EP0557785A1 - Photographic assembly - Google Patents
Photographic assembly Download PDFInfo
- Publication number
- EP0557785A1 EP0557785A1 EP93101989A EP93101989A EP0557785A1 EP 0557785 A1 EP0557785 A1 EP 0557785A1 EP 93101989 A EP93101989 A EP 93101989A EP 93101989 A EP93101989 A EP 93101989A EP 0557785 A1 EP0557785 A1 EP 0557785A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- styrene
- butyl acrylate
- latex
- emulsion layer
- acrylate
- 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.)
- Granted
Links
- 239000000839 emulsion Substances 0.000 claims abstract description 35
- -1 silver halide Chemical class 0.000 claims abstract description 29
- 229920000126 latex Polymers 0.000 claims abstract description 28
- 239000004816 latex Substances 0.000 claims abstract description 24
- 229910052709 silver Inorganic materials 0.000 claims abstract description 21
- 239000004332 silver Substances 0.000 claims abstract description 21
- 239000000178 monomer Substances 0.000 claims abstract description 18
- 108010010803 Gelatin Proteins 0.000 claims abstract description 17
- 229920000159 gelatin Polymers 0.000 claims abstract description 17
- 239000008273 gelatin Substances 0.000 claims abstract description 17
- 235000019322 gelatine Nutrition 0.000 claims abstract description 17
- 235000011852 gelatine desserts Nutrition 0.000 claims abstract description 17
- 229920002284 Cellulose triacetate Polymers 0.000 claims abstract description 12
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 claims abstract description 12
- 229920006217 cellulose acetate butyrate Polymers 0.000 claims abstract description 11
- 125000003118 aryl group Chemical group 0.000 claims abstract description 10
- 229920000642 polymer Polymers 0.000 claims abstract description 8
- 229920001577 copolymer Polymers 0.000 claims abstract description 3
- 230000009477 glass transition Effects 0.000 claims abstract description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 34
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 18
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 4
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 claims description 4
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 3
- ZWEDFBKLJILTMC-UHFFFAOYSA-N ethyl 4,4,4-trifluoro-3-hydroxybutanoate Chemical compound CCOC(=O)CC(O)C(F)(F)F ZWEDFBKLJILTMC-UHFFFAOYSA-N 0.000 claims description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 3
- CHRJZRDFSQHIFI-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;styrene Chemical compound C=CC1=CC=CC=C1.C=CC1=CC=CC=C1C=C CHRJZRDFSQHIFI-UHFFFAOYSA-N 0.000 claims description 2
- 239000010410 layer Substances 0.000 description 24
- 239000004094 surface-active agent Substances 0.000 description 13
- 238000012545 processing Methods 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- 239000003999 initiator Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000004159 Potassium persulphate Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- 230000000712 assembly Effects 0.000 description 3
- 238000000429 assembly Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000002736 nonionic surfactant Substances 0.000 description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 3
- 235000019394 potassium persulphate Nutrition 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- JESXATFQYMPTNL-UHFFFAOYSA-N 2-ethenylphenol Chemical compound OC1=CC=CC=C1C=C JESXATFQYMPTNL-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
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 125000002467 phosphate group Chemical class [H]OP(=O)(O[H])O[*] 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 2
- 239000004296 sodium metabisulphite Substances 0.000 description 2
- 235000010262 sodium metabisulphite Nutrition 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 229910021653 sulphate ion Inorganic materials 0.000 description 2
- QGKMIGUHVLGJBR-UHFFFAOYSA-M (4z)-1-(3-methylbutyl)-4-[[1-(3-methylbutyl)quinolin-1-ium-4-yl]methylidene]quinoline;iodide Chemical compound [I-].C12=CC=CC=C2N(CCC(C)C)C=CC1=CC1=CC=[N+](CCC(C)C)C2=CC=CC=C12 QGKMIGUHVLGJBR-UHFFFAOYSA-M 0.000 description 1
- OEVVKKAVYQFQNV-UHFFFAOYSA-N 1-ethenyl-2,4-dimethylbenzene Chemical compound CC1=CC=C(C=C)C(C)=C1 OEVVKKAVYQFQNV-UHFFFAOYSA-N 0.000 description 1
