US3025163A - Photographic element having polycarbonate sub-layer - Google Patents
Photographic element having polycarbonate sub-layer Download PDFInfo
- Publication number
- US3025163A US3025163A US722464A US72246458A US3025163A US 3025163 A US3025163 A US 3025163A US 722464 A US722464 A US 722464A US 72246458 A US72246458 A US 72246458A US 3025163 A US3025163 A US 3025163A
- Authority
- US
- United States
- Prior art keywords
- layer
- dihydroxy
- polycarbonate
- film
- vinyl
- 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
- 239000004417 polycarbonate Substances 0.000 title claims description 50
- 229920000515 polycarbonate Polymers 0.000 title claims description 49
- 229920002301 cellulose acetate Polymers 0.000 claims description 14
- 229920001169 thermoplastic Polymers 0.000 claims description 6
- 239000004416 thermosoftening plastic Substances 0.000 claims description 6
- 230000002209 hydrophobic effect Effects 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 description 31
- -1 silver halide Chemical class 0.000 description 29
- 229920001577 copolymer Polymers 0.000 description 22
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 21
- 239000001828 Gelatine Substances 0.000 description 21
- 229920000159 gelatin Polymers 0.000 description 21
- 235000019322 gelatine Nutrition 0.000 description 21
- 239000000203 mixture Substances 0.000 description 20
- 238000000034 method Methods 0.000 description 18
- 239000000839 emulsion Substances 0.000 description 17
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 150000001299 aldehydes Chemical class 0.000 description 14
- 229940081735 acetylcellulose Drugs 0.000 description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- 229920001567 vinyl ester resin Polymers 0.000 description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 10
- 229910052709 silver Inorganic materials 0.000 description 10
- 239000004332 silver Substances 0.000 description 10
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 9
- SMEGJBVQLJJKKX-HOTMZDKISA-N [(2R,3S,4S,5R,6R)-5-acetyloxy-3,4,6-trihydroxyoxan-2-yl]methyl acetate Chemical compound CC(=O)OC[C@@H]1[C@H]([C@@H]([C@H]([C@@H](O1)O)OC(=O)C)O)O SMEGJBVQLJJKKX-HOTMZDKISA-N 0.000 description 9
- 125000003118 aryl group Chemical group 0.000 description 9
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 9
- 229940117958 vinyl acetate Drugs 0.000 description 9
- 229920002678 cellulose Polymers 0.000 description 8
- 239000004372 Polyvinyl alcohol Substances 0.000 description 7
- 150000001241 acetals Chemical class 0.000 description 7
- 239000002253 acid Substances 0.000 description 7
- 125000001931 aliphatic group Chemical group 0.000 description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- 229920002451 polyvinyl alcohol Polymers 0.000 description 7
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 6
- 150000002430 hydrocarbons Chemical group 0.000 description 6
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 6
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 6
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 5
- 239000000020 Nitrocellulose Substances 0.000 description 5
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 5
- FJWGYAHXMCUOOM-QHOUIDNNSA-N [(2s,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6s)-4,5-dinitrooxy-2-(nitrooxymethyl)-6-[(2r,3r,4s,5r,6s)-4,5,6-trinitrooxy-2-(nitrooxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-3,5-dinitrooxy-6-(nitrooxymethyl)oxan-4-yl] nitrate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O)O[C@H]1[C@@H]([C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@@H](CO[N+]([O-])=O)O1)O[N+]([O-])=O)CO[N+](=O)[O-])[C@@H]1[C@@H](CO[N+]([O-])=O)O[C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O FJWGYAHXMCUOOM-QHOUIDNNSA-N 0.000 description 5
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 5
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 5
- 238000007598 dipping method Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 5
- 229920001220 nitrocellulos Polymers 0.000 description 5
- 239000001294 propane Substances 0.000 description 5
- 125000001174 sulfone group Chemical group 0.000 description 5
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 238000004873 anchoring Methods 0.000 description 4
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- BVJSUAQZOZWCKN-UHFFFAOYSA-N p-hydroxybenzyl alcohol Chemical compound OCC1=CC=C(O)C=C1 BVJSUAQZOZWCKN-UHFFFAOYSA-N 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- OIXGILBUABDWRY-UHFFFAOYSA-N 1,2,3,4,4a,5,6,7,8,8a-decahydronaphthalene-2,6-diol Chemical compound C1C(O)CCC2CC(O)CCC21 OIXGILBUABDWRY-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000012442 inert solvent Substances 0.000 description 3
- PCILLCXFKWDRMK-UHFFFAOYSA-N naphthalene-1,4-diol Chemical compound C1=CC=C2C(O)=CC=C(O)C2=C1 PCILLCXFKWDRMK-UHFFFAOYSA-N 0.000 description 3
- MNZMMCVIXORAQL-UHFFFAOYSA-N naphthalene-2,6-diol Chemical compound C1=C(O)C=CC2=CC(O)=CC=C21 MNZMMCVIXORAQL-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 150000003568 thioethers Chemical class 0.000 description 3
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 3
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical group C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical group C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- BWVAOONFBYYRHY-UHFFFAOYSA-N [4-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=C(CO)C=C1 BWVAOONFBYYRHY-UHFFFAOYSA-N 0.000 description 2
- 150000003934 aromatic aldehydes Chemical class 0.000 description 2
- 150000005840 aryl radicals Chemical class 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000002843 carboxylic acid group Chemical group 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical group NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- 150000001987 diarylethers Chemical class 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 125000002541 furyl group Chemical group 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- FZZQNEVOYIYFPF-UHFFFAOYSA-N naphthalene-1,6-diol Chemical compound OC1=CC=CC2=CC(O)=CC=C21 FZZQNEVOYIYFPF-UHFFFAOYSA-N 0.000 description 2
- YCWSUKQGVSGXJO-NTUHNPAUSA-N nifuroxazide Chemical group C1=CC(O)=CC=C1C(=O)N\N=C\C1=CC=C([N+]([O-])=O)O1 YCWSUKQGVSGXJO-NTUHNPAUSA-N 0.000 description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N p-dimethylbenzene Natural products CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 239000010695 polyglycol Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 230000003763 resistance to breakage Effects 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 239000011877 solvent mixture Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- 239000001117 sulphuric acid Substances 0.000 description 2
- 235000011149 sulphuric acid Nutrition 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- YODZTKMDCQEPHD-UHFFFAOYSA-N thiodiglycol Chemical compound OCCSCCO YODZTKMDCQEPHD-UHFFFAOYSA-N 0.000 description 2
- 229950006389 thiodiglycol Drugs 0.000 description 2
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- UTCOUOISVRSLSH-UHFFFAOYSA-N 1,2-Anthracenediol Chemical compound C1=CC=CC2=CC3=C(O)C(O)=CC=C3C=C21 UTCOUOISVRSLSH-UHFFFAOYSA-N 0.000 description 1
- IVSZLXZYQVIEFR-UHFFFAOYSA-N 1,3-Dimethylbenzene Natural products CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 1
- ZVYSYCLZXICWLH-UHFFFAOYSA-N 1,3-dioxetan-2-one Chemical compound O=C1OCO1 ZVYSYCLZXICWLH-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-dioxonaphthalene Natural products C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 description 1
- BOKGTLAJQHTOKE-UHFFFAOYSA-N 1,5-dihydroxynaphthalene Chemical compound C1=CC=C2C(O)=CC=CC2=C1O BOKGTLAJQHTOKE-UHFFFAOYSA-N 0.000 description 1
- SNMRZPACMQWBAE-UHFFFAOYSA-N 1-hydroxy-2H-quinolin-4-ol Chemical compound C1=CC=C2N(O)CC=C(O)C2=C1 SNMRZPACMQWBAE-UHFFFAOYSA-N 0.000 description 1
