may be advantageously spectrally sensitized with various known dyes including cyanine, merocyanine, styryl, hemicyanine, oxonol, hemioxonol and xanthene dyes.
- Useful cyanine dyes include those having a basic nucleus, such as a thiazoline nucleus, an oxazoline nucleus, a pyrroline nucleus, a pyridine nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus and an imidazole nucleus.
- Useful merocyanine dyes which are preferred include those having not only the above described basic nuclei but also acid nuclei, such as a thiohydantoin nucleus, a rhodanine nucleus, an oxazolidinedione nucleus, a thiazolidinedione nucleus, a barbituric acid nucleus, a thiazolinone nucleus, a malononitrile nucleus and a pyrazolone nucleus.
- acid nuclei such as a thiohydantoin nucleus, a rhodanine nucleus, an oxazolidinedione nucleus, a thiazolidinedione nucleus, a barbituric acid nucleus, a thiazolinone nucleus, a malononitrile nucleus and a pyrazolone nucleus.
- imino groups or carboxyl groups are particularly effective.
- the sensitizing dyes to be used in the present invention may be properly selected from known dyes such as those described in U.S. Pat. Nos. 3,761,279, 3,719,495, and 3,877,943, British Pat. Nos. 1,466,201, 1,469,117 and 1,422,057, and can be located in the vicinity of the photocatalyst according to known methods.
- Spectral sensitizing dyes may be typically used in amounts of about 10 -4 mol to about 1 mol per 1 mol of silver halide.
- the reducing agent for the organic silver salt may be any material, preferably organic material, that can reduce silver ion to metallic silver.
- Conventional photographic developers such as phenidone, hydroquinones, and catechol are useful but hindered phenol reducing agents are preferred.
- the reducing agent should be present as 1 to 10 percent by weight of the imaging layer. In multilayer constructions, if the reducing agent is added to a layer other than an emulsion layer, slightly higher proportions, of from about 2 to 15 percent tend to be more desirable.
- amidoximes such as phenylamidoxime, 2-thienylamidoxime and p -phenoxyphenylamidoxime, azines (e.g., 4-hydroxy-3,5-dimethoxybenzaldehydeazine); a combination of aliphatic carboxylic acid aryl hydrazides and ascorbic acid, such as 2,2'-bis(hydroxymethyl)propionyl- ⁇ -phenylhydrazide in combination with ascorbic acid; a combination of polyhydroxybenzene and hydroxylamine, a reductone and/or a hydrazine (e.g., a combination of hydroquinone and bis(ethoxyethyl)hydroxylamine, piperidinohexose reductone or formyl-4-methylphenylhydrazine); hydroxamic acids such as phenylhydroxamic acid, p -hydroxyphenylhydroxamic acid, and
- Toners additives known as "toners” that improve the image.
- Toner materials may be present, for example, in amounts from 0.1 to 10 percent by weight of all silver bearing components. Toners are well known materials in the photothermographic art as shown in U.S. Pat. Nos. 3,080,254; 3,847,612 and 4,123,282.
- toners examples include phthalimide and N -hydroxyphthalimide; cyclic imides such as succinimide, pyrazoline-5-ones, and a quinazolinone, 3-phenyl-2- pyrazoline-5-one, 1-phenylurazole, quinazoline, and 2,4- thiazolidinedione; naphthalimides (e.g., N -hydroxy-1,8-naphthalimide); cobalt complexes (e.g., cobaltic hexammine trifluoroacetate); mercaptans as illustrated by 3-mercapto-1,2,4-triazole, 2,4-dimercaptopyrimidine, 3-mercapto-4,5-diphenyl-1,2,4-triazole and 2,5-dimercapto-1,3,4-thiadiazole; N -(aminomethyl)aryldicarboximides, (e.g., ( N , N -dimethylaminomethyl)phthalimide
- a number of methods are known in the art for obtaining color images with dry silver systems including: a combination of silver benzotriazole, well known magenta, yellow and cyan dye-forming couplers, aminophenol developing agents, a base release agent such as guanidinium trichloroacetate and silver bromide in poly(vinyl butyral) as described in U.S. Pat. Nos. 4,847,188 and 5,064,742; preformed dye release systems such as those described in U.S. Pat. No.
- Silver halide emulsions containing the antifoggants used in this invention can be protected further against the additional production of fog and can be stabilized against loss of sensitivity during shelf storage.
- Suitable antifoggants, stabilizers, and stabilizer precursors which can be used alone or in combination, include thiazolium salts as described in U.S. Pat. Nos. 2,131,038 and 2,694,716; azaindenes as described in U.S. Pat. Nos. 2,886,437 and 2,444,605; mercury salts as described in U.S. Pat. No. 2,728,663; urazoles as described in U.S. Pat. No. 3,287,135; sulfocatechols as described in U.S. Pat.
- Emulsions of the invention can contain plasticizers and lubricants such as polyalcohols (e.g., glycerin and diols of the type described in U.S. Pat. No. 2,960,404); fatty acids or esters such as those described in U.S. Pat. No. 2,588,765 and U.S. Pat. No. 3,121,060; and silicone resins such as those described in British Pat. No. 955,061.
- polyalcohols e.g., glycerin and diols of the type described in U.S. Pat. No. 2,960,404
- fatty acids or esters such as those described in U.S. Pat. No. 2,588,765 and U.S. Pat. No. 3,121,060
- silicone resins such as those described in British Pat. No. 955,061.
- the photothermographic elements used in the present invention may include image dye stabilizers.
- image dye stabilizers are illustrated by British Pat. No. 1,326,889; U.S. Pat. Nos. 3,432,300; 3,698,909; 3,574,627; 3,573,050; 3,764,337 and 4,042,394.
- Photothermographic elements containing emulsion layers according to the present invention can be used in photographic elements which contain light absorbing materials and filter dyes such as those described in U.S. Pat. Nos. 3,253,921; 2,274,782; 2,527,583 and 2,956,879. If desired, the dyes can be mordanted, for example, as described in U.S. Pat. No. 3,282,699.
- Photothermographic elements containing emulsion layers as described herein can contain matting agents such as starch, titanium dioxide, zinc oxide, silica, polymeric beads including beads of the type described in U.S. Pat. No. 2,992,101 and U.S. Pat. No. 2,701,245.
- matting agents such as starch, titanium dioxide, zinc oxide, silica, polymeric beads including beads of the type described in U.S. Pat. No. 2,992,101 and U.S. Pat. No. 2,701,245.
- Emulsions in accordance with this invention can be used in photothermographic elements which contain antistatic or conducting layers, such as layers that comprise soluble salts (e.g., chlorides or nitrates), evaporated metal layers, ionic polymers such as those described in U.S. Pat. Nos. 2,861,056 and 3,206,312 or insoluble inorganic salts such as those described in U.S. Pat. No. 3,428,451.
- soluble salts e.g., chlorides or nitrates
- evaporated metal layers ionic polymers such as those described in U.S. Pat. Nos. 2,861,056 and 3,206,312 or insoluble inorganic salts such as those described in U.S. Pat. No. 3,428,451.
- the binder may be selected from any of the well-known natural or synthetic resins such as gelatin, polyvinyl acetals, polyvinyl chloride, polyvinyl acetate, cellulose acetate, polyolefins, polyesters, polystyrene, polyacrylonitrile or polycarbonates. Copolymers and terpolymers are of course included in these definitions.
- the preferred photothermographic silver containing polymers are polyvinyl butyral, ethyl cellulose, methacrylate copolymers, maleic anhydride ester copolymers, polystyrene, and butadiene-styrene copolymers.