- SYZVQXIUVGKCBJ-UHFFFAOYSA-N 1-ethenyl-3-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC(C=C)=C1 SYZVQXIUVGKCBJ-UHFFFAOYSA-N 0.000 description 1
- UAJRSHJHFRVGMG-UHFFFAOYSA-N 1-ethenyl-4-methoxybenzene Chemical compound COC1=CC=C(C=C)C=C1 UAJRSHJHFRVGMG-UHFFFAOYSA-N 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- IEORSVTYLWZQJQ-UHFFFAOYSA-N 2-(2-nonylphenoxy)ethanol Chemical compound CCCCCCCCCC1=CC=CC=C1OCCO IEORSVTYLWZQJQ-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- NICLKHGIKDZZGV-UHFFFAOYSA-N 2-cyanopentanoic acid Chemical compound CCCC(C#N)C(O)=O NICLKHGIKDZZGV-UHFFFAOYSA-N 0.000 description 1
- 229940044192 2-hydroxyethyl methacrylate Drugs 0.000 description 1
- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical compound CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-UHFFFAOYSA-N 0.000 description 1
- ILZXXGLGJZQLTR-UHFFFAOYSA-N 2-phenylethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC1=CC=CC=C1 ILZXXGLGJZQLTR-UHFFFAOYSA-N 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- SJOOOZPMQAWAOP-UHFFFAOYSA-N [Ag].BrCl Chemical compound [Ag].BrCl SJOOOZPMQAWAOP-UHFFFAOYSA-N 0.000 description 1
- XCFIVNQHHFZRNR-UHFFFAOYSA-N [Ag].Cl[IH]Br Chemical compound [Ag].Cl[IH]Br XCFIVNQHHFZRNR-UHFFFAOYSA-N 0.000 description 1
- UGZICOVULPINFH-UHFFFAOYSA-N acetic acid;butanoic acid Chemical compound CC(O)=O.CCCC(O)=O UGZICOVULPINFH-UHFFFAOYSA-N 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- XYXNTHIYBIDHGM-UHFFFAOYSA-N ammonium thiosulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 1
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 description 1
- 239000003139 biocide Substances 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 150000001719 carbohydrate derivatives Chemical class 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- AFSIMBWBBOJPJG-UHFFFAOYSA-N ethenyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC=C AFSIMBWBBOJPJG-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- LDLDYFCCDKENPD-UHFFFAOYSA-N ethenylcyclohexane Chemical compound C=CC1CCCCC1 LDLDYFCCDKENPD-UHFFFAOYSA-N 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229930182478 glucoside Natural products 0.000 description 1
- 150000008131 glucosides Chemical class 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 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 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- BPCNEKWROYSOLT-UHFFFAOYSA-N n-phenylprop-2-enamide Chemical compound C=CC(=O)NC1=CC=CC=C1 BPCNEKWROYSOLT-UHFFFAOYSA-N 0.000 description 1
- 229920000847 nonoxynol Polymers 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- QIWKUEJZZCOPFV-UHFFFAOYSA-N phenyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1=CC=CC=C1 QIWKUEJZZCOPFV-UHFFFAOYSA-N 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L sodium sulphate Substances [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 239000000080 wetting agent 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
- G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
- G03C1/04—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with macromolecular additives; with layer-forming substances
- G03C1/053—Polymers obtained by reactions involving only carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
Definitions
- This invention relates to photographic silver halide emulsion assemblies.
- Most camera films consist of a photographic assembly which comprises at least one silver halide emulsion layer coated on a cellulose triacetate or cellulose acetate-butyrate base.
- Gelatin layers can be coated on to such base materials without the need to treat the base to the same extent as that which is required to render polyethylene terephthalate (polyester) bases capable of being coated with a gelatin layer.
- all cellulose triacetate or cellulose acetate-butyrate base is supplied to the manufacturers of photographic materials treated in some way to help a gelatin coat to adhere thereto better than untreated base.
- Each base manufacturer has his own method of treating cellulose-derived bases and often the photographic manufacturer is not privy to the method employed by the base manufacturer.
- cellulose triacetate or cellulose acetate-butyrate base which has been treated by the base manufacturer to render it more susceptible to be coated with a gelatin layer is hereinafter referred to as sub-coated cellulose triacetate or cellulose acetate-butyrate base.