- RKSBPFMNOJWYSB-UHFFFAOYSA-N 3,3-Bis(4-hydroxyphenyl)pentane Chemical compound C=1C=C(O)C=CC=1C(CC)(CC)C1=CC=C(O)C=C1 RKSBPFMNOJWYSB-UHFFFAOYSA-N 0.000 description 1
- YGCZTXZTJXYWCO-UHFFFAOYSA-N 3-phenylpropanal Chemical compound O=CCCC1=CC=CC=C1 YGCZTXZTJXYWCO-UHFFFAOYSA-N 0.000 description 1
- VHLLJTHDWPAQEM-UHFFFAOYSA-N 4-[2-(4-hydroxyphenyl)-4-methylpentan-2-yl]phenol Chemical compound C=1C=C(O)C=CC=1C(C)(CC(C)C)C1=CC=C(O)C=C1 VHLLJTHDWPAQEM-UHFFFAOYSA-N 0.000 description 1
- ZQTPHEAGPRFALE-UHFFFAOYSA-N 4-[2-(4-hydroxyphenyl)hexan-2-yl]phenol Chemical compound C=1C=C(O)C=CC=1C(C)(CCCC)C1=CC=C(O)C=C1 ZQTPHEAGPRFALE-UHFFFAOYSA-N 0.000 description 1
- WZBHALGYPYRUNN-UHFFFAOYSA-N 4-[2-(4-hydroxyphenyl)tridecan-2-yl]phenol Chemical compound C=1C=C(O)C=CC=1C(C)(CCCCCCCCCCC)C1=CC=C(O)C=C1 WZBHALGYPYRUNN-UHFFFAOYSA-N 0.000 description 1
- 241001479434 Agfa Species 0.000 description 1
- 241001136792 Alle Species 0.000 description 1
- QEIQEORTEYHSJH-UHFFFAOYSA-N Armin Natural products C1=CC(=O)OC2=C(O)C(OCC(CCO)C)=CC=C21 QEIQEORTEYHSJH-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- VOWWYDCFAISREI-UHFFFAOYSA-N Bisphenol AP Chemical compound C=1C=C(O)C=CC=1C(C=1C=CC(O)=CC=1)(C)C1=CC=CC=C1 VOWWYDCFAISREI-UHFFFAOYSA-N 0.000 description 1
- HTVITOHKHWFJKO-UHFFFAOYSA-N Bisphenol B Chemical compound C=1C=C(O)C=CC=1C(C)(CC)C1=CC=C(O)C=C1 HTVITOHKHWFJKO-UHFFFAOYSA-N 0.000 description 1
- SDDLEVPIDBLVHC-UHFFFAOYSA-N Bisphenol Z Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)CCCCC1 SDDLEVPIDBLVHC-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229920008347 Cellulose acetate propionate Polymers 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 208000007101 Muscle Cramp Diseases 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 208000005392 Spasm Diseases 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- XMUZQOKACOLCSS-UHFFFAOYSA-N [2-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=CC=C1CO XMUZQOKACOLCSS-UHFFFAOYSA-N 0.000 description 1
- YWMLORGQOFONNT-UHFFFAOYSA-N [3-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=CC(CO)=C1 YWMLORGQOFONNT-UHFFFAOYSA-N 0.000 description 1
- 238000006359 acetalization reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000002730 additional effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- IMNFDUFMRHMDMM-UHFFFAOYSA-N anhydrous n-heptane Natural products CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 1
- AGTBKJDELLDEOQ-UHFFFAOYSA-N anthracene-1,5-diol Chemical compound C1=CC=C2C=C3C(O)=CC=CC3=CC2=C1O AGTBKJDELLDEOQ-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- YNKMHABLMGIIFX-UHFFFAOYSA-N benzaldehyde;methane Chemical compound C.O=CC1=CC=CC=C1 YNKMHABLMGIIFX-UHFFFAOYSA-N 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 1
- KYNFOMQIXZUKRK-UHFFFAOYSA-N bishydroxyethyldisulfide Natural products OCCSSCCO KYNFOMQIXZUKRK-UHFFFAOYSA-N 0.000 description 1
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- HKQOBOMRSSHSTC-UHFFFAOYSA-N cellulose acetate Chemical compound OC1C(O)C(O)C(CO)OC1OC1C(CO)OC(O)C(O)C1O.CC(=O)OCC1OC(OC(C)=O)C(OC(C)=O)C(OC(C)=O)C1OC1C(OC(C)=O)C(OC(C)=O)C(OC(C)=O)C(COC(C)=O)O1.CCC(=O)OCC1OC(OC(=O)CC)C(OC(=O)CC)C(OC(=O)CC)C1OC1C(OC(=O)CC)C(OC(=O)CC)C(OC(=O)CC)C(COC(=O)CC)O1 HKQOBOMRSSHSTC-UHFFFAOYSA-N 0.000 description 1
- 229920006217 cellulose acetate butyrate Polymers 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000004833 diarylthioethers Chemical class 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical class C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- PBBGSZCBWVPOOL-UHFFFAOYSA-N hexestrol Chemical compound C=1C=C(O)C=CC=1C(CC)C(CC)C1=CC=C(O)C=C1 PBBGSZCBWVPOOL-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical compound C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000002895 organic esters Chemical group 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 125000006308 propyl amino group Chemical group 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical compound OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- FWMUJAIKEJWSSY-UHFFFAOYSA-N sulfur dichloride Chemical compound ClSCl FWMUJAIKEJWSSY-UHFFFAOYSA-N 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Images
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
- G03C1/91—Photosensitive materials characterised by the base or auxiliary layers characterised by subbing layers or subbing means
- G03C1/93—Macromolecular substances therefor
Definitions
- the present invention relates to photographic film supports having improved anchoring layers for water permeable colloid layers, and more particularly to cellulose film supports having polycarbonate sublayers.
- thermoplastic polycarbonates of high molecular weight especially those derived from di-(monohydroxyaryl) alkanes,'are very suitable for improving the resistance to breakage without showing the disadvantages of the other processes.
- X is selected from thegroup consisting of monovalent cycloaliphatic and aromatic hydrocarbon fying the bonding layer that the maintenance of an adequate bonding effect is coupled with improved resist-
- R R and R standing for the same or for different radicals.
- - Preferred polycarbonates are such in which R"s are hydrogen atoms and Rs are aliphatic or cycloaliphatic hydrocarbon residues of the kind mentioned above, whereby the two R's may be the same or different members of action is very quickly produced.
- the emulsion When subjected to mechanical stress, the emulsion lifts from the film material and it floats off in the photographic baths.
- intermediate layers the polarity of whichconforms better to the gelatine than the acetyl cellulose, so that they can be provided with a gelatine anchoring layer without the; gelatine being firmly incorporated into the, surface of. the intermediate layer.
- the intermediate layer can be so applied that the fracture of the emulsion layer is taken up at the boundary surface between the intermediate layer and support.
- nitrocellulose lacquer intermediate layers has been proposed, it being known that these can be coated without additives with weakly acting solvents containing gelatine.
- nitrocellulose is however not desirable owing to the fact that it is readily inflammable.
- each R represents a hydrogen atom or the same or a different member of the groups mentioned above and each R represents a member of the group consisting of the methyl, the ethyl, the propyl, the isopr'opyl, the n-butyl, the tert. butyl, the isobutyl, the tert. amyl, thecyc'lopentyl, the cyclohexyl, and the phenyl being hydrogen.
- each R is the same or Under these polycarbonates typical representatives are for instance the poly-(2,2-(4,4-dihydroxy-diphenylen)- propane-carbonate), the poly (2,2 (4,4-dihydroxy-diphenylen)-butane-carbonate), the poly-(2,2-(4,4'-dihydroxydiphenylen)-pentane-carbonate), the poly-(1,1-(4, 4'-dihydroxydiphenylen)-cyclohexane-carbonate), and the mixed poly (2,2 (4,4'-dihydroxy-diphenylen)-propaneand (4,4-dihydroxy-diphenylen)methane-carbonate).
- Aliphatic dihydroxy compounds such as: ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, thiodiglycol, ethylene dithiodiglyeol, the di-, and polyglycols produced from propyleneoxide-l,2, o, m, or p-xylylene glycol, propanediol-1,3, butanediol-1,3, butanediol-l,4, 2-methylpropanediol-L3, pentanediol-l,5, 2-ethylpropanediol-l,3, hexanediol-1,6, octanediol-1,8, l-ethylhexane diol-l,3, and decanediol-l,l0, cycloaliphatic dihydroxy compounds such as cyclohexanediol-l,4, cyclohexanediol-1,2, 2,2-(
- the aryl residues can be the same or different.
- the aryl residues can furthermore carry hydrogen atoms or substituents which are incapable of taking part in the reaction to polycarbonates, e.g. the halogens and alkyl groups such as ethyl, methyl, propyl or tertiary butyl.