- these polymers may be used in combinations of two or more thereof.
- Such a polymer is used in an amount sufficient to carry the components dispersed therein, that is, within the effective range of the action as the binder.
- the effective range can be appropriately determined by one skilled in the art.
- a preferable ratio of the binder to the organic silver salt ranges from 15:1 to 1:2, and particularly from 8:1 to 1:1.
- Photothermographic emulsions containing a stabilizer according to the present invention may be coated on a wide variety of supports.
- Typical supports include polyester film, subbed polyester film, poly(ethylene terephthalate) film, cellulose nitrate film, cellulose ester film, poly(vinyl acetal) film, polycarbonate film and related or resinous materials, as well as glass, paper or metal.
- a flexible support is employed, especially a paper support, which may be partially acetylated or coated with baryta and/or an ⁇ -olefin polymer, particularly a polymer of an ⁇ -olefin containing 2 to 10 carbon atoms such as polyethylene, polypropylene, ethylene-butene copolymers and the like. Substrates may be transparent or opaque.
- Substrates with a backside resistive heating layer may also be used in photothermographic imaging systems such as shown in U.S. Pat. Nos. 4,460,681 and 4,374,921.
- Photothermographic emulsions of this invention can be coated by various coating procedures including dip coating, air knife coating, curtain coating, or extrusion coating using hoppers of the type described in U.S. Pat. No. 2,681,294. If desired, two or more layers may be coated simultaneously by the procedures described in U.S. Pat. No. 2,761,791 and British Pat. No. 837,095.
- Additional layers may be incorporated into photothermographic articles of the present invention such as dye receptive layers for receiving a mobile dye image, an opacifying layer when reflection prints are desired, a protective topcoat layer and a primer layer as is known in the photothermographic art. Additionally, it may be desirable in some instances to coat different emulsion layers on both sides of a transparent substrate, especially when it is desirable to isolate the imaging chemistries of the different emulsion layers.
- Examples A to H are comparative Examples.
- a silver halide-silver behenate dry soap was prepared by the procedures described in U.S. Pat. No. 3,839,049.
- the silver halide totalled 9% of the total silver while silver behenate comprised 91% of the total silver.
- the silver halide was a 0.055 micron silver bromoiodide emulsion with 2% iodide.
- a photothermographic emulsion was prepared by homogenizing 300 g of the silver halide-silver behenate dry soap described above with 525 g toluene, 1675 g 2-butanone and 50 g poly(vinylbutyral) (B-76, Monsanto).
- IR dye solution (8.8 mg D-1 dye in 7.1 g DMF), 4.2 g of supersensitizer solution (0.22 g 2-mercaptobenzimidazole, MBI, and 4 g methanol) and 16.6 of developer 1,1-bis(2-hydroxy-3,5-dimethylphenyl)-3,5,5-trimethylhexane.
- the photothermographic emulsion was divided into 40 g portions. The control was coated at this stage without any additions. The remaining aliquots were treated with 3 levels of each isocyanate test compound added as 16% (w/w) solutions in 2-butanone. Table 1 contains the conversions from the amount of 16% isocyanate (IC) solution added per 40 g portion to actual grams of IC. Multiplying the grams of IC by the percent NCO content gives the NCO equivalents.
- the photothermographic emulsion was coated on 3 mil (0.76 x 10 -4 m) polyester base by means of a knife coater and dried at 175°F (80°C) for four minutes.
- the dry coating weight was 23 g/m 2 .
- An active, protective topcoat solution was prepared with the following ingredients: 256.0 g acetone 123.0 g 2-butanone 50.0 g methanol 20.2 g cellulose acetate 2.89 g phthalazine 1.55 g 4-methylphthalic acid 1.01 g tetrachlorophthalic acid 0.90 g tetrabromophthalic anhydride 1.50 g tetrachlorophthalic anhydride 2.25 g 2-(tribromomethylsulfone)benzothiazole [AF-1]
- topcoat solutions were coated over the silver layer a a dry weight of 3.0 g/m 2 .
- the layer was dried at 165°F (74°C) for four minutes.
- the coated materials were then exposed with a laser sensitometer incorporating a 780 nm diode. After exposure, the film strips were processed at 260°F (127°C) for ten seconds. The images obtained were evaluated by a densitometer. Sensitometric results include Dmin, Dmax, Spd (relative speed at a density of 1.0 above Dmin versus a control with no added isocyanate set at 100) and average contrast (Cont, measured from a density of 0.25 to 2.0 above Dmin). Sensitometry was also evaluated after shelf aging at room temperature and under accelerated aging conditions (120°F (49°C) and 50% RH). The results are listed in Table 2 and show the strong antifoggant effect of the isocyanates on shelf aging and accelerated aging.
- IC-1 isocyanate
- AF-1 to AF-4 antifoggants
- the position of AF-1 in either the silver or topcoat formula was also tested. These examples were run with the IR formula described for examples 1-27 except with the changes listed in Table 4.
- the quantity of IC-1 was 0.006 moles per mole of silver when it was added to the coatings in Table 4. The results show improved fog control on shelf aging and accelerated aging when a combination of antifoggant (AF-1 to AF-4) and isocyanate are used.
- the isocyanates were tested to determine whether the improved fog levels on aging was specific to the infrared or a more general effect.
- the silver and topcoat formulas were the same as those used in examples 1-27 except for the omission of the infrared dye, D-1, and the supersensitizer, MBI, and the addition of AF-1 to the silver layer and not the topcoat layer at 27.6 x 10 -3 moles AF-1 per mole of silver.
- the two coatings (F and 33) in Table 5 were coated without any sensitizing dye.
- the coated materials were exposed with an EG&G sensitometer at 10 -3 seconds through a P-16 filter.
- Sensitometric results include Dmin, Dmax, Spd (speed at a density of 1.0), Ergs (speed or sensitivity at a density of 1.0) and Cont (contrast).
- a silver halide-silver behenate dry soap was prepared by the procedures described in U.S. Pat. No. 3,839,049.
- the silver halide totalled 9% of the total silver while silver behenate comprised 91% of the total silver.
- the silver halide was a 0.055 ⁇ m silver bromoiodide emulsion with 2% iodide.
- a photothermographic emulsion was prepared by homogenizing 300 g of the silver halide-silver behenate dry soap described above with 525 g toluene, 1666 g 2-butanone and 9.0 g poly(vinylbutyral) (B-76, Monsanto).
- the silver photothermographic emulsion was completed on the second day by warming to 70°F (21°C) and then adding 5 g of green sensitizing dye solution (0.0013 g D-2 dye and 5 g MeOH).
- a premix (100 g) was also prepared by combining the chemicals listed below: 0.97 g ethyl ketazine 1.89 g phthalazinone 0.24 g AF-1 85.80 g tetrahydrofuran 6.76 g polyvinyl(chloride-acetate-alcohol) tripolymer (VAGH, Union Carbide) 4.34 g poly(vinylbutyral) (B-76, Monsanto)
- a mixture was prepared by combining 6 grams of the silver formulation with 13.5 grams of premix.
- the photothermographic mixture was coated on 3 mil (0.76 x 10 -4 m) opaque polyester film filled with barium sulfate and dried at 170°F (77°C) for four minutes.
- the dry coating weight was 5 g/m 2 .
- An active, protective topcoat solution (100 g) was prepared with the following ingredients: 53.56 g acetone 26.44 g 2-butanone 10.68 g toluene 8.65 g polystyrene(Styrone 685D, Dow) 0.67 g (Solvent or isocyanate test compound)
- topcoat solutions were coated over the silver layer at a dry weight of 3.5 g/m 2 .