- a photographic film assembly which comprises coated on a sub-coated cellulose triacetate or cellulose acetate-butyrate base at least one gelatino silver halide emulsion layer wherein the silver halide emulsion layer which is closest to the base comprises from 1 to 30% by weight of the gelatin in the emulsion layer, a latex polymer whose glass transition temperature does not exceed 30°C and which is a copolymer of an ethylenically unsaturated monomer containing an aromatic moeity, with an acrylate or methacrylate ester monomer.
- the latex polymer may also contain additional ethylenically unsaturated monomers, as described below.
- the amount of latex present in the silver halide emulsion layer is from 2 to 10% by weight of the gelatin in the layer.
- Examples of the monomers which are useful to prepare the latex used in the present invention are:- As monomers containing an aromatic moeity:- styrene, vinyl toluene, 2,4-dimethylstyrene, -methyl styrene, divinyl benzene, vinylnaphthalene, 4-methoxystyrene, 3-nitrostyrene, vinyl phenol, vinyl benzoate, diallyl phthalate, benzyl methacrylate, phenyl methacrylate, N-phenylacrylamide, 2-phenylethylmethacrylate.
- acrylate or methacrylate monomers Cyclohexyl methacrylate, 2-hydroxy-propylmethacrylate, 2-hydroxyethylmethacrylate, ethylene glycol dimethacrylate, butyl acrylate, methyl acrylate, ethyl acrylate, 2-ethylhexylacrylate, methyl methacrylate, n-heptyl acrylate.
- comonomers which may be present vinyl cyclohexane, acrylonitrile, vinylidene chloride, vinyl acetate, vinyl propionate, vinyl stearate, acrylic acid and its salts, 2-acrylamido-2-methyl propane sulphonic acid and its salts, acrylamide, methacrylamide, N-vinyl pyrrolidone, ethylene sulphonic acid and its salts.
- Preferred combinations of monomers are styrene/butyl acrylate; vinyl toluene/butyl acrylate; styrene/ethylhexyl acrylate; styrene/ethyl acrylate; styrene/n-heptyl acrylate; -methyl styrene/butyl acrylate; styrene/divinyl benzene/butyl acrylate; styrene/methyl methacrylate/ butyl acrylate; styrene/2-hydoxypropylmethacrylate/butyl acrylate; styrene/butyl acrylate/2-acrylamido-2-methylpropane sulphonic acid sodium salt.
- These combinations may include monomers in varying proportions but they preferably contain at least about 10% by weight of the aromatic ethylenically unsaturated monomer. Preferably they contain at least 20% by weight of the acrylate or methacrylate ester monomers.
- Particularly preferred combinations are styrene 50 parts, butyl acrylate 50 parts; vinyl toluene 50 parts, butyl acrylate 50 parts; and styrene 50 parts, ethyl hexyl acrylate 50 parts. The parts being by weight.
- latices of the above type requires the use of one or more surface active agents, and these may be any of the types well known in the art.
- anionic surfactants are very useful and these may be used optionally in the presence of a nonionic surfactant.
- the anionic surfactants may be the sodium, potassium or ammonium salts (but preferably the sodium salt) of a sulphate, sulphonate, phosphonate or phosphate derivative.
- the hydrophobic part of the surfactant may be an alkyl group, an aryl group, or a combination of an alkyl and an aryl group.
- the hydrophilic part of the surfactant may contain, in addition to an anionic group, an alkylene oxide chain with up to 50 alkylene oxide units in the chain. In addition, there may be present ethylenically unsaturated units in the surfactant thus enabling it to copolymerise with the other units and thus render the surfactant substantive.
- the non-ionic surfactants may contain alkyl, aryl or alkyl-aryl groups together with alkylene oxide chains; there are many other suitable nonionic surfactants well known in the art, and these include: alkylolamides; carbohydrate derivatives such as glucosides; alkylesters; and amine oxides.
- alkylolamides include: alkylolamides; carbohydrate derivatives such as glucosides; alkylesters; and amine oxides.
- a large number of surfactants are commercially available and details of many suitable types may be found for example in "Surfactants UK", ed. G.L. Hollis, published by Tergo-Data, England.
- the surfactants may comprise from 0.1 to 15% by weight of the total latex.