- dihydroxydiaryl sulphones of the specified type the following may be mentioned:
- dihydroxy compounds which may be used in admixture with the dihydroxydiaryl sulphones if desired, there may be mentioned the following: ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, the corresponding thioglycols, di- 01' poly-glycols obtained from propylene oxide-1,2, propanediol-l,2, propanediol-l,3, butanediol-1,3, butanediol-1,4, 2-methylpropanediol-1,3, pentanediol-l,5, 2-ethylpropanediol-l,3, hexanediol-l,6, octanediol-1,8, 2-ethylhexanediol-l,3 and decanediol-l,l0; cyclohexanediol-l,4, cyclohexanediol-l,
- Di-monohydroxyarylalkanes as disclosed in copending application Serial No. 577,362, filed April 4, 1956, and in British specification No. 772,627, such as di-(p-hydroxyphenyl)-methane, 2,2- di-(p-hydroxyphenyl)-propane, 1,1-di-(p-hydroxyphenyl)- cyclohexane, l,1-di-(p-hydroxy-m-methylphenyl) cyclohexane, 2,2 di (o-hydroxy-p-tert.-butylphenyl) -propane and 3,4-di-(p-hydroxy-phenyl)-hexane and 1,1-di-(p-hydroxy-phenyl) 1 phenyl-ethane, furthermore methane derivatives which carry besides two hydroxylaryl groups, a further alkyl residue with at least two, and a second alkyl residue with one or more carbon atoms, e.g.
- 2,2-di- (p-hydroxyphenyl) -butane 2,2 di (p-hydroxyphenyD- pentane, 3,3-di-(p-hydroxyphenyl)-pentane, 2,2-d1-(p-hydroxyphenyl)-2-methylbutane, 2,2-di-(p-hydroxy-phenyl)- hexane, 2,2-di-(p-hydroxyphenyl)-4-methylpentane, 2,2- di (p hydroxyphcnyl)-heptane, 4,4-(p-hydroxyphenyl)- heptane and 2,2-di-(p-hydroxyphenyl)tridecane.
- the polyesters may be produced it, for example, bischloro-carbonates of dihydroxy diaryl sulphones or mixture thereof with the aforementioned dihydroxy com pounds, "are condensed with dihydroxy diaryl sulphones, or mixtures thereof with other dihydroxy compounds. These condensations are suitably brought about in the presence of inert solvents and acid-binding agents such as tertiary amines as described for analogous processes in British specification No. 772,627.
- a further method of carrying out the process consists in passing phosgene either into an aqueous alkali solution or suspension of the dihydroxy diaryl sulphone, optionally in the presence of other dihydroxy compounds and inert solvents, or into a solution or suspension of these materials in an inert solvent optionally in the pres ence of acid-binding agents such as tertiary amines also as described for analogous processes in British specification No. 772,627. According to both methods of carrying out the process it is an advantage to accelerate the polycondensation by adding to the reaction mixture quaternary ammonium compounds in the form of their free bases or as salts.
- the polycarbonates by inter-esterifying dihydroxy diaryl sulphones, optionally mixed with the aforementioned dihydroxy compounds and suitably in the presence of acidic or basic catalysts, with dialkyl or diaryl carbonates.
- the basic catalysts preferably used are suitably neutralized in the course of, or at the end of, the polycondensation by adding base-binding substances are especially suitable since an excess thereof can be removed by evaporation or sublimation from the melt.
- the aryl radicals may further carry substituents which are incapable of reacting during the conversion into the poly-carbonates such as halogen, or alkyl groups such as the methyl-, ethyl-, propylor the tert. butyl group.
- Suitable dihydroxy-diaryl ethers or -thioethers are, for example:
- the further dihydroxy compound which may be used in combination with the said ethers and thioethers may be the same as those disclosed above in connection with the production of polycarbonates derived from diaryl sulfones.
- the polycarbonates produced from the above ethers and thioethers or mixtures of said compounds with further dihydroxy compounds may be produced by the same methods as the polycarbonates derived from diarylsulphones and mixtures of said sulphones with further dihydro compounds.
- aromatic dihydroxy compounds derived from mixtures of aliphatic and/or cycloaliphatic dihydroxy compounds with aromatic dihydroxy compounds other than the above dihydroxy diarylalkanes, dihydroxydiarylsulfones, and dihydroxydiarylethers and -thioethers there may be used the following aromatic dihydroxy compounds:
- ethylene glycol diethylene glycol, triethylene glycol, polyethylene glycol, thiodiglycol, ethylene dithiodiglycol, propane diol-1,2, propanediol-l,3, butanediol-1,3, butanediol-1,4, 2-methylpropanediol-1,3, pentanediol-1,5, 2-ethylpropanediol-1,3, hexanediol-1,6, octanediol-1,8, 2-ethylhexanediol-l,3, decanediol-1,l0, cyclohexanediol-1,4, cyclohexanediol-1,2- 0-, mor p-xylylene glycol, 2,2'-(4,4- dihydroxydichlorohexyl)-prop
- polycarbonates derived from the disclosed sulphones, ethers and thioethers may be represented by way of example by the following formula:
- R stands for one of the following bivalent radicals: SOFQ G G G O the phenyl radicals of which may be substituted and n stands for a whole number preferably greater than 10.
- the mixed polycarbonates may contain the following units:
- the polycarbonates may also be produced by the processes indicated in the following patents: British Patent 772,627; French Patents 1,149,261; 1,152,155; 1,152,156; 1,152,157; 1,152,158; Belgian Patents 546,375; 555,894.
- the application of the polycarbonate intermediate layer to the organic cellulose ester film takes place from specific solvent mixtures, since otherwise adequate bonding to the support is not-produced.
- Nonsolvents are preferably in quantities of 60 to 40 parts by weight and the solvent in quantities of 40 to 60 parts by weight.
- the polycarbonates can be used alone, but can be admixed with other plastics, provided the various components are compatible with one another.
- plastics are: nitrocellulose (nitrogen content 11.7- 12.3%), ethyl cellulose (ethoxyl content 48.049.5%) and co-polymers of ethylene and vinyl acetate or vinylpropionate preferably such containing 30 to 50 percent by weight of vinylester. It is possible in many cases to produce additional effects therewith.
- intermediate layers are preferably provided with a further anchoring or bonding layer varying from about 0.05 to 2 microns in thickness.
- additional layers may be produced from a mixture of (1) Gelatine and copolymers containing hydroxyl groups, preferably a partially saponified copolymer of vinyl chloride and vinyl acetate, or
- the intermediate polycarbonate layer must have a certain minimum thickness, since otherwise the preparation penetrates in spite of the slight attacking action, and this results in poor bonding and also in lower resistance to breakage.
- the aforementioned additional layer of gelatine and a polymer containing hydroxyl groups preferably consists essentially of gelatine and a partially hydrolysed copolymer of 40 to 60 parts by weight of vinyl chloride and 60 to 40 parts by weight of an organic vinyl ester, such as vinylacetate, vinylpropionate, vinylbutyrate, vinyl benzoate, this copolymer advantageously containing from 45 to 70% by Weight of vinyl chloride, 530% by weight of vinyl hydroxide and 10 to 40% by weight of organic vinyl ester.
- the proportion of gelatine with respect to the copolymer can fluctuate within Wide limits; it is however advantageous to use a ratio of 2:3 parts by weight of gelatine to 3:2 parts of copolymer.
- the aforementioned mixed acetals can be obtained bya conventional process, for example by heating the components for several hours in methanolic solution with sulphuric acid as catalyst.
- aldehydes with water-solubilizing groups are aromatic aldehydes which are substituted in the aromatic nucleus by carboxyl, sulphonic acid or hydroxy groups, for example benzaldehyde-Z-sulphonic acid, benzaldehyde-2,2-disulphonic acid and p-hy- -droxy benzaldehyde.
- the acid groups may be neutralized with bases capable of yielding water-soluble salts such as alkali metals (sodium, potassium, lithium) ammonia, amines such as primary, secondary and tertiary methyl-, ethyl-, propylamines, cyclohexylamine, morpholine, piperidine.
