US3658546A - Method of incorporating photographic ingredients into photographic colloid compositions - Google Patents
Method of incorporating photographic ingredients into photographic colloid compositions Download PDFInfo
- Publication number
- US3658546A US3658546A US21470A US3658546DA US3658546A US 3658546 A US3658546 A US 3658546A US 21470 A US21470 A US 21470A US 3658546D A US3658546D A US 3658546DA US 3658546 A US3658546 A US 3658546A
- Authority
- US
- United States
- Prior art keywords
- water
- photographic
- ingredient
- hydrophilic colloid
- substantially water
- 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
- 239000000084 colloidal system Substances 0.000 title claims abstract description 46
- 239000004615 ingredient Substances 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims description 44
- 239000000203 mixture Substances 0.000 title abstract description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000002904 solvent Substances 0.000 claims abstract description 42
- 239000000839 emulsion Substances 0.000 claims abstract description 38
- 239000002270 dispersing agent Substances 0.000 claims abstract description 16
- 239000008199 coating composition Substances 0.000 claims abstract description 12
- 239000003960 organic solvent Substances 0.000 claims abstract description 12
- -1 silver halide Chemical class 0.000 claims description 28
- 239000004332 silver Substances 0.000 claims description 21
- 229910052709 silver Inorganic materials 0.000 claims description 21
- 238000001704 evaporation Methods 0.000 claims description 11
- 230000008020 evaporation Effects 0.000 claims description 11
- 238000009835 boiling Methods 0.000 claims description 5
- 230000001235 sensitizing effect Effects 0.000 claims description 5
- 239000003381 stabilizer Substances 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 239000003945 anionic surfactant Substances 0.000 claims description 2
- 238000009792 diffusion process Methods 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 abstract description 50
- 239000000463 material Substances 0.000 abstract description 12
- 239000011248 coating agent Substances 0.000 abstract description 9
- 238000000576 coating method Methods 0.000 abstract description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 39
- 229920000159 gelatin Polymers 0.000 description 19
- 235000019322 gelatine Nutrition 0.000 description 19
- 108010010803 Gelatin Proteins 0.000 description 18
- 239000008273 gelatin Substances 0.000 description 18
- 235000011852 gelatine desserts Nutrition 0.000 description 18
- 150000001875 compounds Chemical class 0.000 description 16
- 239000000243 solution Substances 0.000 description 15
- 239000000080 wetting agent Substances 0.000 description 15
- 239000000975 dye Substances 0.000 description 14
- 239000012153 distilled water Substances 0.000 description 7
- 238000010168 coupling process Methods 0.000 description 6
- 238000005859 coupling reaction Methods 0.000 description 6
- 230000008878 coupling Effects 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000009736 wetting Methods 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 238000010348 incorporation Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- NMJJFJNHVMGPGM-UHFFFAOYSA-N butyl formate Chemical compound CCCCOC=O NMJJFJNHVMGPGM-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- YKYONYBAUNKHLG-UHFFFAOYSA-N propyl acetate Chemical compound CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- KNKRKFALVUDBJE-UHFFFAOYSA-N 1,2-dichloropropane Chemical compound CC(Cl)CCl KNKRKFALVUDBJE-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- 241001479434 Agfa Species 0.000 description 1
- 102000009027 Albumins Human genes 0.000 description 1
- 108010088751 Albumins Proteins 0.000 description 1
- 238000012935 Averaging Methods 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 1
- 239000001828 Gelatine Substances 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
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 229920002494 Zein Polymers 0.000 description 1
- 241000933336 Ziziphus rignonii Species 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 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
- 229940043232 butyl acetate Drugs 0.000 description 1
- 229930188620 butyrolactone Natural products 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 229960001760 dimethyl sulfoxide Drugs 0.000 description 1
- HWQXBVHZYDELQG-UHFFFAOYSA-L disodium 2,2-bis(6-methylheptyl)-3-sulfobutanedioate Chemical compound C(CCCCC(C)C)C(C(C(=O)[O-])S(=O)(=O)O)(C(=O)[O-])CCCCCC(C)C.[Na+].[Na+] HWQXBVHZYDELQG-UHFFFAOYSA-L 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 description 1
- 229940011051 isopropyl acetate Drugs 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 150000004780 naphthols Chemical class 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000191 poly(N-vinyl pyrrolidone) Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- ZIGVUIYVPLQEAL-UHFFFAOYSA-M sodium;2-tetradecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O ZIGVUIYVPLQEAL-UHFFFAOYSA-M 0.000 description 1