- Preferred surfactants to use to prepare the latexes used in the present invention are alkyl phenol ethoxylate sulphates, alkyl sulphonates, sulphosuccinate esters and aryl-and alkyl ethoxylate phosphates, in combination with or in the absence of alkyl phenol ethoxylates, alkylphenol polyglycidolethers or alkanol ethoxylates.
- Initiators suitable for the preparation of the latexes used in the present invention may be selected from those well known in the prior art. These are usually water soluble azo compounds or water soluble per-oxo compounds.
- the sodium salt of azobis (cyanopentanoic acid) is a commonly available water soluble azo initiator.
- Sodium and potassium persulphate are very commonly used in emulsion polymerisation.
- Hydrogen peroxide and some other peroxides such as tertiary butyl hydroperoxide are also useful initiators.
- the initiation process may be effected either at higher temperatures (e.g. above about 70°C) by using an initiator which decomposes thermally or at lower temperatures (e.g.
- initiator couples which act by a redox system. Details of these initiation processes may be found for example in "Emulsion Polymerisation” by D.C. Blackley, Applied Science Publishers, London, 1975.
- the initiators may comprise from 0.1 to 1.0% by weight of the reaction mixture.
- the procedure for preparing the latexes used in the present invention follows that commonly used in emulsion polymerisation. Typically, the mixture of monomers is added, over a period of from thirty minutes to three hours, to a heated, oxygen-free solution of the chosen surfactant in water and the selected initiators and further surfactant are added either continuously or portionwise over the same period. Following the polymerisation it is necessary to cool the reaction mixture to ambient temperature followed by filtration to remove small quantities of coagulated polymer.
- additives including biocides and colloid stabilisers.
- biocides and colloid stabilisers During the polymerisation it may be desirable to limit the molecular weight of the polymer by adding small amounts of chain transfer agents. Additives such as this are covered in Blackley's book (see above).
- a mixture of 934g of butyl acrylate and 944g of styrene was added at a constant rate over a period of 3 hours to a stirred, aqueous solution consisting of water (1739g), potassium persulphate (4.65g), sodium metabisulphite (2.05g), and the sodium salt of a nonylphenol ethoxylate sulphate surfactant (167g of a 25% active solution), maintained at 70°C.
- a further solution of the same surfactant 500g of a 25% solution
- potassium persulphate (2.32g) and sodium metabisulphite (1.02g) in 650g water was added.
- the mixture was maintained at 70°C for 4 hours before cooling to below 30°C and filtering through a 100um sieve.
- latex 1 having a solids content of 40%, particle size 114nm.
- the Tg of the polymer is +3°C. This is latex 1.
- the silver halide present in the emulsions used in the assembly of the present invention may be of any silver halide composition, eg. pure silver bromide, silver iodobromide, silver chloroiodobromide, silver chloride, silver chlorobromide.
- the silver halide grains in the emulsion may be of any habit eg, tabular or cubic. They may have been chemically sensitised for example by gold and/or sulphur. They may have been optically sensitised by use of any of the well known merocyanine or methin cyanine dyes used for this purpose.
- the emulsion may contain any of the well known stabilisers, hardening agent and any of the other well known additives often present in camera film silver halide emulsions.
- silver halide emulsion layers There may be at least two silver halide emulsion layers and the top-most silver halide emulsion layer may be coated with a gelatin supercoat or non-stress layer which may comprise antiblocking agents. There may be gelatin based inter-layers between any of the silver halide emulsion layers.
- cellulose triacetate or cellulose acetate butyrate base there may be on the reverse side of the cellulose triacetate or cellulose acetate butyrate base to that side which carries the emulsion layer or layers at least one backing layer which may be an anti-halation backing layer.
- Strips of a photographic material were prepared from a typical assembly made from a sub-coated base of cellulose triacetate film to prepare a high sensitivity black and white negative photographic material.
- the total silver content of the film was 8.0 - 7.0 g/m2.
- the amount of coating is expressed for each of the layers in terms of g/m2; the amount of silver halide expressed in terms of the weight of silver.
- 0.2g/m2 of latex corresponds to 5% of the weight of the gelatin present in the first emulsion layer.