- bases capable of yielding water-soluble salts such as alkali metals (sodium, potassium, lithium) ammonia, amines such as primary, secondary and tertiary methyl-, ethyl-, propylamines, cyclohexylamine, morpholine, piperidine.
- the mixed acetals are preferably dissolved in a proportion of 0.75 to 1.25% in a mixture of methanol and one or more other organic solvents, for example acetone, tetrahydrofurane or dioxane.
- a partially saponified copolymer of vinyl chloride and an organic vinyl ester for example vinyl acetate, vinyl propionate or vinyl butyrate, for example a paritially saponified copolymer of vinyl chloride and vinyl acetate.
- organic vinyl ester for example vinyl acetate, vinyl propionate or vinyl butyrate
- a paritially saponified copolymer of vinyl chloride and vinyl acetate are produced by known methods by saponification in methanol solution with sulphuric acid as catalyst, merely the organic ester groups being partially saponified.
- Suitable saponified copolymers contain approximately 45- 70% by weight of vinyl chloride, 30% by weight of vinyl hydroxide and -40% by weight of vinyl acetate or another organic vinyl ester such as vinyl propionate, vinyl butyrate or vinyl benzoate.
- Copolymers of vinyl chloride and e s-unsaturated carboxylic acids or partially saponified copolymers of vinyl chloride and esters of the aforementioned acids can alternatively be used.
- the coating is advantageously produced by one of the conventional dipping processes.
- Example 1 An acetyl cellulose film (61.0% acetic acid) is treated with the following base or substrate solution by the dipping process:
- the film is thereafter provided with a gelatino silver halide emulsion layer having a thickness of 8 to 18 microns.
- the resistance to breaking is good; the bonding effect is adequate. It is true that the emulsion breaks at low relative air humidities, but the breakage is not transferred to the support.
- the layer is dried at 90-1 10 C. and subbed with the following solution:
- the film support After being dried, the film support is cast with a gelatino silver halide emulsion. It has the same properties as in Example 1.
- Example 3 A film support of acetyl cellulose (57% combined acetic acid) has applied thereto an intermediate layer consisting of the following solution:
- the film support cast with photographic emulsion has the properties indicated in Example 1.
- Example 4 An acetyl cellulose film support has applied thereto an intermediate layer from the following solution:
- the film support cast with a gelatino silver halide emulsion has the properties indicated in Example 1.
- the aforementioned combinations may not only be used for treating cellulose acetate films but also film supports of other organic cellulose esters such as cellulose acetate-butyrate, cellulose acetate-propionate.
- the film supports usually have a thickness varying between about 60 to 200 microns, preferably 80 to 120 microns.
- FIGURE is an enlarged cross-sectional view of one type of structure according to the present invention.
- 1 represents a support of an organic cellulose ester
- 2 represents an intermediate polycarbonate layer
- 3 represents a subbing layer, such as one composed of a mixture of gelatine and a polymer containing hydroxyl groups or of a mixed acetal produced from polyvinylalcohol and aldehydes having acid groups and such being free of acid groups
- 4 represents a water-permeable colloid layer, such as a gelatine silver halide emulsion layer.
- a photographic element comprising a support composed of an acetyl cellulose ester; an intermediate layer comprising a high molecular weight linear thermoplastic polycarbonate coated on said support, said polycarbonate consisting essentially of recurring units of the formula:
- OAOMHF a subbing layer coated on said polycarbonate layer and comprising a film-forming agent selected from the group consisting of (l) a mixed acetal of polyvinyl alcohol with an aldehyde devoid of water-solubilizing groups as well as an aldehyde containing a group selected from the class consisting of carboxylic and sulfonic acid groups and their water-soluble salts, and (2) a combination of gelatine with a partially hydrolyzed copolymer of vinyl chloride with a vinyl ester of a carboxylic acid; said subbing layer being coated with a gelatine-silver halide emulsion layer.
- a film-forming agent selected from the group consisting of (l) a mixed acetal of polyvinyl alcohol with an aldehyde devoid of water-solubilizing groups as well as an aldehyde containing a group selected from the class consisting of carboxylic and sulfonic acid groups and their water-soluble salts
- a photographic element comprising a support composed of an acetyl cellulose ester; an intermediate layer comprising a high molecular weight linear thermoplastic polycarbonate coated on said support, said polycarbonate consisting essentially of recurring units of the formula:
- a hydrophobic film comprising a cellulose acetate support 60-200 microns thick, an adjacent break-resistant layer l-lO microns thick of a film-forming resinous theri16 5iasa polycarbonate ring units of the formula:
- R R R R wherein X is selected from the group consisting of S, O,
- R and R are selected from the groups consisting of H, branched and unbranched monovalent aliphatic hydrocarbons containing up to 10 carbon atoms, monovalent cycloaliphatic hydrocarbons, monovalent araliphatic hydrocarbons containing up to 4 carbon atoms as side chains, phenyl and furyl, Z represents the carbon and hydrogen atoms which complete a cycloaliphatic ring, and R is a member selected from the group consisting of hydrogen, monovalent branched and unbranched aliphatic hydrocarbon radicals of up to 5 carbon atoms, monovalent cycloaliphatic hydrocarbon, and monovalent aromatic hydrocarbon radicals; and a gelatine-silver halide emulsion bonded to said break-resistant layer through a subbing layer of a mixed acetal of polyvinyl alcohol with (I) an aromatic aldehyde containing a water-solubilizing group and (II) an aldehyde free of water-solubilizing groups, 50
- subbing layer also contains a minor proportion of a partially saponified copolymer of vinyl chloride and a vinyl ester of a carboxylic acid, said copolymer being 45 to 70% by weight vinyl chloride, 5 to 30% by weight vinyl hydroxide, and 10 to 40% by weight said vinyl ester.
- R R R R R R R having a molecular weight of about 40,000 -80,000 and consisting essentially 0t recurwherein R is a member selected from the group consisting of ethyl and methyl.
Description
March 13, 1962 A. OSSENBRUNNER ETAL 3,025,163
PHOTOGRAPHIC ELEMENT HAVING POLYCARBONATE SUB-LAYER Filed March 19, 1958 GE LAT/N0 SILVER -HALlDE-EMULS/0N SUBB/NG LAYER POLYCARBONATE INTERMEDIATE LAYER CELLULOSE ESTER SUPPORT BY w -25M W A TTORNEYS 3,025,163 r PHOTOGRAPHIC ELEMENT HAVING POLY- I CARBONATE SUB-LAYER Armin Ossenbrunner and Helfried kusen, and Peter Kruck, Koln-Stammheim, Germany, assignors to Agfa Aktiengesellschaft, Leverkusen, Germany, a corporation of Germany Filed Mar. 19,1958, Ser. No. 722,464 Claims priority. application Germany Mar. 29, 1957 8 Claims. (Cl. 9687) The present invention relates to photographic film supports having improved anchoring layers for water permeable colloid layers, and more particularly to cellulose film supports having polycarbonate sublayers.
It is known that, with any photographic film material having a cellulose ester base, the danger of the material breaking is very high, especially with a low relative air humidity and of considerable thickness. With types of film which are subjected to strain in the camera or in the projector, this has a particularly disadvantageous effect.
United States Pateiit C Klockgether, Lever- I with gelatine silver halide emulsion layers This liability to breakage is caused by the .known great 1 brittleness of the gelatineused in the silver halide emul sion and by the unfavorable propertiesof the intermediate layer which is usualwith acetyl cellulose film and which promotes the bonding of the emulsion layer. This intermediate layer generally consists of gelatine, but; owing the acetyl cellulose, this gelatine in order. to produce,
m This anchoringin the su r to its low aflinity with must be incorporated in the surface an adequate bonding action. face is producedby the use of solvent in the base solution which have: a strong action on the film surface.
Furthermore, provision can be made for particularly good anchoring effect by the addition of acetyl cellulose,
which is soluble in acetone. After casting, the emulsion is united firmly to the gelatine under-layer, and, since,
this is incorporated in the surface of the film, the whole forms a rigid structure and consequently any breakage in the emulsion is transferred directly to the support.
Many experiments have been carried out for so modi- Patented Mar. 13, 1962 comesticky or tacky at the drying temperatures usual in :the manufacture ofacetyl cellulose film. Moreover, they can only be coated with ditficulty, so that another intermediate layer of nitrocellulose is still necessary.