- the topcoat was dried at 170°F (77°C) for four minutes.
- 0.11 moles of IC-1 were added per mole of silver in example 34.
- the coated materials were exposed for 10 -3 seconds with a xenon flash from an EG&G sensitometer.
- the flash exposure was filtered with a green, Wratten 58 filter which has a maximum output at 530 nm.
- the film strips were then processed at 277°F (136°C) for 8 seconds to generate a magenta colored image.
- Sensitometric results include Dmin, Dmax, Spd (speed at a density of 0.6 above fog), Ergs (speed or sensitivity at a density of 0.6 above fog) and Cont (average contrast).
- a further improvement on the present invention is to combine the antifoggant (AF-1 to AF-4) and isocyanate with compounds covered in EP-A-0600589.
- the formula was the same as presented in Examples 34-41 except that the preformed silver halide was 0.075 ⁇ m and 100% bromide.
- Example 43 contained isocyanate (IC-2) and also 0.135 g of vinyl sulfone, VS, in 100 grams of topcoat.
- Table 7 shows that the best fog stability under accelerated aging conditions for the green sensitized, color photothermographic formula was obtained with a combination of isocyanate and vinyl sulfone (VS).
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Description
- The invention relates to a photothermographic silver halide material and method for producing in such a material improved fog stability on shelf aging by a combination of an isocyanate and a halogenated compound.
- Silver halide photothermographic imaging materials, often referred to as "dry silver" compositions because no liquid development is necessary to produce the final image, have been known in the art for many years. These imaging materials basically comprise a light insensitive, reducible silver source, a light sensitive material which generates silver when irradiated, and a reducing agent for the silver source. The light sensitive material is generally photographic silver halide which must be in catalytic proximity to the light insensitive silver source. Catalytic proximity is an intimate physical association of these two materials so that when silver specks or nuclei are generated by the irradiation or light exposure of the photographic silver halide, those nuclei are able to catalyze the reduction of the silver source by the reducing agent. It has been long understood that silver is a catalyst for the reduction of silver ions and the silver-generating light sensitive silver halide catalyst progenitor may be placed into catalytic proximity with the silver source in a number of different fashions, such as partial metathesis of the silver source with a halogen-containing source (e.g., U.S. Pat. No. 3,457,075), coprecipitation of the silver halide and silver source material (e.g., U.S. Pat. No. 3,839,049), and any other method which intimately associates the silver halide and the silver source.
- Photothermographic emulsions, in a manner similar to photographic emulsions and other light sensitive systems, tend to suffer from fog. Fog is spurious image density which appears in unexposed areas of the element and is often reported in sensitometric results as Dmin. Traditionally, photothermographic materials have suffered from fog instability on shelf aging. The fog level rises steadily as the materials reach extended age such as one year at room temperature (ambient conditions). Adding to the difficulty of fog control on shelf aging is the fact that the developer is incorporated in the photothermographic element which is not the case in most silver halide photographic systems. The need for shelf life extenders in photothermographic elements is therefore considered to be very important. The fog level of freshly prepared photothermographic materials will be referred to as initial fog. A great deal of effort has been directed towards minimizing the initial fog and stabilizing the fog level on shelf aging. Mercuric salts are described as antifoggants in U.S. Patent No. 3,589,903. Fog reduction has been described for organic carboxylic acids such as benzoic and phthalic acids in U.S. Patent No. 4,152,160, for benzoyl benzoic acid compounds in U.S. Patent No. 4,784,939, for indane or tetralin carboxylic acids in U.S. Patent No. 4,569,906, for dicarboxylic acids in U.S. Patent No. 4,820,617 and for heteroaromatic carboxylic acids in U.S. Patent No. 4,626,500. Halogenated compounds have also been shown to be strong antifoggants and are described in U.S. Patents 4,546,075, 4,756,999, 4,452,885, 3,874,946 and 3,955,982. Halogen molecules or halogen molecules associated with a heteroatom ring are also useful antifoggants and are described in U.S. Patent No. 5,028,523. However, these compounds individually or in combination were not found to produce sufficient fog stability on shelf aging of the photothermographic element.
- Diisocyanates have been used to improve the physical properties of photothermographic materials. They will crosslink the resin or binder which toughens the layer and reduces or eliminates scratching during hot roll processing. Crosslinking by diisocyanates is described in U.S. Patent No. 4,281,060 and in combination with boric acid in U.S. Patent No. 4,558,003. These patents used diisocyanates to harden or crosslink the resin.
- According to the present invention there is provided a photothermographic emulsion comprising in one or two layers a silver salt of an organic acid, silver halide, a reducing agent for silver ion, and a binder, the silver salt of an organic acid and the silver halide being present in one layer, characterised in that the emulsion contains, as an antifoggant, the combination of 1) at least one compound having an isocyanate group, and 2) a halogenated antifoggant compound which has an aromatic or heteroaromatic group having at least one perhalogenated alkyl group thereon.
- It has been found the generation of fog, in particular on shelf aging, in photothermographic elements comprising photosensitive silver halide, organic silver salt oxidizing agent and reducing agent for silver ion can be reduced by the combination of an isocyanate and the recited halogenated compound.
- In the emulsions of the invention the ability of the isocyanate to harden or crosslink is not critical to whether the isocyanate will act as a fog stabilizer on shelf aging. Octadecyl isocyanate, which has only a single isocyanate group, cannot crosslink the resin but still improves the fog stability on shelf aging.
- Suitable isocyanate compounds are those of the formula (I):
O=C=N-L-(N=C=O)v (I)
in which: - v represents 0, 1, or 2,
- L represents a linking group which can be an alkyl, alkene, aryl or a mixed alkylaryl group, or when v = 0, L represents a terminating group.
- The aryl ring may also carry substituents with examples of preferred substituents being selected from the class consisting of halogen (e.g. Br and Cl), hydroxy, amino, carboxy and alkoxy.
- Specific examples of isocyanate compounds along with the manufacturer and class are set forth below. The examples include aliphatic, aromatic and polymeric isocyanates.
- IC-1
- Desmodur N100, Mobay, aliphatic isocyanate
- IC-2
- Desmodur N3300, Mobay, aliphatic isocyanate
- IC-3
- Mondur TD-80, Mobay, aromatic isocyanate
- IC-4
- Mondur M, Mobay, aromatic isocyanate
- IC-5
- Mondur MRS, Mobay, polymeric isocyanate
- IC-6
- Desmodur W, Mobay, aliphatic isocyanate
- IC-7
- Papi 27, Dow, polymeric isocyanate
- IC-8
- Isocyanate T 1890, Huels, aliphatic isocyanate
- IC-9
- Octadecyl Isocyanate, Aldrich, aliphatic isocyanate
- The isocyanates are used in general amount of at least 0.0002 moles/mole of silver. Usually the range is between 0.002 and 2 moles of the compound per mole of silver and preferably between 0.003 and 0.3 moles of compound per mole of silver.
- Isocyanates improve the fog stability on shelf aging of photothermographic systems incorporating a halogenated antifoggant compound. The antifoggant preferably has at least one brominated alkyl group thereon, more preferably at least one tribromomethane group which may be directly attached to the aromatic or heteroaromatic group or bonded through a linking group, e.g. sulphonyl.
- The preferred antifoggant compounds are represented by the formula:
Ar-(SO2)y-CX3 (II)
in which: - y represents 0 or 1,
- X represents a halogen atom, and
- Ar represents an aromatic or heteroaromatic group.
- A detailed listing of compounds included in formula II is contained in U.S. Patent Nos. 4,546,075, 4,756,999, 4,452,885, 3,874,946 and 3,955,982.