- Latex (0.4g/m2) Adhesion Grade after/days 7 14 21 29 1 1 1 1 1 1 2 4 4 5 4 3 2 2 5 2 4 5 4 3 4 5 1 2 1 1 6 1 1 1 1 # Control 5 5 5 5 # Control no Latex
- the film is scratched at various stages of the processing cycle and then rubbed with the finger.
- Adhesion grade is assigned according to the amount of emulsion removed when the film is rubbed. The grades are described as follows:
- Strips of the photographic material prepared in Examples 1, 5 and 6 together with a control strip which comprised no latex were exposed to a step wedge and the sensitometric properties were compared with the control.
- the photographic foot speed S0.1 of all the strips was substantially the same as was the contrast G. This showed that the presence of the latex in the emulsion had no deleterious effect on the sensitometric properties of the assembly.
- the photographic assemblies were processed in a developer at 25°C. They were then fixed in an ammonium thiosulphate fixing bath and the water washed.
- the developer used had the following formula:- Metol 2.0g Hydroquinone 5.0g Sodium sulphite 100.0g Borax 2.0g Water to 1 litre
- latexes which comprise an aromatic moiety provide good adhesion, that is to say latexes 1, 5 and 6.
- latexes which comprise no aromatic moiety had inferior or bad adhesion that is to say latexes 2, 3 and 4.
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Abstract
Description
- This invention relates to photographic silver halide emulsion assemblies.
- Most camera films consist of a photographic assembly which comprises at least one silver halide emulsion layer coated on a cellulose triacetate or cellulose acetate-butyrate base. Gelatin layers can be coated on to such base materials without the need to treat the base to the same extent as that which is required to render polyethylene terephthalate (polyester) bases capable of being coated with a gelatin layer. Nevertheless all cellulose triacetate or cellulose acetate-butyrate base is supplied to the manufacturers of photographic materials treated in some way to help a gelatin coat to adhere thereto better than untreated base. Each base manufacturer has his own method of treating cellulose-derived bases and often the photographic manufacturer is not privy to the method employed by the base manufacturer. It is thought that some base manufacturers apply a coating of partially hydrolysed cellulose mixed with gelatin to the surface of the cellulose triacetate or cellulose acetate-butyrate. Sometimes this first coating is coated with a thin gelatin layer. Such cellulose triacetate or cellulose acetate-butyrate base which has been treated by the base manufacturer to render it more susceptible to be coated with a gelatin layer is hereinafter referred to as sub-coated cellulose triacetate or cellulose acetate-butyrate base.
- Unfortunately due to the increasingly vigorous processing conditions now being used to process camera films such as roller processors using fairly high temperature processing solutions, constant agitation of the processing solutions and high temperature drying conditions, camera films coated on sub-coated cellulose triacetate or cellulose acetate-butyrate are apt to exhibit poor adhesion of the emulsion layers to the base.
- It is the object of the present invention to provide a photographic film assembly wherein the base is sub-coated cellulose triacetate or acetate butyrate which exhibits markedly improved adhesion of the emulsion layers to the base even when subjected to vigorous processing conditions.
- Therefore according to the present invention there is provided a photographic film assembly which comprises coated on a sub-coated cellulose triacetate or cellulose acetate-butyrate base at least one gelatino silver halide emulsion layer wherein the silver halide emulsion layer which is closest to the base comprises from 1 to 30% by weight of the gelatin in the emulsion layer, a latex polymer whose glass transition temperature does not exceed 30°C and which is a copolymer of an ethylenically unsaturated monomer containing an aromatic moeity, with an acrylate or methacrylate ester monomer. The latex polymer may also contain additional ethylenically unsaturated monomers, as described below.
- Preferably the amount of latex present in the silver halide emulsion layer is from 2 to 10% by weight of the gelatin in the layer.