It has nowbeen found that intermediate layers consisting wholly or in part of thermoplastic polycarbonates of high molecular weight, especially those derived from di-(monohydroxyaryl) alkanes,'are very suitable for improving the resistance to breakage without showing the disadvantages of the other processes.
Such polycarbonates correspond to the general formula:
wherein X is selected from thegroup consisting of monovalent cycloaliphatic and aromatic hydrocarbon fying the bonding layer that the maintenance of an adequate bonding effect is coupled with improved resist- These experiments have so far not If there is not.a verythorough-infilm surface, an inadequate bonding ance to breakage. led to any success. corporation into the residues, and n represents a number greater than 20,
especially than 50, R R and R standing for the same or for different radicals.
- Preferred polycarbonates are such in which R"s are hydrogen atoms and Rs are aliphatic or cycloaliphatic hydrocarbon residues of the kind mentioned above, whereby the two R's may be the same or different members of action is very quickly produced. When subiected to mechanical stress, the emulsion lifts from the film material and it floats off in the photographic baths.
'- tion are such of The difficulties canlargelybe avoided'by the ;use of}; I
intermediate layers the polarity of whichconforms better to the gelatine than the acetyl cellulose, so that they can be provided with a gelatine anchoring layer without the; gelatine being firmly incorporated into the, surface of. the intermediate layer. In this,,case, the resistance to,,.
breakage is clearly improved, sufiicient bonding being maintained, since the emulsion bonded to the intermediate layer can obviously still so that a fracture is not transmitted directly through this intermediate layer to the support; In other cases, the intermediate layer can be so applied that the fracture of the emulsion layer is taken up at the boundary surface between the intermediate layer and support. For example, the use of nitrocellulose lacquer intermediate layers has been proposed, it being known that these can be coated without additives with weakly acting solvents containing gelatine.
The use of nitrocellulose is however not desirable owing to the fact that it is readily inflammable.
The intermediate layers consisting of vinyl polymers as disclosed in USA. Patent No. 2,133,110 have the disadvantage that they are generally'thermoplastic and be be displaced on the film surface, 1
. the propyl, the isopropyl, the
the hexyl, the heptyl, the octyl, the nonyl, the decyl, the l-methyl-l-butenyl,
the group mentioned above, for instance an aliphatic or cycloaliphatic hydrocarbon residue.
Examples ofpolycarbonates according to the inventhe above formula, in which both R and all R"s are hydrogen atoms, further in which one R is a hydrogen atom,- the-other R-is the methyl, the ethyl, butyl, the isobutyl, the amyl,
the l-ethyl-l-pentenyl, the cyclopentyl, the cyclohexyl, thebenzyl, the 4 -m'eth yl-, ethyl-,
propyl-, i'sopropyl-gand butyl phenylen, the phenyl, and the furyl residue, and'all a different member of the ,hydrocarbon residues mentioned here above and all R"s group, the remaining R are hydrogen atoms, in which X is Z representing the carbon and atoms completing the cyclopentane or the cyclohexane ring and R is hydrogen, and such, in which each R represents a hydrogen atom or the same or a different member of the groups mentioned above and each R represents a member of the group consisting of the methyl, the ethyl, the propyl, the isopr'opyl, the n-butyl, the tert. butyl, the isobutyl, the tert. amyl, thecyc'lopentyl, the cyclohexyl, and the phenyl being hydrogen.
the group consisting" of by to 10'carbon atoms, ono:
having up to'4 carbon atoms as side- Rs are hydrogen atoms, in ;which each R is the same or Under these polycarbonates typical representatives are for instance the poly-(2,2-(4,4-dihydroxy-diphenylen)- propane-carbonate), the poly (2,2 (4,4-dihydroxy-diphenylen)-butane-carbonate), the poly-(2,2-(4,4'-dihydroxydiphenylen)-pentane-carbonate), the poly-(1,1-(4, 4'-dihydroxydiphenylen)-cyclohexane-carbonate), and the mixed poly (2,2 (4,4'-dihydroxy-diphenylen)-propaneand (4,4-dihydroxy-diphenylen)methane-carbonate).
For the formation of the polycarbonates, it is also possible to use mixtures of various di-monohydroxyaryl alkanes as well as mixtures of di-monohydroxyarylen alkanes with other dihydroxy compounds, such as aliphatic, cycloaliphatic dihydroxy compounds as well as aromatic dihydroxy compounds which are different from those mentioned above.
As examples of the accompanying dihydroxy compounds which may be used according to the invention, the following are named by way of example:
Aliphatic dihydroxy compounds such as: ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, thiodiglycol, ethylene dithiodiglyeol, the di-, and polyglycols produced from propyleneoxide-l,2, o, m, or p-xylylene glycol, propanediol-1,3, butanediol-1,3, butanediol-l,4, 2-methylpropanediol-L3, pentanediol-l,5, 2-ethylpropanediol-l,3, hexanediol-1,6, octanediol-1,8, l-ethylhexane diol-l,3, and decanediol-l,l0, cycloaliphatic dihydroxy compounds such as cyclohexanediol-l,4, cyclohexanediol-1,2, 2,2-(4,4'-dihydroxy-dicyclohexylen)-propane and 2,6-dihydroxydecahydronaphthalene and aromatic dihydroxy compounds such as hydroquinone, resorcinol,
pyrocatechol, 4,4-dihydroxydiphenyl, 2,2-dihydroxydiphenyl, 1,4-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 1,2-dihydroxynaphthalene, l,S-dihydroxynaphthalene, dihydroxyanthracene,
2,2-dihydroxydinaphthyl-l,I and o, m, p-hydroxybenzylalcohol.
These polycarbonates may be replaced wholly or partially by further polycarbonates. Such further thermoplastic polycarbonates of high molecular weight can be obtained by reacting dihydroxy diaryl sulphones or mixtures of dihydroxy diaryl sulphones with other bifunctional dihydroxy compounds and from dihydroxy diaryl ethers or dihydroxy diaryl thioeters or from mixtures of the said compounds with other dihydroxy compounds, according to German patent application No. F 17 168 IVc/39c (D.A.S. 1,007,996, published May 9, 1957), and from dihydroxy diaryl ethers or dihydroxy diaryl thioeters or from mixtures of the said compounds with other dihydroxy compounds according to German patent application Nos. F 21 459 IVb/39c and F 21 662 IVc/39c.
Further suitable polycarbonates are those which are derived from mixtures of aliphatic and/or cycloaliphatic dihydroxy compounds with at least one aromatic dihydroxy compound other than the above cited aromatic dihydroxy compounds.
In the dihydroxydiaryl sulphones used for forming the polycarbonates, the aryl residues can be the same or different. The aryl residues can furthermore carry hydrogen atoms or substituents which are incapable of taking part in the reaction to polycarbonates, e.g. the halogens and alkyl groups such as ethyl, methyl, propyl or tertiary butyl.
As examples of dihydroxydiaryl sulphones of the specified type, the following may be mentioned:
4,4'-dihydroxydiphenylsulphone, 2,2-dihydroxydiphenylsulphone, 3,3'-dihydroxydiphenylsulphone, 4,4-dihydroxy-2,2-dimethyldiphenyl-sulphone, 4,4-dihydroxy-3, 3'-dimethyl-diphenyl-sulphone, 2,2 dihydroxy 4,4 dimethyl-diphenyl-sulphone and 2,2-dihydroxy-1,l'-dinaphthyl-sulphones.