- Where the term group is used in describing substituents, substitution is anticipated on the substituent for example, alkyl group includes for example ether groups (e.g., CH3-CH2-CH2-O-CH2-), haloalkyls, nitroalkyls, carboxyalkyls, hydroxyalkyls, sulfoalkyls while the term alkyl includes only hydrocarbons. Substituents which react with active ingredients, such as very strongly electrophilic or oxidizing substituents, would of course be excluded as not being inert or harmless.
- The halogenated compounds used in the present invention are generally incorporated in the silver or topcoat layer in a content of 5 x 10-4 mole to 0.5 mole preferably 5 x 10-3 to 5 x 10-2 mole, per mole of total silver.
-
- The photothermographic dry silver emulsions of this invention may be constructed of one or more layers on a substrate. Single layer constructions must contain the silver source material, the silver halide, the developer and binder as well as optional additional materials such as toners, coating aids, and other adjuvants. Two-layer constructions must contain the silver source and silver halide in one emulsion layer (usually the layer adjacent to the substrate) and some of the other ingredients in the second layer or both layers, although two layer constructions comprising a single emulsion layer containing all the ingredients and a protective topcoat are envisioned. Multicolor photothermographic dry silver constructions may contain sets of these bilayers for each color, or they may contain all ingredients within a single layer as described in U.S. Pat. No. 4,708,928. In the case of multilayer multicolor photothermographic articles the various emulsion layers are generally maintained distinct from each other by the use of functional or non-functional barrier layers between the various photosensitive layers as described in U.S. Pat. No. 4,460,681.
- While not necessary for practice of the present invention, it may be advantageous to add mercury (II) salts to the emulsion layer(s) as an antifoggant. Preferred mercury (II) salts for this purpose are mercuric acetate and mercuric bromide.
- The light sensitive silver halide used in the present invention may typically be employed in a range of 0.75 to 25 mol percent and, preferably, from 2 to 20 mol percent of organic silver salt.
- The silver halide may be any photosensitive silver halide such as silver bromide, silver iodide, silver chloride, silver bromoiodide, silver chlorobromoiodide and silver chlorobromide. The silver halide may be in any form which is photosensitive including, but not limited to cubic, orthorhombic, tabular and tetrahedral, and may have epitaxial growth of crystals thereon.
- The silver halide used in the present invention may be employed without modification. However, it may be chemically sensitized with a chemical sensitizing agent such as a compound containing sulfur, selenium or tellurium, or a compound containing gold, platinum, palladium, rhodium or iridium, a reducing agent such as a tin halide, or a combination thereof. The details of these procedures are described in T.N. James "The Theory of the Photographic Process", Fourth Edition, Chapter 5, pages 149 to 169.
- The silver halide may be added to the emulsion layer in any fashion which places it in catalytic proximity to the silver source. Silver halide and the organic silver salt which are separately formed or "preformed" in a binder can be mixed prior to use to prepare a coating solution, but it is also effective to blend both of them in a ball mill for a long period of time. Further, it is effective to use a process which comprises adding a halogen-containing compound in the organic silver salt prepared to partially convert the silver of the organic silver salt to silver halide.
- Methods of preparing these silver halide and organic silver salts and manners of blending them are known in the art and described in Research Disclosure, June 1978, item 17029, and U.S. Pat. No. 3,700,458.
- The use of preformed silver halide emulsions of this invention can be unwashed or washed to remove soluble salts. In the latter case the soluble salts can be removed by chill-setting and leaching or the emulsion can be coagulation washed, e.g., by the procedures described in U.S. Pat. Nos. 2,618,556; 2,614,928; 2,565,418; 3,241,969; and 2,489,341. The silver halide grains may have any crystalline habit including, but not limited to cubic, tetrahedral, orthorhombic, tabular, laminar and platelet.
- The organic silver salt may be any organic material which. contains a reducible source of silver ions. Silver salts of organic acids, particularly long chain (10 to 30 preferably 15 to 28 carbon atoms) fatty carboxylic acids are preferred. Complexes of organic or inorganic silver salts wherein the ligand has a gross stability constant between 4.0 and 10.0 are also desirable. The silver source material should preferably constitute from about 5 to 30 percent by weight of the imaging layer.
- The organic silver salt which can be used in the present invention is a silver salt which is comparatively stable to light, but forms a silver image when heated to 80°C or higher in the presence of an exposed photocatalyst (such as photographic silver halide) and a reducing agent.
- Preferred organic silver salts include silver salts of organic compounds having a carboxy group. Non-limiting examples thereof include silver salts of an aliphatic carboxylic acid and a silver salt of an aromatic carboxylic acid. Preferred examples of the silver salts of aliphatic carboxylic acids include silver behenate, silver stearate, silver oleate, silver laurate, silver caproate, silver myristate, silver palmitate, silver maleate, silver fumarate, silver tartrate, silver linoleate, silver butyrate and silver camphorate and mixtures thereof. Silver salts with a halogen atom or a hydroxyl on the aliphatic carboxylic acid can also be effectively used. Preferred examples of the silver salts of aromatic carboxylic acids and other carboxyl group-containing compounds include silver benzoate, a silver substituted benzoate such as silver 3,5-dihydroxybenzoate, silver o-methylbenzoate, silver m-methylbenzoate, silver p-methylbenzoate, silver 2,4-dichlorobenzoate, silver acetamidobenzoate, silver p-phenyl benzoate, silver gallate, silver tannate, silver phthalate, silver terephthalate, silver salicylate, silver phenylacetate, silver pyromellitate, a silver salt of 3-carboxymethyl-4-methyl-4-thiazoline-2-thione as described in U.S. Pat. No. 3,785,830, and silver salt of an aliphatic carboxylic acid containing a thioether group as described in U.S. Pat. No. 3,330,663.
- Silver salts of compounds containing mercapto or thione groups and derivatives thereof can also be used. Preferred examples of these compounds include a silver salt of 3-mercapto-4-phenyl-1,2,4-triazole, a silver salt of 2-mercaptobenzimidazole, a silver salt of 2-mercapto-5-aminothiadiazole, a silver salt of 2-(ethylglycolamido)benzothiazole, a silver salt of thioglycolic acid such as a silver salt of an S-alkyl thioglycolic acid (wherein the alkyl group has from 12 to 22 carbon atoms), a silver salt of a dithiocarboxylic acid such as a silver salt of dithioacetic acid, a silver salt of a thioamide, a silver salt of 5-carboxylic-1-methyl-2-phenyl-4-thiopyridine, a silver salt of mercaptotriazine, a silver salt of 2-mercaptobenzoxazole, a silver salt as described in U.S. Pat. No. 4,123,274, for example, a silver salt of 1,2,4-mercaptotriazole derivative such as a silver salt of 3-amino-5-benzylthio-1,2,4-triazole, a silver salt of a thione compound such as a silver salt of 3-(2-carboxyethyl)-4-methyl-4-thiazoline-2-thione as disclosed in U.S. Pat. No. 3,301,678.
- Furthermore, a silver salt of a compound containing an imino group may be used. Preferred examples of these compounds include silver salts of benzotriazole and derivatives thereof, for example, silver salts of benzotriazoles such as silver methylbenzotriazolate, silver salt of halogen-substituted benzotriazoles, such as silver 5-chlorobenzotriazolate, silver salts of carboimidobenzotriazole, silver salt of 1,2,4-triazoles or 1-H-tetrazoles as described in U.S. Pat. No. 4,220,709, silver salts of imidazoles and imidazole derivatives. Various silver acetylide compounds can also be used, for instance, as described in U.S. Pat. Nos. 4,761,361 and 4,775,613.