- Examples of the monomers which are useful to prepare the latex used in the present invention are:-
As monomers containing an aromatic moeity:-
styrene, vinyl toluene, 2,4-dimethylstyrene, -methyl styrene, divinyl benzene, vinylnaphthalene, 4-methoxystyrene, 3-nitrostyrene, vinyl phenol, vinyl benzoate, diallyl phthalate, benzyl methacrylate, phenyl methacrylate, N-phenylacrylamide, 2-phenylethylmethacrylate. As acrylate or methacrylate monomers Cyclohexyl methacrylate, 2-hydroxy-propylmethacrylate, 2-hydroxyethylmethacrylate, ethylene glycol dimethacrylate, butyl acrylate, methyl acrylate, ethyl acrylate, 2-ethylhexylacrylate, methyl methacrylate, n-heptyl acrylate. As comonomers which may be present vinyl cyclohexane, acrylonitrile, vinylidene chloride, vinyl acetate, vinyl propionate, vinyl stearate, acrylic acid and its salts, 2-acrylamido-2-methyl propane sulphonic acid and its salts, acrylamide, methacrylamide, N-vinyl pyrrolidone, ethylene sulphonic acid and its salts. - Preferred combinations of monomers are styrene/butyl acrylate; vinyl toluene/butyl acrylate; styrene/ethylhexyl acrylate; styrene/ethyl acrylate; styrene/n-heptyl acrylate; -methyl styrene/butyl acrylate; styrene/divinyl benzene/butyl acrylate; styrene/methyl methacrylate/ butyl acrylate; styrene/2-hydoxypropylmethacrylate/butyl acrylate; styrene/butyl acrylate/2-acrylamido-2-methylpropane sulphonic acid sodium salt.
- These combinations may include monomers in varying proportions but they preferably contain at least about 10% by weight of the aromatic ethylenically unsaturated monomer. Preferably they contain at least 20% by weight of the acrylate or methacrylate ester monomers.
- Particularly preferred combinations are styrene 50 parts, butyl acrylate 50 parts; vinyl toluene 50 parts, butyl acrylate 50 parts; and styrene 50 parts, ethyl hexyl acrylate 50 parts. The parts being by weight.
- The preparation of latices of the above type requires the use of one or more surface active agents, and these may be any of the types well known in the art. In particular, anionic surfactants are very useful and these may be used optionally in the presence of a nonionic surfactant.
- The anionic surfactants may be the sodium, potassium or ammonium salts (but preferably the sodium salt) of a sulphate, sulphonate, phosphonate or phosphate derivative. The hydrophobic part of the surfactant may be an alkyl group, an aryl group, or a combination of an alkyl and an aryl group. The hydrophilic part of the surfactant may contain, in addition to an anionic group, an alkylene oxide chain with up to 50 alkylene oxide units in the chain. In addition, there may be present ethylenically unsaturated units in the surfactant thus enabling it to copolymerise with the other units and thus render the surfactant substantive. The non-ionic surfactants may contain alkyl, aryl or alkyl-aryl groups together with alkylene oxide chains; there are many other suitable nonionic surfactants well known in the art, and these include: alkylolamides; carbohydrate derivatives such as glucosides; alkylesters; and amine oxides. A large number of surfactants are commercially available and details of many suitable types may be found for example in "Surfactants UK", ed. G.L. Hollis, published by Tergo-Data, England. The surfactants may comprise from 0.1 to 15% by weight of the total latex.
- Preferred surfactants to use to prepare the latexes used in the present invention are alkyl phenol ethoxylate sulphates, alkyl sulphonates, sulphosuccinate esters and aryl-and alkyl ethoxylate phosphates, in combination with or in the absence of alkyl phenol ethoxylates, alkylphenol polyglycidolethers or alkanol ethoxylates.
- Initiators suitable for the preparation of the latexes used in the present invention may be selected from those well known in the prior art. These are usually water soluble azo compounds or water soluble per-oxo compounds. For example, the sodium salt of azobis (cyanopentanoic acid) is a commonly available water soluble azo initiator. Sodium and potassium persulphate are very commonly used in emulsion polymerisation. Hydrogen peroxide and some other peroxides such as tertiary butyl hydroperoxide are also useful initiators. The initiation process may be effected either at higher temperatures (e.g. above about 70°C) by using an initiator which decomposes thermally or at lower temperatures (e.g. below about 70°C) by initiator couples which act by a redox system. Details of these initiation processes may be found for example in "Emulsion Polymerisation" by D.C. Blackley, Applied Science Publishers, London, 1975. The initiators may comprise from 0.1 to 1.0% by weight of the reaction mixture.
- The procedure for preparing the latexes used in the present invention follows that commonly used in emulsion polymerisation. Typically, the mixture of monomers is added, over a period of from thirty minutes to three hours, to a heated, oxygen-free solution of the chosen surfactant in water and the selected initiators and further surfactant are added either continuously or portionwise over the same period. Following the polymerisation it is necessary to cool the reaction mixture to ambient temperature followed by filtration to remove small quantities of coagulated polymer.