As examples of the other dihydroxy compounds which may be used in admixture with the dihydroxydiaryl sulphones if desired, there may be mentioned the following: ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, the corresponding thioglycols, di- 01' poly-glycols obtained from propylene oxide-1,2, propanediol-l,2, propanediol-l,3, butanediol-1,3, butanediol-1,4, 2-methylpropanediol-1,3, pentanediol-l,5, 2-ethylpropanediol-l,3, hexanediol-l,6, octanediol-1,8, 2-ethylhexanediol-l,3 and decanediol-l,l0; cyclohexanediol-l,4, cyclohexanediol-l,2, o-. p-, or m-xylene glycol, 2,2-(4,4'-dihydroxy dicyclohexyl) propane, 2,6 dihydroxy-decahydronaphthalene, hydroquinone, resorcinol, pyrocatechol, 4,4- dihydroxydiphenyl, 2,2 dihydroxydiphenyl, 1,4 dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 1.Z-dihydroxynaphthalene, 1,5-dihydroxyanthracene, 2,2'-dihydroxydinaphthalene-1,l', and 0-, m-, or p-hydroxybenzylaleohol. Di-monohydroxyarylalkanes as disclosed in copending application Serial No. 577,362, filed April 4, 1956, and in British specification No. 772,627, such as di-(p-hydroxyphenyl)-methane, 2,2- di-(p-hydroxyphenyl)-propane, 1,1-di-(p-hydroxyphenyl)- cyclohexane, l,1-di-(p-hydroxy-m-methylphenyl) cyclohexane, 2,2 di (o-hydroxy-p-tert.-butylphenyl) -propane and 3,4-di-(p-hydroxy-phenyl)-hexane and 1,1-di-(p-hydroxy-phenyl) 1 phenyl-ethane, furthermore methane derivatives which carry besides two hydroxylaryl groups, a further alkyl residue with at least two, and a second alkyl residue with one or more carbon atoms, e.g. 2,2-di- (p-hydroxyphenyl) -butane, 2,2 di (p-hydroxyphenyD- pentane, 3,3-di-(p-hydroxyphenyl)-pentane, 2,2-d1-(p-hydroxyphenyl)-2-methylbutane, 2,2-di-(p-hydroxy-phenyl)- hexane, 2,2-di-(p-hydroxyphenyl)-4-methylpentane, 2,2- di (p hydroxyphcnyl)-heptane, 4,4-(p-hydroxyphenyl)- heptane and 2,2-di-(p-hydroxyphenyl)tridecane.
The polyesters may be produced it, for example, bischloro-carbonates of dihydroxy diaryl sulphones or mixture thereof with the aforementioned dihydroxy com pounds, "are condensed with dihydroxy diaryl sulphones, or mixtures thereof with other dihydroxy compounds. These condensations are suitably brought about in the presence of inert solvents and acid-binding agents such as tertiary amines as described for analogous processes in British specification No. 772,627.
A further method of carrying out the process consists in passing phosgene either into an aqueous alkali solution or suspension of the dihydroxy diaryl sulphone, optionally in the presence of other dihydroxy compounds and inert solvents, or into a solution or suspension of these materials in an inert solvent optionally in the pres ence of acid-binding agents such as tertiary amines also as described for analogous processes in British specification No. 772,627. According to both methods of carrying out the process it is an advantage to accelerate the polycondensation by adding to the reaction mixture quaternary ammonium compounds in the form of their free bases or as salts.
Finally it is also possible to produce the polycarbonates by inter-esterifying dihydroxy diaryl sulphones, optionally mixed with the aforementioned dihydroxy compounds and suitably in the presence of acidic or basic catalysts, with dialkyl or diaryl carbonates. The basic catalysts preferably used are suitably neutralized in the course of, or at the end of, the polycondensation by adding base-binding substances are especially suitable since an excess thereof can be removed by evaporation or sublimation from the melt.
For the production of the polycarbonates derived from diphenyl ethers and -thioethers diphenyl ethers and/or -thioethers may be used in which the two aryl radicals are the same or different.
The aryl radicals may further carry substituents which are incapable of reacting during the conversion into the poly-carbonates such as halogen, or alkyl groups such as the methyl-, ethyl-, propylor the tert. butyl group.
Suitable dihydroxy-diaryl ethers or -thioethers are, for example:
4.4'-dihydroxy-diphenyl ether, 4,4-dihydroxy-2,2'-dimethyldiphenyl ether, 4,4 dihydroxy 3,3 dimethyldiphenyl ether or their homologues, as well as 4,4'-dihydroxydiphenyl sulphide, 4,4 dihydroxy 2,2 dimethyldiphenyl-sulphide, 4,4 dihydroxy-3,3'-dimethyldiphenylsulphide and their homologues. The latter are readily obtainable by condensation of sulphur dichloride with the corresponding phenols.
The further dihydroxy compound which may be used in combination with the said ethers and thioethers may be the same as those disclosed above in connection with the production of polycarbonates derived from diaryl sulfones. The polycarbonates produced from the above ethers and thioethers or mixtures of said compounds with further dihydroxy compounds may be produced by the same methods as the polycarbonates derived from diarylsulphones and mixtures of said sulphones with further dihydro compounds.
For the production of polycarbonates derived from mixtures of aliphatic and/or cycloaliphatic dihydroxy compounds with aromatic dihydroxy compounds other than the above dihydroxy diarylalkanes, dihydroxydiarylsulfones, and dihydroxydiarylethers and -thioethers there may be used the following aromatic dihydroxy compounds:
Hydroquinone, resorcinol, pyrocatechol, 4,4 -dihydroxydiphenyl, 2,2-dihydroxydiphenyl, 1,4-dihydroxynaphthalene, 1,G-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 1,Z-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,4-dihydroxyquinoline, 2,2-dihydroxydinaphthyl-1,1 and mor p-hydroxybenzyl alcohol. As aliphatic or cycloaliphatic dihydroxy compounds to be used according to the invention, there may be named: ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, thiodiglycol, ethylene dithiodiglycol, propane diol-1,2, propanediol-l,3, butanediol-1,3, butanediol-1,4, 2-methylpropanediol-1,3, pentanediol-1,5, 2-ethylpropanediol-1,3, hexanediol-1,6, octanediol-1,8, 2-ethylhexanediol-l,3, decanediol-1,l0, cyclohexanediol-1,4, cyclohexanediol-1,2- 0-, mor p-xylylene glycol, 2,2'-(4,4- dihydroxydichlorohexyl)-propane, 4,4-dihydroxydicyclohexyl methane and 2,6-dihydroxydecahydronaphthalene.
The transformation of the foregoing dihydroxy compounds into high molecular polycarbonates can be carried out by the methods disclosed above.
The aforementioned polycarbonates derived from the disclosed sulphones, ethers and thioethers may be represented by way of example by the following formula:
in which R stands for one of the following bivalent radicals: SOFQ G G G O the phenyl radicals of which may be substituted and n stands for a whole number preferably greater than 10. The mixed polycarbonates may contain the following units:
6 Formulae I and II, these dihydroxy compounds can all be considered as bisphenols.
The polycarbonates may also be produced by the processes indicated in the following patents: British Patent 772,627; French Patents 1,149,261; 1,152,155; 1,152,156; 1,152,157; 1,152,158; Belgian Patents 546,375; 555,894.
The application of the polycarbonate intermediate layer to the organic cellulose ester film takes place from specific solvent mixtures, since otherwise adequate bonding to the support is not-produced. Certain mixtures of solvents and nonsolvents for acetyl cellulose and other organic cellulose esters, and preferably chlorinated hydrocarbons since the polycarbonate dissolves well in the latter, have proved to be particularly suitable.
Mixtures of methylene chloride and trichloroethylene, chloroform and benzene, methylene chloride, acetone and trichloroethylene are examples. The nonsolvents are preferably in quantities of 60 to 40 parts by weight and the solvent in quantities of 40 to 60 parts by weight.
The polycarbonates can be used alone, but can be admixed with other plastics, provided the various components are compatible with one another. Examples of such plastics are: nitrocellulose (nitrogen content 11.7- 12.3%), ethyl cellulose (ethoxyl content 48.049.5%) and co-polymers of ethylene and vinyl acetate or vinylpropionate preferably such containing 30 to 50 percent by weight of vinylester. It is possible in many cases to produce additional effects therewith.
These intermediate layers are preferably provided with a further anchoring or bonding layer varying from about 0.05 to 2 microns in thickness. Such additional layers may be produced from a mixture of (1) Gelatine and copolymers containing hydroxyl groups, preferably a partially saponified copolymer of vinyl chloride and vinyl acetate, or
(2) A polyvinyl alcohol mixed acetal obtained from polyvinyl alcohol and aldehydes with and without watersolubilising groups and co-polymers containing hydroxyl groups.
These mixtures are preferably applied from a solvent mixture which gives hardly any swelling of the polycarbonate, so that no incorporation into the surface of the intermediate polycarbonate layer takes place. The use of methanol to which a small proportion of acetone has been added has proved particularly satisfactory.