- It is also found convenient to use silver half soaps, of which an equimolar blend of silver behenate and behenic acid, prepared by precipitation from aqueous solution of the sodium salt of commercial behenic acid and analyzing about 14.5 percent silver, represents a preferred example. Transparent sheet materials made on transparent film backing require a transparent coating and for this purpose the silver behenate full soap, containing not more than about four or five percent of free behenic acid and analyzing about 25.2 percent silver may be used.
- The method used for making silver soap dispersions is well known in the art and is disclosed in Research Disclosure, April 1983, item 22812, Research Disclosure, October 1983, item 23419 and U.S. Pat. No. 3,985,565.
- The light-sensitive silver halides may be advantageously spectrally sensitized with various known dyes including cyanine, merocyanine, styryl, hemicyanine, oxonol, hemioxonol and xanthene dyes. Useful cyanine dyes include those having a basic nucleus, such as a thiazoline nucleus, an oxazoline nucleus, a pyrroline nucleus, a pyridine nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus and an imidazole nucleus. Useful merocyanine dyes which are preferred include those having not only the above described basic nuclei but also acid nuclei, such as a thiohydantoin nucleus, a rhodanine nucleus, an oxazolidinedione nucleus, a thiazolidinedione nucleus, a barbituric acid nucleus, a thiazolinone nucleus, a malononitrile nucleus and a pyrazolone nucleus. In the above described cyanine and merocyanine dyes, those having imino groups or carboxyl groups are particularly effective. Practically, the sensitizing dyes to be used in the present invention may be properly selected from known dyes such as those described in U.S. Pat. Nos. 3,761,279, 3,719,495, and 3,877,943, British Pat. Nos. 1,466,201, 1,469,117 and 1,422,057, and can be located in the vicinity of the photocatalyst according to known methods. Spectral sensitizing dyes may be typically used in amounts of about 10-4 mol to about 1 mol per 1 mol of silver halide.
- The reducing agent for the organic silver salt may be any material, preferably organic material, that can reduce silver ion to metallic silver. Conventional photographic developers such as phenidone, hydroquinones, and catechol are useful but hindered phenol reducing agents are preferred. The reducing agent should be present as 1 to 10 percent by weight of the imaging layer. In multilayer constructions, if the reducing agent is added to a layer other than an emulsion layer, slightly higher proportions, of from about 2 to 15 percent tend to be more desirable.
- A wide range of reducing agents have been disclosed in dry silver systems including amidoximes such as phenylamidoxime, 2-thienylamidoxime and p-phenoxyphenylamidoxime, azines (e.g., 4-hydroxy-3,5-dimethoxybenzaldehydeazine); a combination of aliphatic carboxylic acid aryl hydrazides and ascorbic acid, such as 2,2'-bis(hydroxymethyl)propionyl-β-phenylhydrazide in combination with ascorbic acid; a combination of polyhydroxybenzene and hydroxylamine, a reductone and/or a hydrazine (e.g., a combination of hydroquinone and bis(ethoxyethyl)hydroxylamine, piperidinohexose reductone or formyl-4-methylphenylhydrazine); hydroxamic acids such as phenylhydroxamic acid, p-hydroxyphenylhydroxamic acid, and β-alaninehydroxamic acid; a combination of azines and sulfonamidophenols, (e.g., phenothiazine and 2,6-dichloro-4-benzenesulfonamidophenol); α-cyanophenylacetic acid derivatives such as ethyl-α-cyano-2-methylphenylacetate, ethyl α-cyanophenylacetate; bis-β-naphthols as illustrated by 2,2'-dihydroxyl-1-binaphthyl, 6,6'-dibromo-2,2'-dihydroxy-1,1'-binaphthyl, and bis(2-hydroxy-1-naphthyl)methane; a combination of bis-β-naphthol and a 1,3-dihydroxybenzene derivative, (e.g., 2,4-dihydroxybenzophenone or 2,4-dihydroxyacetophenone); 5-pyrazolones such as 3-methyl-1-phenyl-5-pyrazolone; reductones as illustrated by dimethylaminohexose reductone, anhydrodihydroaminohexose reductone, and anhydrodihydropiperidonehexose reductone; sulfonamido-phenol reducing agents such as 2,6-dichloro-4-benzenesulfonamidophenol, and p-benzenesulfonamidophenol; 2-phenylindane-1,3-dione; chromans such as 2,2-dimethyl-7-t-butyl-6-hydroxychroman; 1,4-dihydropyridines such as 2,6-dimethoxy-3,5-dicarboethoxy-1,4-dihydropyridine; bisphenols (e.g., bis(2-hydroxy-3-t-butyl-5-methylphenyl)methane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 4,4-ethylidene-bis(2-t-butyl-6-methylphenol), and 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane); ascorbic acid derivatives (e.g., 1-ascorbyl palmitate, ascorbyl stearate); and unsaturated aldehydes and ketones, such as benzil and biacetyl; 3-pyrazolidones and certain indane-1,3-diones.
- In addition to the aforementioned ingredients, it may be advantageous to include additives known as "toners" that improve the image. Toner materials may be present, for example, in amounts from 0.1 to 10 percent by weight of all silver bearing components. Toners are well known materials in the photothermographic art as shown in U.S. Pat. Nos. 3,080,254; 3,847,612 and 4,123,282.
- Examples of toners include phthalimide and N-hydroxyphthalimide; cyclic imides such as succinimide, pyrazoline-5-ones, and a quinazolinone, 3-phenyl-2- pyrazoline-5-one, 1-phenylurazole, quinazoline, and 2,4- thiazolidinedione; naphthalimides (e.g., N-hydroxy-1,8-naphthalimide); cobalt complexes (e.g., cobaltic hexammine trifluoroacetate); mercaptans as illustrated by 3-mercapto-1,2,4-triazole, 2,4-dimercaptopyrimidine, 3-mercapto-4,5-diphenyl-1,2,4-triazole and 2,5-dimercapto-1,3,4-thiadiazole; N-(aminomethyl)aryldicarboximides, (e.g., (N, N-dimethylaminomethyl)phthalimide, and N,N-(dimethylaminomethyl)naphthalene-2,3-dicarboximide); and a combination of blocked pyrazoles, isothiuronium derivatives and certain photobleaching agents (e.g., a combination of N,N'-hexamethylene bis(1-carbamoyl-3,5-dimethylpyrazole), 1,8-(3,6-diazaoctane)bis(isothiuronium trifluoroacetate) and 2-(tribromomethylsulfonyl)benzothiazole); and merocyanine dyes such as 3-ethyl-5[(3-ethyl-2-benzothiazolinylidene)-1-methylethylidene]-2-thio-2,4-oxazolidinedione; phthalazinone and phthalazinone derivatives or metal salts or these derivatives such as 4-(1-naphthyl)phthalazinone, 6-chlorophthalazinone, 5,7-dimethoxyphthalazinone, and 2,3-dihydro-1,4-phthalazinedione; a combination of phthalazinone plus sulfinic acid derivatives (e.g., phthalic acid, 4-methylphthalic acid, 4-nitrophthalic acid, and tetrachlorophthalic anhydride); quinazolinediones, benzoxazine or naphthoxazine derivatives; rhodium complexes functioning not only as tone modifiers, but also as sources of halide ion for silver halide formation in situ, such as ammonium hexachlororhodate (III), rhodium bromide, rhodium nitrate and potassium hexachlororhodate (III); inorganic peroxides and persulfates (e.g., ammonium peroxydisulfate and hydrogen peroxide); benzoxazine-2,4-diones such as 1,3-benzoxazine-2,4-dione, 8-methyl-1,3-benzoxazine-2,4-dione, and 6-nitro-1,3-benzoxazine-2,4-dione; pyrimidines and asymmetric triazines (e.g., 2,4-dihydroxypyrimidine, 2-hydroxy-4-aminopyrimidine), azauracils, and tetrazapentalene derivatives (e.g, 3,6-dimercapto-1,4-diphenyl-1H,4H-2,3a,5,6a-tetrazapentalene, and 1,4-di(o-chlorophenyl)-3,6-dimercapto-1H,4H-2,3a,5,6a-tetrazapentalene).