- QMAOVUPQHIOELS-UHFFFAOYSA-M sodium;4-heptadec-1-enyl-1h-benzimidazole-2-sulfonate Chemical compound [Na+].CCCCCCCCCCCCCCCC=CC1=CC=CC2=C1N=C(S([O-])(=O)=O)N2 QMAOVUPQHIOELS-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001256 steam distillation Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000005019 zein Substances 0.000 description 1
- 229940093612 zein Drugs 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
- G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
- G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
- G03C7/388—Processes for the incorporation in the emulsion of substances liberating photographically active agents or colour-coupling substances; Solvents therefor
Definitions
- a substantially water-insoluble photographic ingredient is incorporated into a hydrophilic colloid coating composition, used for instance in coating a photographic material such as a light-sensitive emulsion composition or the like, by dissolving such ingredient in at least one substantially water-immiscible organic solvent for the ingredient, admixing the organic solvent solution with water in the presence of a dispersing agent and in the absence of any hydrophilic colloid, removing-from this admixture substantially all of the water-immiscible organic solvent used in dissolving the ingredient, and incorporating the aqueous dispersion obtained following such solvent removal in the desired hydrophilic colloid composition.
- the present invention is concerned with a method ofincororating water-insoluble photographic ingredients into hydrophiliccolloid compositions, more especially with a methodof making dispersions in water of such ingredients from which they can be homogeneously distributed into hydrophilic colloid compositions.
- additives In the manufacture of a photographic material numerous additives should be brought into operative association in one or more of the hydrophilic colloid layers of the said material. These additives include amongst others color couplers, maskforming compounds, dyes, e.g., filter dyes, antihalation dyes and sensitizing dyes, stabilizers, etc.
- color coupler any compound which in silver halide photography couples with an oxidized aromatic primary amino color developing agent to forma dye image.
- maskforming compound is meant a compound which oxidatively emulsions remain immobile and do not wander or diffuse through the emulsion from their original site otherwise color separation will be imperfect and result in final dye images that are degraded.
- a common method employed to render color couplers and mask-formers non-diffusible in. hydrophilic colloid media is to provide them in the course of their synthesis with one or more ballast groups, e.g., a longstraight-chain or branched-chain aliphatic group such as an alkyl or alkylene group comprising from five to carbonatoms.
- these non-diffusible color couplers and mask-formers are generally also provided with one or more salt-forming groups, e.g., carboxy groups and preferably sulpho groups, so that these compounds can be dissolved in the photographic emulsions in the form of their soluble alkali salts.
- salt-forming groups e.g., carboxy groups and preferably sulpho groups
- color couplersand mask-formers may be used which contain no salt-forming groups.
- this process also poses difficulties. Removal of the solvent from the non-light-sensitive hydrophilic colloid composition may be difficult to effect and when any of the solvent isleft in the gelatin, its presence may be harmful, e.g., the color coupler or mask-former particles then'have the tendency to grow.
- the solution of color coupler or mask-former in the organic water-immiscible solvent should first be admixed with an aqueous non-sensitive hydrophilic gelatin composition before admixture with the light-sensitive silver halide emulsion in order to avoid that the water-immiscible solvent should be removed from the emulsion itself, that the emulsion itself should be excessively agitated for obtaining a sufficiently finely divided dispersion of the color coupler or mask-former solution in the emulsion which could cause fogging, and that a large bulk should be subjected to agitation an extra amount of gelatin is added to the light-sensitive emulsion which increases the coating thickness or conversely decreases the dye density which can be obtained for a given coating thickness.
- the preformed non-light-sensitive gelatin compositions comprising color coupler or mask-former should be stored attemperatures below room-temperature and remelted at the moment of admixture with the light-sensitive emulsion. Further, preservatives such as phenol should be added to the gelatin composition in order to protect the gelatin against degeneratron.