The intermediate polycarbonate layer must have a certain minimum thickness, since otherwise the preparation penetrates in spite of the slight attacking action, and this results in poor bonding and also in lower resistance to breakage.
It has proved to be desirable to use polycarbonates having a molecular weight of about 40,000-80,000. Substances havinghigher molecular weights are difficult to dissolve and dry on an irregular form, whereas a lower molecular weight produces less satisfactory film-forming properties and too easy swellability.
The aforementioned additional layer of gelatine and a polymer containing hydroxyl groups preferably consists essentially of gelatine and a partially hydrolysed copolymer of 40 to 60 parts by weight of vinyl chloride and 60 to 40 parts by weight of an organic vinyl ester, such as vinylacetate, vinylpropionate, vinylbutyrate, vinyl benzoate, this copolymer advantageously containing from 45 to 70% by Weight of vinyl chloride, 530% by weight of vinyl hydroxide and 10 to 40% by weight of organic vinyl ester. The proportion of gelatine with respect to the copolymer can fluctuate within Wide limits; it is however advantageous to use a ratio of 2:3 parts by weight of gelatine to 3:2 parts of copolymer. The coating solution has added thereto an organic carboxylic acid, such as acetic acid, propionic acid, phthalic acid, salicylic acid, maleic acid in amounts of about 5 to 50 percent calculated on the weight of gelatine. Furthermore, hardening agents for the gelatine can be incorporated into this auxiliary layer, for example formaldehyde or gyloxal. The
spasms 7 aforementioned components are dissolved in conventional organic solvents as disclosed above and the solutions are applied to the support by one of the known dipping processes.
The aforementioned mixed acetals can be obtained bya conventional process, for example by heating the components for several hours in methanolic solution with sulphuric acid as catalyst. Examples of aldehydes with water-solubilizing groups are aromatic aldehydes which are substituted in the aromatic nucleus by carboxyl, sulphonic acid or hydroxy groups, for example benzaldehyde-Z-sulphonic acid, benzaldehyde-2,2-disulphonic acid and p-hy- -droxy benzaldehyde. Examples of aldehydes without water-solubilizing groups are araliphatic and aliphatic aldehydes, for example benzaldehyde, tolyl aldehyde, pchlorobenzaldehyde and hydrocinnamaldehyde. For the bonding action which is to be produced, it is of decisive importance that both the hydrophilic and the by drophobic components shall be used. The degree of acetalisation can fluctuate within wide limits, but the best re-- sults are produced with products in which 50-60% of all hydroxyl groups of the polyvinyl alcohol are acetalised. The most favorable ratio between aldehydes with watersolubilizing groups and those without water-solubilizing groups depends upon the nature of the aldehydes. It has, however, been found that, in general, a molecular excess of aldehydes without water-solubilizing groups is necessary for the production of a sufficient degree of solubility in organic solvents.
The acid groups may be neutralized with bases capable of yielding water-soluble salts such as alkali metals (sodium, potassium, lithium) ammonia, amines such as primary, secondary and tertiary methyl-, ethyl-, propylamines, cyclohexylamine, morpholine, piperidine. For producing the intermediate layer, the mixed acetals are preferably dissolved in a proportion of 0.75 to 1.25% in a mixture of methanol and one or more other organic solvents, for example acetone, tetrahydrofurane or dioxane. For improving the bonding action, it may be advisable to add a small proportion of a partially saponified copolymer of vinyl chloride and an organic vinyl ester, for example vinyl acetate, vinyl propionate or vinyl butyrate, for example a paritially saponified copolymer of vinyl chloride and vinyl acetate. These partially saponified copolymers are produced by known methods by saponification in methanol solution with sulphuric acid as catalyst, merely the organic ester groups being partially saponified. Suitable saponified copolymers contain approximately 45- 70% by weight of vinyl chloride, 30% by weight of vinyl hydroxide and -40% by weight of vinyl acetate or another organic vinyl ester such as vinyl propionate, vinyl butyrate or vinyl benzoate. Copolymers of vinyl chloride and e s-unsaturated carboxylic acids or partially saponified copolymers of vinyl chloride and esters of the aforementioned acids can alternatively be used. The coating is advantageously produced by one of the conventional dipping processes.
With application speeds by the dipping process of 1.5 to 2.5m./min., concentrations of 3-5% of polycarbonates with the mean viscosity mentioned above have proved advisable. The thickness of the intermediate polycarbonate layer may amount to l to 10, preferably 2 to 5 microns.
The process will be explained in the following examples:
Example 1 An acetyl cellulose film (61.0% acetic acid) is treated with the following base or substrate solution by the dipping process:
30 g. of a polycarbonate of 4,4'-dihydroxydiphenyldimethyl methane,
400 cc. of methylene chloride, and
600 cc. of trichloroethylene.
i The layer is thoroughly dried at a temperature of C. and thereafter coated with the following solution:
9 g. of gelatine 3 g. of phthalic acid 3 g. of a partially saponified co-polymer of vinyl chloride and vinyl acetate having the following composition:
63.2% of vinyl chloride, 25.3% of vinyl alcohol, 11.5% of vinyl acetate,
610 cc. of methanol, and
390 cc. of acetone.
The film is thereafter provided with a gelatino silver halide emulsion layer having a thickness of 8 to 18 microns. The resistance to breaking is good; the bonding effect is adequate. It is true that the emulsion breaks at low relative air humidities, but the breakage is not transferred to the support.
Example 2 A film support of acetyl cellulose (59% acetic acid) and the usual plasticisers has applied thereto by a dipping process an intermediate layer consisting of the following solution:
10 g. of 4,4'-dihydroxydiphenyl methyl ethyl methane polycarbonate,
10 g. of cellulose nitrate,
600 cc. of ethyl acetate, and
400 cc. of methylene chloride.
The layer is dried at 90-1 10 C. and subbed with the following solution:
7 g. of gelatine,
2.3 g. of phthalic acid, 1.5 cc. of water,
303 cc. of methanol, 627 cc. of acetone and 0.25 g. of glyoxal.
After being dried, the film support is cast with a gelatino silver halide emulsion. It has the same properties as in Example 1.
Example 3 A film support of acetyl cellulose (57% combined acetic acid) has applied thereto an intermediate layer consisting of the following solution:
25 g. of 4,4'-dihydroxydiphenyl-methyl-ethyl methane polycarbonate,
250 cc. of ethyl acetate,
cc. of acetone, and
600 cc. of trichloroethylene.
After drying of the layer, the following solution is used for subbing purposes:
The film support cast with photographic emulsion has the properties indicated in Example 1.
Example 4 An acetyl cellulose film support has applied thereto an intermediate layer from the following solution:
20 g. of a polycarbonate of 4,4'-dihydroxydiphenyl dirnethyl methane,
5 g. of a co-polymer of ethylene and vinyl acetate (1:1),
600 cc. of methylene chloride, and
400 cc. of trichloroethylene.
After drying of the y the following solution is The film support cast with a gelatino silver halide emulsion has the properties indicated in Example 1.
The aforementioned combinations may not only be used for treating cellulose acetate films but also film supports of other organic cellulose esters such as cellulose acetate-butyrate, cellulose acetate-propionate. The film supports usually have a thickness varying between about 60 to 200 microns, preferably 80 to 120 microns.
In the accompanying drawing the FIGURE is an enlarged cross-sectional view of one type of structure according to the present invention. In this figure, 1 represents a support of an organic cellulose ester, 2 represents an intermediate polycarbonate layer, 3 represents a subbing layer, such as one composed of a mixture of gelatine and a polymer containing hydroxyl groups or of a mixed acetal produced from polyvinylalcohol and aldehydes having acid groups and such being free of acid groups, 4 represents a water-permeable colloid layer, such as a gelatine silver halide emulsion layer.
We claim:
1. A photographic element comprising a support composed of an acetyl cellulose ester; an intermediate layer comprising a high molecular weight linear thermoplastic polycarbonate coated on said support, said polycarbonate consisting essentially of recurring units of the formula:
C fl
OAOMHF a subbing layer coated on said polycarbonate layer and comprising a film-forming agent selected from the group consisting of (l) a mixed acetal of polyvinyl alcohol with an aldehyde devoid of water-solubilizing groups as well as an aldehyde containing a group selected from the class consisting of carboxylic and sulfonic acid groups and their water-soluble salts, and (2) a combination of gelatine with a partially hydrolyzed copolymer of vinyl chloride with a vinyl ester of a carboxylic acid; said subbing layer being coated with a gelatine-silver halide emulsion layer.