- A number of methods are known in the art for obtaining color images with dry silver systems including: a combination of silver benzotriazole, well known magenta, yellow and cyan dye-forming couplers, aminophenol developing agents, a base release agent such as guanidinium trichloroacetate and silver bromide in poly(vinyl butyral) as described in U.S. Pat. Nos. 4,847,188 and 5,064,742; preformed dye release systems such as those described in U.S. Pat. No. 4,678,739; a combination of silver bromoiodide, sulfonamidophenol reducing agent, silver behenate, poly(vinyl butyral), an amine such as n-octadecylamine and 2-equivalent or 4-equivalent cyan, magenta or yellow dye-forming couplers; leuco dye bases which oxidize to form a dye image (e.g., Malachite Green, Crystal Violet and para-rosaniline); a combination of in situ silver halide, silver behenate, 3-methyl-1-phenylpyrazolone and N,N'-dimethyl-p-phenylenediamine hydrochloride; incorporating phenolic leuco dye reducing agents such as 2(3,5-di-(t-butyl)-4-hydroxyphenyl)-4,5-diphenylimidazole, and bis(3,5-di-(t-butyl)-4-hydroxyphenyl)phenylmethane, incorporating azomethine dyes or azo dye reducing agents; silver dye bleach processes (for example, an element comprising silver behenate, behenic acid, poly(vinyl butyral), poly(vinyl-butyral)peptized silver bromoiodide emulsion, 2,6-dichloro-4-benzenesulfonamidophenol, 1,8-(3,6-diazaoctane)bis(isothiuronium-p-toluenesulfonate) and an azo dye can be exposed and heat processed to obtain a negative silver image with a uniform distribution of dye, and then laminated to an acid activator sheet comprising polyacrylic acid, thiourea and p-toluenesulfonic acid and heated to obtain well defined positive dye images); and amines such as aminoacetanilide (yellow dye-forming), 3,3'-dimethoxybenzidine (blue dye-forming) or sulfanilide (magenta dye forming) that react with the oxidized form of incorporated reducing agents such as 2,6-dichloro-4-benzenesulfonamidophenol to form dye images. Neutral dye images can be obtained by the addition of amines such as behenylamine and p-anisidine.
- Leuco dye oxidation in such silver halide systems for color formation is disclosed in U.S. Pat. Nos. 4,021,240, 4,374,821, 4,460,681 and 4,883,747.
- Silver halide emulsions containing the antifoggants used in this invention can be protected further against the additional production of fog and can be stabilized against loss of sensitivity during shelf storage. Suitable antifoggants, stabilizers, and stabilizer precursors which can be used alone or in combination, include thiazolium salts as described in U.S. Pat. Nos. 2,131,038 and 2,694,716; azaindenes as described in U.S. Pat. Nos. 2,886,437 and 2,444,605; mercury salts as described in U.S. Pat. No. 2,728,663; urazoles as described in U.S. Pat. No. 3,287,135; sulfocatechols as described in U.S. Pat. No. 3,235,652; oximes as described in British Pat. No. 623,448; nitrones; nitroindazoles; polyvalent metal salts as described in U.S. Pat. No. 2,839,405; thiouronium salts as described in U.S. Pat. No. 3,220,839; and palladium, platinum and gold salts described in U.S. Pat. Nos. 2,566,263 and 2,597,915; halogen-substituted organic compounds as described in U.S. Pat. Nos. 4,108,665 and 4,442,202; triazines as described in U.S. Pat. Nos. 4,128,557; 4,137,079; 4,138,265; and 4,459,350; and phosphorous compounds as described in U.S. Pat. No. 4,411,985.
- Emulsions of the invention can contain plasticizers and lubricants such as polyalcohols (e.g., glycerin and diols of the type described in U.S. Pat. No. 2,960,404); fatty acids or esters such as those described in U.S. Pat. No. 2,588,765 and U.S. Pat. No. 3,121,060; and silicone resins such as those described in British Pat. No. 955,061.
- The photothermographic elements used in the present invention may include image dye stabilizers. Such image dye stabilizers are illustrated by British Pat. No. 1,326,889; U.S. Pat. Nos. 3,432,300; 3,698,909; 3,574,627; 3,573,050; 3,764,337 and 4,042,394.
- Photothermographic elements containing emulsion layers according to the present invention can be used in photographic elements which contain light absorbing materials and filter dyes such as those described in U.S. Pat. Nos. 3,253,921; 2,274,782; 2,527,583 and 2,956,879. If desired, the dyes can be mordanted, for example, as described in U.S. Pat. No. 3,282,699.
- Photothermographic elements containing emulsion layers as described herein can contain matting agents such as starch, titanium dioxide, zinc oxide, silica, polymeric beads including beads of the type described in U.S. Pat. No. 2,992,101 and U.S. Pat. No. 2,701,245.
- Emulsions in accordance with this invention can be used in photothermographic elements which contain antistatic or conducting layers, such as layers that comprise soluble salts (e.g., chlorides or nitrates), evaporated metal layers, ionic polymers such as those described in U.S. Pat. Nos. 2,861,056 and 3,206,312 or insoluble inorganic salts such as those described in U.S. Pat. No. 3,428,451.
- The binder may be selected from any of the well-known natural or synthetic resins such as gelatin, polyvinyl acetals, polyvinyl chloride, polyvinyl acetate, cellulose acetate, polyolefins, polyesters, polystyrene, polyacrylonitrile or polycarbonates. Copolymers and terpolymers are of course included in these definitions. The preferred photothermographic silver containing polymers are polyvinyl butyral, ethyl cellulose, methacrylate copolymers, maleic anhydride ester copolymers, polystyrene, and butadiene-styrene copolymers.
- Optionally, these polymers may be used in combinations of two or more thereof. Such a polymer is used in an amount sufficient to carry the components dispersed therein, that is, within the effective range of the action as the binder. The effective range can be appropriately determined by one skilled in the art. As a guide in the case of carrying at least an organic silver salt, it can be said that a preferable ratio of the binder to the organic silver salt ranges from 15:1 to 1:2, and particularly from 8:1 to 1:1.
- Photothermographic emulsions containing a stabilizer according to the present invention may be coated on a wide variety of supports. Typical supports include polyester film, subbed polyester film, poly(ethylene terephthalate) film, cellulose nitrate film, cellulose ester film, poly(vinyl acetal) film, polycarbonate film and related or resinous materials, as well as glass, paper or metal. Typically, a flexible support is employed, especially a paper support, which may be partially acetylated or coated with baryta and/or an α-olefin polymer, particularly a polymer of an α-olefin containing 2 to 10 carbon atoms such as polyethylene, polypropylene, ethylene-butene copolymers and the like. Substrates may be transparent or opaque.
- Substrates with a backside resistive heating layer may also be used in photothermographic imaging systems such as shown in U.S. Pat. Nos. 4,460,681 and 4,374,921.