- In the preparation of the latex there may be small quantities of a variety of additives including biocides and colloid stabilisers. During the polymerisation it may be desirable to limit the molecular weight of the polymer by adding small amounts of chain transfer agents. Additives such as this are covered in Blackley's book (see above).
- A mixture of 934g of butyl acrylate and 944g of styrene was added at a constant rate over a period of 3 hours to a stirred, aqueous solution consisting of water (1739g), potassium persulphate (4.65g), sodium metabisulphite (2.05g), and the sodium salt of a nonylphenol ethoxylate sulphate surfactant (167g of a 25% active solution), maintained at 70°C. Simultaneously with the monomer solution, a further solution of the same surfactant (500g of a 25% solution), potassium persulphate (2.32g) and sodium metabisulphite (1.02g) in 650g water was added.
- The mixture was maintained at 70°C for 4 hours before cooling to below 30°C and filtering through a 100um sieve.
- There was obtained a latex having a solids content of 40%, particle size 114nm. The Tg of the polymer is +3°C. This is latex 1.
-
- The silver halide present in the emulsions used in the assembly of the present invention may be of any silver halide composition, eg. pure silver bromide, silver iodobromide, silver chloroiodobromide, silver chloride, silver chlorobromide. The silver halide grains in the emulsion may be of any habit eg, tabular or cubic. They may have been chemically sensitised for example by gold and/or sulphur. They may have been optically sensitised by use of any of the well known merocyanine or methin cyanine dyes used for this purpose. The emulsion may contain any of the well known stabilisers, hardening agent and any of the other well known additives often present in camera film silver halide emulsions.
- There may be at least two silver halide emulsion layers and the top-most silver halide emulsion layer may be coated with a gelatin supercoat or non-stress layer which may comprise antiblocking agents. There may be gelatin based inter-layers between any of the silver halide emulsion layers.
- There may be on the reverse side of the cellulose triacetate or cellulose acetate butyrate base to that side which carries the emulsion layer or layers at least one backing layer which may be an anti-halation backing layer.
- The accompanying examples will serve to illustrate the invention.
- Strips of a photographic material were prepared from a typical assembly made from a sub-coated base of cellulose triacetate film to prepare a high sensitivity black and white negative photographic material. The total silver content of the film was 8.0 - 7.0 g/m².
-
- In this Example, 0.2g/m² of latex corresponds to 5% of the weight of the gelatin present in the first emulsion layer.
-
- As set forth in TABLE 1
TABLE 2 Effect of latex addition on wet adhesion after processing. Latex (0.4g/m²) Adhesion Grade after/days 7 14 21 29 1 1 1 1 1 2 4 4 5 4 3 2 2 5 2 4 5 4 3 4 5 1 2 1 1 6 1 1 1 1 # Control 5 5 5 5 # Control no Latex -
TABLE 3 Effect of Latex Quantity on Wet Adhesion after processing Latex 1 g/m² Adhesion Grade after/days 8 14 21 30 0 5 2 4 5 1% 0.05 5 1 2 3 2% 0.1 1 1 1 1 5% 0.2 1 1 1 1 10% 0.4 1 1 1 1 The percentages are the percent of latex of the gelatin in the emulsion. - In the wet adhesion test, the film is scratched at various stages of the processing cycle and then rubbed with the finger.
- Adhesion grade is assigned according to the amount of emulsion removed when the film is rubbed. The grades are described as follows:
- Grade 1 -
- No adhesion failure observed
- Grade 2 -
- Minor frilling of emulsion at scratch edge
- Grade 3 -
- Minor stripping of emulsion at scratch edge
- Grade 4 -
- Obvious stripping of emulsion
- Grade 5 -
- Severe stripping of emulsion
- Strips of the photographic material prepared in Examples 1, 5 and 6 together with a control strip which comprised no latex were exposed to a step wedge and the sensitometric properties were compared with the control. The photographic foot speed S0.1 of all the strips was substantially the same as was the contrast G. This showed that the presence of the latex in the emulsion had no deleterious effect on the sensitometric properties of the assembly.