2. A photographic element comprising a support composed of an acetyl cellulose ester; an intermediate layer comprising a high molecular weight linear thermoplastic polycarbonate coated on said support, said polycarbonate consisting essentially of recurring units of the formula:
(32KB a subbing layer coated on said polycarbonate layer and comprising a film-forming agent selected from the group consisting of (1) a mixed acetal of polyvinyl alcohol with an aldehyde devoid of water-solubilizing groups as well as an aldehyde containing a group selected from the class consisting of carboxylic and sulfonic acid groups and their water-soluble salts, and (2) a combination of gelatine with a partially hydrolyzed copolymer of vinyl chloride with a vinyl ester of a carboxylic acid; said subbing layer being coated with a gelatine-silver halide emulsion layer.
3. A hydrophobic film comprising a cellulose acetate support 60-200 microns thick, an adjacent break-resistant layer l-lO microns thick of a film-forming resinous theri16 5iasa polycarbonate ring units of the formula:
R R R wherein X is selected from the group consisting of S, O,
and
wherein R and R are selected from the groups consisting of H, branched and unbranched monovalent aliphatic hydrocarbons containing up to 10 carbon atoms, monovalent cycloaliphatic hydrocarbons, monovalent araliphatic hydrocarbons containing up to 4 carbon atoms as side chains, phenyl and furyl, Z represents the carbon and hydrogen atoms which complete a cycloaliphatic ring, and R is a member selected from the group consisting of hydrogen, monovalent branched and unbranched aliphatic hydrocarbon radicals of up to 5 carbon atoms, monovalent cycloaliphatic hydrocarbon, and monovalent aromatic hydrocarbon radicals; and a gelatine-silver halide emulsion bonded to said break-resistant layer through a subbing layer of a mixed acetal of polyvinyl alcohol with (I) an aromatic aldehyde containing a water-solubilizing group and (II) an aldehyde free of water-solubilizing groups, 50 to 60% of the hydroxy groups being acetalized and the (II) aldehyde being in molar excess with respect to the (I) aldehyde.
4. The film of claim 3 wherein said subbing layer is a mixture of 2 to 3 parts gelatme by weight with 3 to 2 parts by weight of a partially hydrolyzed copolymer of vinyl chloride and a vinyl ester of a carboxylic acid, the copolymer being 45 to by weight vinyl chloride, 5 to 30% by weight vinyl hydroxide, and 10 to 40% by weight said vinyl ester.
5. The film of claim 3 wherein the subbing layer also contains a minor proportion of a partially saponified copolymer of vinyl chloride and a vinyl ester of a carboxylic acid, said copolymer being 45 to 70% by weight vinyl chloride, 5 to 30% by weight vinyl hydroxide, and 10 to 40% by weight said vinyl ester.
6. The film of claim 3 wherein the polycarbonate consists of recurring units resulting from the use of a mixture of dihydroxy compounds in the preparation of the polycarbonate, one portion of said dihydroxy compounds having the formula:
R R R R R R having a molecular weight of about 40,000 -80,000 and consisting essentially 0t recurwherein R is a member selected from the group consisting of ethyl and methyl.
References Cited in the file of this patent UNITED STATES PATENTS Alles et a1. Dec. 28, 1954 Saner Dec. 28, 1954 Caldwell July 16, 1957 Klockgether et a1 Feb. 17, 1959
Claims (1)
- 3. A HYDROPHOBIC FILM COMPRISING A CELLULOSE ACETATE SUPPORT 60-200 MICRONS THICK, AN ADJACENT BREAK-RESISTANT LAYER 1-10 MICRONS THICK OF A FILM-FORMING RESINOUS THERMOPLASTIC POLYCARBONATE HAVING A MOLECULAR WEIGHT OF ABOUT 40,000-80,000 AND CONSISTING ESSENTIALLY OF RECURRING UNITS OF THE FORMULA:
Applications Claiming Priority (1)
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DEA26849A DE1055949B (en) | 1957-03-29 | 1957-03-29 | Process for the pretreatment of film bases for the application of hydrophilic colloid layers |
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US3025163A true US3025163A (en) | 1962-03-13 |
Family
ID=6926256
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Application Number | Title | Priority Date | Filing Date |
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US722464A Expired - Lifetime US3025163A (en) | 1957-03-29 | 1958-03-19 | Photographic element having polycarbonate sub-layer |
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US (1) | US3025163A (en) |
BE (1) | BE566227A (en) |
CH (1) | CH368378A (en) |
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3236678A (en) * | 1960-08-29 | 1966-02-22 | Gen Aniline & Film Corp | Subbing layer for polycarbonate filmbase |
US3316118A (en) * | 1963-11-29 | 1967-04-25 | Gen Aniline & Film Corp | Mixed resin adhesive composition for securing hydrophobic calcium tungstate stale salt laver to hydrophilic base |
US3506445A (en) * | 1964-12-09 | 1970-04-14 | Bexford Ltd | Synthetic film materials |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1236935B (en) * | 1961-10-17 | 1967-03-16 | Agfa Ag | Transparent photographic amplifier films |
IT1170997B (en) * | 1981-05-26 | 1987-06-03 | Minnesota Mining & Mfg | IMPROVEMENT IN SUBSTRATING POLYETHYLENE TEREPHTHALATE SUPPORTS AND PHOTOGRAPHIC FILMS INCLUDING THESE IMPROVED SUPPORTS |
US5290672A (en) * | 1984-11-24 | 1994-03-01 | The Wiggins Teape Group Limited | Base paper for photographic prints |
GB8429729D0 (en) * | 1984-11-24 | 1985-01-03 | Wiggins Teape Group Ltd | Base paper |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2698241A (en) * | 1952-06-07 | 1954-12-28 | Du Pont | Photographic elements and process of preparing the same |
US2698240A (en) * | 1950-03-22 | 1954-12-28 | Du Pont | Photographic films and their preparation |
US2799666A (en) * | 1956-01-26 | 1957-07-16 | Eastman Kodak Co | Linear polycarbonates from bis (hydroxyethoxy) aromatic compounds |
US2874046A (en) * | 1955-06-25 | 1959-02-17 | Agfa Ag | Process for the retreatment of foils consisting of highly polymeric substances for the application of hydrophilic colloids |
-
0
- BE BE566227D patent/BE566227A/xx unknown
-
1957
- 1957-03-29 DE DEA26849A patent/DE1055949B/en active Pending
-
1958
- 1958-03-19 US US722464A patent/US3025163A/en not_active Expired - Lifetime
- 1958-03-24 CH CH5745358A patent/CH368378A/en unknown
- 1958-03-27 GB GB9858/58A patent/GB862205A/en not_active Expired
- 1958-03-28 FR FR1204417D patent/FR1204417A/en not_active Expired
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2698240A (en) * | 1950-03-22 | 1954-12-28 | Du Pont | Photographic films and their preparation |
US2698241A (en) * | 1952-06-07 | 1954-12-28 | Du Pont | Photographic elements and process of preparing the same |
US2874046A (en) * | 1955-06-25 | 1959-02-17 | Agfa Ag | Process for the retreatment of foils consisting of highly polymeric substances for the application of hydrophilic colloids |
US2799666A (en) * | 1956-01-26 | 1957-07-16 | Eastman Kodak Co | Linear polycarbonates from bis (hydroxyethoxy) aromatic compounds |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3236678A (en) * | 1960-08-29 | 1966-02-22 | Gen Aniline & Film Corp | Subbing layer for polycarbonate filmbase |
US3316118A (en) * | 1963-11-29 | 1967-04-25 | Gen Aniline & Film Corp | Mixed resin adhesive composition for securing hydrophobic calcium tungstate stale salt laver to hydrophilic base |
US3506445A (en) * | 1964-12-09 | 1970-04-14 | Bexford Ltd | Synthetic film materials |
Also Published As
Publication number | Publication date |
---|---|
GB862205A (en) | 1961-03-01 |
DE1055949B (en) | 1959-04-23 |
BE566227A (en) | |
FR1204417A (en) | 1960-01-26 |
CH368378A (en) | 1963-03-31 |
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