- Photothermographic emulsions of this invention can be coated by various coating procedures including dip coating, air knife coating, curtain coating, or extrusion coating using hoppers of the type described in U.S. Pat. No. 2,681,294. If desired, two or more layers may be coated simultaneously by the procedures described in U.S. Pat. No. 2,761,791 and British Pat. No. 837,095.
- Additional layers may be incorporated into photothermographic articles of the present invention such as dye receptive layers for receiving a mobile dye image, an opacifying layer when reflection prints are desired, a protective topcoat layer and a primer layer as is known in the photothermographic art. Additionally, it may be desirable in some instances to coat different emulsion layers on both sides of a transparent substrate, especially when it is desirable to isolate the imaging chemistries of the different emulsion layers.
- The present invention will be illustrated in detail in the following examples, but the embodiment of the present invention is not limited thereto. Examples A to H are comparative Examples.
- A silver halide-silver behenate dry soap was prepared by the procedures described in U.S. Pat. No. 3,839,049. The silver halide totalled 9% of the total silver while silver behenate comprised 91% of the total silver. The silver halide was a 0.055 micron silver bromoiodide emulsion with 2% iodide.
- A photothermographic emulsion was prepared by homogenizing 300 g of the silver halide-silver behenate dry soap described above with 525 g toluene, 1675 g 2-butanone and 50 g poly(vinylbutyral) (B-76, Monsanto).
- The homogenized photothermographic emulsion (500 g) and 100 g 2-butanone were cooled to 55°F (13°C) with stirring. Additional poly(vinylbutyral) (75.7 g B-76) was added and stirred for 20 minutes. Pyridinium hydrobromide perbromide (PHP, 0.45 g) was added and stirred for 2 hours. The addition of 3.25 ml of a calcium bromide solution (1 g of CaBr2 and 10 ml of methanol) was followed by 30 minutes of stirring. The temperature was raised to 70°F (21°C) and the following were added in 15 minute increments with stirring: IR dye solution (8.8 mg D-1 dye in 7.1 g DMF), 4.2 g of supersensitizer solution (0.22 g 2-mercaptobenzimidazole, MBI, and 4 g methanol) and 16.6 of developer 1,1-bis(2-hydroxy-3,5-dimethylphenyl)-3,5,5-trimethylhexane.
- The photothermographic emulsion was divided into 40 g portions. The control was coated at this stage without any additions. The remaining aliquots were treated with 3 levels of each isocyanate test compound added as 16% (w/w) solutions in 2-butanone. Table 1 contains the conversions from the amount of 16% isocyanate (IC) solution added per 40 g portion to actual grams of IC. Multiplying the grams of IC by the percent NCO content gives the NCO equivalents.
- The photothermographic emulsion was coated on 3 mil (0.76 x 10-4m) polyester base by means of a knife coater and dried at 175°F (80°C) for four minutes. The dry coating weight was 23 g/m2.
- An active, protective topcoat solution was prepared with the following ingredients:
256.0 g acetone 123.0 g 2-butanone 50.0 g methanol 20.2 g cellulose acetate 2.89 g phthalazine 1.55 g 4-methylphthalic acid 1.01 g tetrachlorophthalic acid 0.90 g tetrabromophthalic anhydride 1.50 g tetrachlorophthalic anhydride 2.25 g 2-(tribromomethylsulfone)benzothiazole [AF-1] - The topcoat solutions were coated over the silver layer a a dry weight of 3.0 g/m2. The layer was dried at 165°F (74°C) for four minutes.
- The coated materials were then exposed with a laser sensitometer incorporating a 780 nm diode. After exposure, the film strips were processed at 260°F (127°C) for ten seconds. The images obtained were evaluated by a densitometer. Sensitometric results include Dmin, Dmax, Spd (relative speed at a density of 1.0 above Dmin versus a control with no added isocyanate set at 100) and average contrast (Cont, measured from a density of 0.25 to 2.0 above Dmin). Sensitometry was also evaluated after shelf aging at room temperature and under accelerated aging conditions (120°F (49°C) and 50% RH). The results are listed in Table 2 and show the strong antifoggant effect of the isocyanates on shelf aging and accelerated aging.
- An experiment was run to compare the effect of adding the isocyanate to the protective topcoat versus to the silver layer. The formulas were the same as described for examples 1-27. Example 2 and example 28 in Table 3 both contained 0.006 moles of IC-1 per one mole of total silver. The results are listed in Table 3 and show that the isocyanates act as strong antifoggants whether added to the silver or topcoat formulas.
- The additive effect of the isocyanate, IC-1, on different antifoggants (AF-1 to AF-4) were evaluated in the following examples. The position of AF-1 in either the silver or topcoat formula was also tested. These examples were run with the IR formula described for examples 1-27 except with the changes listed in Table 4. The quantity of IC-1 was 0.006 moles per mole of silver when it was added to the coatings in Table 4. The results show improved fog control on shelf aging and accelerated aging when a combination of antifoggant (AF-1 to AF-4) and isocyanate are used.
- The isocyanates were tested to determine whether the improved fog levels on aging was specific to the infrared or a more general effect. The silver and topcoat formulas were the same as those used in examples 1-27 except for the omission of the infrared dye, D-1, and the supersensitizer, MBI, and the addition of AF-1 to the silver layer and not the topcoat layer at 27.6 x 10-3 moles AF-1 per mole of silver. The two coatings (F and 33) in Table 5 were coated without any sensitizing dye.
- The coated materials were exposed with an EG&G sensitometer at 10-3 seconds through a P-16 filter.
- After exposure, the film strips were processed at 260°F (127°C) for ten seconds. Sensitometric results include Dmin, Dmax, Spd (speed at a density of 1.0), Ergs (speed or sensitivity at a density of 1.0) and Cont (contrast).
-
- A green sensitized color photothermographic formula was tested to decide if isocyanates could again reduce the fog increase on shelf aging.
- A silver halide-silver behenate dry soap was prepared by the procedures described in U.S. Pat. No. 3,839,049. The silver halide totalled 9% of the total silver while silver behenate comprised 91% of the total silver. The silver halide was a 0.055 µm silver bromoiodide emulsion with 2% iodide.
- A photothermographic emulsion was prepared by homogenizing 300 g of the silver halide-silver behenate dry soap described above with 525 g toluene, 1666 g 2-butanone and 9.0 g poly(vinylbutyral) (B-76, Monsanto).
- The homogenized photothermographic emulsion (73 g) and 14.6 g 2-butanone were cooled to 55°F (13°C) with stirring. The following were added while the temperature was maintained at 55°F (13°C).
Ingredient Mix 11.7 g poly(vinylbutyral) (B-76) 25 min 0.02 g PHP 1 hour 0.02 g PHP 1 hour 0.02 g PHP 4 hour 0.39 g CaBr2 solution (10% w/v in MeOH) hold overnight at 55°F 0.5 hour -
- A premix (100 g) was also prepared by combining the chemicals listed below:
0.97 g ethyl ketazine 1.89 g phthalazinone 0.24 g AF-1 85.80 g tetrahydrofuran 6.76 g polyvinyl(chloride-acetate-alcohol) tripolymer (VAGH, Union Carbide) 4.34 g poly(vinylbutyral) (B-76, Monsanto) - A mixture was prepared by combining 6 grams of the silver formulation with 13.5 grams of premix. The photothermographic mixture was coated on 3 mil (0.76 x 10-4m) opaque polyester film filled with barium sulfate and dried at 170°F (77°C) for four minutes. The dry coating weight was 5 g/m2.