- For the wet adhesion tests the photographic assemblies were processed in a developer at 25°C. They were then fixed in an ammonium thiosulphate fixing bath and the water washed.
- All this processing took place in an automatic roller processing machine in which there was constant agitation of the processing solutions and the wash water.
- The developer used had the following formula:-
Metol 2.0g Hydroquinone 5.0g Sodium sulphite 100.0g Borax 2.0g Water to 1 litre - From these results it can be seen that the latexes which comprise an aromatic moiety provide good adhesion, that is to say latexes 1, 5 and 6. However, latexes which comprise no aromatic moiety had inferior or bad adhesion that is to say latexes 2, 3 and 4.
Claims (3)
- A photographic film assembly which comprises coated on a sub-coated cellulose triacetate or cellulose acetate-butyrate base at least one gelatino silver halide emulsion layer characterised in that the silver halide emulsion layer which is closest to the base comprises a latex polymer whose glass transition temperature does not exceed 30°C and which is a copolymer of an ethylenically unsaturated monomer containing an aromatic moeity, with an acrylate or methacrylate ester monomer, the latex comprising from 1 to 30% by weight of the gelatin in the emulsion layer.
- A photographic film assembly according to claim 1 characterised in that the amount of latex present in the silver halide emulsion layer is from 2 to 10% by weight of the gelatin in the layer.
- A photographic film assembly according to either claim 1 or claim 2 characterised in that the latex is derived from one of the following combinations of monomers:- styrene/butyl acrylate; vinyl toluene/butyl acrylate; styrene/ethylhexyl acrylate; styrene/ethyl acrylate; styrene/n-heptyl acrylate; -methyl styrene/butyl acrylate; styrene/divinyl benzene/butyl acrylate; styrene/methyl methacrylate/butyl acrylate; styrene/2-hydoxypropylmethacrylate/butyl acrylate; styrene/butyl acrylate/2-acrylamido-2-methylpropane sulphonic acid sodium salt.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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GB9203951 | 1992-02-25 | ||
GB929203951A GB9203951D0 (en) | 1992-02-25 | 1992-02-25 | Photographic assembly |
Publications (2)
Publication Number | Publication Date |
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EP0557785A1 true EP0557785A1 (en) | 1993-09-01 |
EP0557785B1 EP0557785B1 (en) | 1997-08-06 |
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EP19930101989 Expired - Lifetime EP0557785B1 (en) | 1992-02-25 | 1993-02-09 | Photographic assembly |
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EP (1) | EP0557785B1 (en) |
DE (1) | DE69312761T2 (en) |
GB (1) | GB9203951D0 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0615158A1 (en) * | 1993-03-04 | 1994-09-14 | Konica Corporation | A silver halide photographic light-sensitive material |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2208136A1 (en) * | 1972-11-22 | 1974-06-21 | Ilford Ltd | |
US4197127A (en) * | 1976-10-08 | 1980-04-08 | Eastman Kodak Company | Photographic silver halide composition and element containing sulfonate copolymers |
EP0358187A2 (en) * | 1988-09-08 | 1990-03-14 | Eastman Kodak Company | Tabular grain photographic elements exhibiting reduced pressure sensitivity (II) |
-
1992
- 1992-02-25 GB GB929203951A patent/GB9203951D0/en active Pending
-
1993
- 1993-02-09 EP EP19930101989 patent/EP0557785B1/en not_active Expired - Lifetime
- 1993-02-09 DE DE1993612761 patent/DE69312761T2/en not_active Expired - Fee Related
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2208136A1 (en) * | 1972-11-22 | 1974-06-21 | Ilford Ltd | |
US4197127A (en) * | 1976-10-08 | 1980-04-08 | Eastman Kodak Company | Photographic silver halide composition and element containing sulfonate copolymers |
EP0358187A2 (en) * | 1988-09-08 | 1990-03-14 | Eastman Kodak Company | Tabular grain photographic elements exhibiting reduced pressure sensitivity (II) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0615158A1 (en) * | 1993-03-04 | 1994-09-14 | Konica Corporation | A silver halide photographic light-sensitive material |
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DE69312761T2 (en) | 1998-02-12 |
DE69312761D1 (en) | 1997-09-11 |
EP0557785B1 (en) | 1997-08-06 |
GB9203951D0 (en) | 1992-04-08 |
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