- this new method may be employed with particular advantage to introduce substantially water-insoluble non-diffusing color couplers and mask-formers into photographic light-sensitive emulsions it can also be used to introduce into light-sensitive emulsions other substantially water-insoluble photographic emulsion auxiliary components such as competing couplers, which are used in color photography as described in United Kingdom Pat. No. 861,138, filed Sept. 17, 1957, by Agfa A.G., light-screening dyes, sensitizing dyes, stabilizers etc. which normally are also preferably introduced from preformeddispersions in hydrophilic non-sensitive colloid compositions, as described e.g., for sensitizing dyes in Belgian Pat. No. 682,413, filed June 10, 1966, by Kodak S.A., to avoidv excessive agitation. of the emulsion and thus fogging.
- competing couplers which are used in color photography as described in United Kingdom Pat. No. 861,138, filed Sept. 17, 1957, by Agfa A.G.
- the method of thepresent invention can also be employed in the preparation of uniform dispersions of substantially water-insoluble photographic compounds in unsensitiz ed photographic colloid compositions.
- it may be used in the production of water-permeable inter- .mediate layers in which it is desireduniformly to disperse a substantially water-insoluble light-absorbing filter or antihalation dye, competing couplers and other photographic active substances.
- a substantially water-insoluble photographic component such as a color coupler, a mask-former, a competing coupler, a stabilizer and a dye, e.g., a light-absorbing or sensitizing dye is dissolved in a low-boiling substantially water-immiscible solvent for said component whereupon the solution formed is admixed with .water in the presence of a wetting or dispersing agent and the solvent is removed thus forming a stable extremely fine dispersion or suspension of the said componentin water.
- the dispersion of component in water thus formed can then be added to the hydrophilic colloid coating composition of the layer into which the said component should be present,
- a light-sensitive silver halide emulsion layer or an intermediate layer e.g., a light-sensitive silver halide emulsion layer or an intermediate layer.
- substantially water-insoluble photographic component must be understood a component of which not more than 3 percent by weight dissolves in water at room temperature C).
- the method of the invention has proved to be particularly valuable for the incorporation of components that do not contain water-solubilizable groups such as carboxy and sulpho groups.
- the extremely finely divided dispersion or suspension of component in water, prepared as described above, has such a high stability that it is possible to create stocks of dispersions of photographic emulsion auxiliary components in water.
- the admixture of these water dispersions with a hydrophilic colloid silver halide emulsion can be delayed until the appropriate moment.
- dispersions of substantially water-insoluble photographic emulsion auxiliary components in water have the advantage over preformed non-light-sensitive gelatin compositions comprising such components dispersed therein, in that the said dispersions of components in water remain liquid whereas the gelatin compositions, even gelatin compositions comprising as low as 1 percent of gelatin, become solid and should be remelted at the stage of addition to the silver halide emulsion, that the dispersions of components in water can be stored at ordinary room-temperature, that the dispersions of components in water can comprise markedly higher concentrations of component than the preformed gelatin compositions and that no additional amount of gelatin is added to the emulsion so that no increase in coating thickness occurs, so that thin layers are obtained, which are less brittle, show improved flatness and result in better image sharpness. Moreover, removal of the substantially water-immiscible solvent from the dispersion in water is much easier to effect than removal from the gelatin composition.
- a minimum of water is used in order to obtain dispersions as concentrated as possible which is particularly suitable for storing purposes. This minimum varies of course with each individual component and can be determined by trial.
- the amount of substantially water-immiscible solvent used is dependent on the solubility of the particular compound therein; it can vary within very wide limits but is also preferably restricted to a minimum.
- the dispersion into water of the solution of the component in a water-immiscible solvent may be assisted by the use of high speed stirrers, homogenizers, colloid mills, ultrasonic wave generators, etc.
- the said colloid coating compositions for forming a layer of a photographic material may of course contain in addition to the colloid carrier all sorts of other ingredients.
- the amount of stored dispersion to be added to the colloid coating composition of the photographic layer is such that the substantially water-insoluble component is present in the resulting layer in the desired concentration. This amount is naturally dependent on the concentration of said component in said dispersion. In accordance with the present invention it was found possible in some instances to make stable dispersions of components in water comprising up to 30 percent of component.