- An active, protective topcoat solution (100 g) was prepared with the following ingredients:
53.56 g acetone 26.44 g 2-butanone 10.68 g toluene 8.65 g polystyrene(Styrone 685D, Dow) 0.67 g (Solvent or isocyanate test compound) - The topcoat solutions were coated over the silver layer at a dry weight of 3.5 g/m2. The topcoat was dried at 170°F (77°C) for four minutes. For comparison, 0.11 moles of IC-1 were added per mole of silver in example 34.
- The coated materials were exposed for 10-3 seconds with a xenon flash from an EG&G sensitometer. The flash exposure was filtered with a green, Wratten 58 filter which has a maximum output at 530 nm. The film strips were then processed at 277°F (136°C) for 8 seconds to generate a magenta colored image. Sensitometric results include Dmin, Dmax, Spd (speed at a density of 0.6 above fog), Ergs (speed or sensitivity at a density of 0.6 above fog) and Cont (average contrast).
-
- A further improvement on the present invention is to combine the antifoggant (AF-1 to AF-4) and isocyanate with compounds covered in EP-A-0600589. The formula was the same as presented in Examples 34-41 except that the preformed silver halide was 0.075 µm and 100% bromide. Example 43 contained isocyanate (IC-2) and also 0.135 g of vinyl sulfone, VS, in 100 grams of topcoat. Table 7 shows that the best fog stability under accelerated aging conditions for the green sensitized, color photothermographic formula was obtained with a combination of isocyanate and vinyl sulfone (VS).
VS CH2=CH-SO2-CH2-O-CH2-SO2-CH=CH2
Claims (10)
- A photothermographic emulsion comprising in one or two layers a silver salt of an organic acid, silver halide, a reducing agent for silver ion, and a binder, the silver salt of an organic acid and the silver halide being present in one layer, characterised in that the emulsion contains, as an antifoggant, the combination of 1) at least one compound having an isocyanate group, and 2) a halogenated antifoggant compound which has an aromatic or heteroaromatic group having at least one perhalogenated alkyl group thereon.
- An emulsion as claimed in Claim 1 in which the halogenated antifoggant compound has a brominated alkyl group thereon.
- An emulsion as claimed in Claim 2 in which the halogenated antifoggant compound has at least one tribromomethane group thereon.
- An emulsion as claimed in Claim 3 in which the tribromomethane group is directly attached to an aromatic or heteroaromatic group or the tribromomethane group is bonded to an aromatic or heteroaromatic group through a linking group.
- An emulsion as claimed in Claim 4 in which said linking group is sulfonyl.
- An emulsion as claimed in any preceding Claim in which the halogenated antifoggant compound has the formula:
Ar-(SO2)y-CX3
in which:Ar is an aromatic or heteroaromatic group, andy is 0 or 1. - An emulsion as claimed in any preceding Claim in which the compound having an isocyanate group is represented by the formula
O=C=N-L-(N=C=O)v
whereinv is 0, 1, or 2, andL is a linking group or when v is 0, L is a terminatinggroup. - An emulsion as claimed in Claim 7 in which L is selected from alkyl, alkene, aryl, and mixed alkylaryl groups.
- An emulsion as claimed in any preceding Claim in which the compound having an isocyanate group is present in an amount in the range 0.002 to 2 moles per mole of silver.
- An emulsion as claimed in any preceding Claim in which the halogenated antifoggant compound is present in an amount in the range 5 x 10-4 to 0.5 mole per mole of silver.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US98312592A | 1992-11-30 | 1992-11-30 | |
US983125 | 1992-11-30 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0600586A1 EP0600586A1 (en) | 1994-06-08 |
EP0600586B1 true EP0600586B1 (en) | 1997-12-10 |
Family
ID=25529797
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP93307739A Expired - Lifetime EP0600586B1 (en) | 1992-11-30 | 1993-09-29 | Photothermographic elements |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP0600586B1 (en) |
JP (1) | JP3241908B2 (en) |
DE (1) | DE69315674T2 (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7348110B2 (en) | 2004-02-27 | 2008-03-25 | Carestream Health, Inc. | Thermally developable imaging material |
WO2015148028A1 (en) | 2014-03-24 | 2015-10-01 | Carestream Health, Inc. | Thermally developable imaging materials |
WO2016073086A1 (en) | 2014-11-04 | 2016-05-12 | Carestream Health, Inc. | Image forming materials, preparations, and compositions |
WO2016195950A1 (en) | 2015-06-02 | 2016-12-08 | Carestream Health, Inc. | Thermally developable imaging materials and methods |
WO2017123444A1 (en) | 2016-01-15 | 2017-07-20 | Carestream Health, Inc. | Method of preparing silver carboxylate soaps |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0642056A3 (en) * | 1993-09-02 | 1995-08-02 | Minnesota Mining & Mfg | Photothermographic elements. |
US6586170B1 (en) | 1997-08-11 | 2003-07-01 | Fuji Photo Film Co., Ltd. | Thermographic recording element |
JP2002131863A (en) * | 2000-10-20 | 2002-05-09 | Konica Corp | Silver salt light and heat photographic material |
JP4369876B2 (en) | 2004-03-23 | 2009-11-25 | 富士フイルム株式会社 | Silver halide photosensitive material and photothermographic material |
US20060057512A1 (en) | 2004-09-14 | 2006-03-16 | Fuji Photo Film Co., Ltd. | Photothermographic material |
US7297658B2 (en) | 2005-06-24 | 2007-11-20 | Carestream Health, Inc. | Direct thermographic materials with crosslinked carrier layer |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4281060A (en) * | 1979-06-27 | 1981-07-28 | Fuji Photo Film Co., Ltd. | Heat-developable photosensitive materials |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB8528545D0 (en) * | 1985-11-20 | 1985-12-24 | Minnesota Mining & Mfg | Photothermographic materials |
JPS6352137A (en) * | 1986-08-22 | 1988-03-05 | Konica Corp | Heat-developable photosensitive material with improved shelf stability of image |
-
1993
- 1993-09-29 EP EP93307739A patent/EP0600586B1/en not_active Expired - Lifetime
- 1993-09-29 DE DE1993615674 patent/DE69315674T2/en not_active Expired - Fee Related
- 1993-11-29 JP JP29789093A patent/JP3241908B2/en not_active Expired - Fee Related
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4281060A (en) * | 1979-06-27 | 1981-07-28 | Fuji Photo Film Co., Ltd. | Heat-developable photosensitive materials |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7348110B2 (en) | 2004-02-27 | 2008-03-25 | Carestream Health, Inc. | Thermally developable imaging material |
WO2015148028A1 (en) | 2014-03-24 | 2015-10-01 | Carestream Health, Inc. | Thermally developable imaging materials |
US9335623B2 (en) | 2014-03-24 | 2016-05-10 | Carestream Health, Inc. | Thermally developable imaging materials |
WO2016073086A1 (en) | 2014-11-04 | 2016-05-12 | Carestream Health, Inc. | Image forming materials, preparations, and compositions |
WO2016195950A1 (en) | 2015-06-02 | 2016-12-08 | Carestream Health, Inc. | Thermally developable imaging materials and methods |
WO2017123444A1 (en) | 2016-01-15 | 2017-07-20 | Carestream Health, Inc. | Method of preparing silver carboxylate soaps |
Also Published As
Publication number | Publication date |
---|---|
EP0600586A1 (en) | 1994-06-08 |
DE69315674T2 (en) | 1998-07-09 |
DE69315674D1 (en) | 1998-01-22 |
JPH06208193A (en) | 1994-07-26 |
JP3241908B2 (en) | 2001-12-25 |
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