- the removal of the substantially water-immiscible solvent may be achieved for instance by evaporation, if necessary, e.g., for accelerating the removal, by applying reduced pressure and/or moderate heating, by steam-distillation (particularly when rather high boiling substantially water-immiscible solvents are used) etc.
- the substantially water-immiscible solvents preferably have a solubility in water of at most 25 percent by weight at room temperature (20 C).
- Substantially water-immiscible solvents having a solubility in water comprised between 2 and 10 percent by weight at room temperature (20 C) are even the more favored.
- said solvents preferably have a boiling point of at most 130 C and a sufficiently high vapor pressure so that they can still be removed readily from the dispersion by applying a vacuum of 500 to 10 mm Hg at a temperature of 25 to C.
- Suitable substantially water-immiscible solvents for use according to the present invention are methylene chloride, ethyl formate, n-butyl formate, ethyl acetate, n-propyl acetate, isopropyl acetate, butyl acetate, methyl propionate, ethyl propionate, carbon tetrachloride, sym.tetrachloroethane, 1,1,2-trich1oroethane, 1,2- dichloropropane, chloroform, n-butyl alcohol, diethyl ketone, methyl n-propyl ketone, diisopropyl ether, cyclohexane, methylcyclohexane, benzene, toluene, nitromethane, etc.
- the substantially water-insoluble component In order to facilitate dissolving of the substantially water-insoluble component it may be interesting in some cases to use mixtures of water-immiscible solvents or to use in conjunction with the substantially water-immiscible solvent a solvent which is miscible with water in all proportions. Of course, the water-miscible solvent should be completely miscible with the water-immiscible solvent used.
- the water-miscible solvents are readily removed from the aqueous dispersion together with the water-immiscible solvents, unless they have too low a vapour-pressure to be removed with the water-immiscible solvents, in which case they are left in the dispersion of component in water from which they are incorporated into the hydrophilic colloid composition for forming a layer of a photographic material.
- the water-miscible solvents left in this hydrophilic colloid composition can be removed therefrom unless this is deemed unnecessary because they will have no disadvantageous effect on the physical or photographic properties by washing the chilled and thereby gelled colloid composition.
- water-miscible solvents that are suitable for use in conjunction with the substantially water-immiscible solvents are methanol, ethanol, isopropyl alcohol, dimethyl sulphoxide, tetrahydrofuran, N-methyl-Z-pyrrolidone, dioxan, dimethyl formamide, dimethoxyethane, formamide, ethylene glycol, acetonitrile, acetone, butyrolactone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diacetone alcohol and tetrahydrothiophene-l ,l-dioxide.
- the wetting or dispersing agent employed in making the dispersion in water according to the present invention is generally added to the water into which the solution of component in water-immiscible solvent is dispersed, it can also be used in the step of dissolving the component in the organic solvent whereby it is possible to eliminate the use of a wetting or dispersing agent at the stage of dispersing the organic solution in water, or two different wetting agents can be used, one in each step.
- wetting agents are the sodium salt of N-methyl oleyltauride, sodium stearate, heptadecenylbenzimidazole sulphonic acid sodium salt, sodium sulphonates of higher aliphatic alcohols, e.g., Z-methyl-hexanol sodium sulphonate; sodium diiso-octyl-sulphosuccinate, sodium dodecyl sulphate, and tetradecyl benzene sulphonic acid sodium salt.
- dispersing or wetting agent derivatives of said components or components of related structure comprising water-solubilizing groups, preferably sulpho groups in salt form.
- a dispersion in water of a substantially water-insoluble naphthol color coupler for cyan a sulphonated naphthol color coupler can be successfully used as dispersing agent.
- these sulphonated components have no influence on the viscosity of the hydrophilic colloid compositions into which the aqueous dispersions are to be incorporated, probably owing to micell-formation.
- the amount of dispersing agent or wetting agent used in making the dispersions in water of photographic components according to the method of the present invention may vary within very wide limits; it is generally comprised between 5 and percent by weight relative to the weight of component to be dispersed.
- hydrophilic colloid media Although in applying the method according to the present invention for incorporating substantially water-insoluble components in hydrophilic colloid media, the use of gelatin as hydrophilic colloid is favored, other water-soluble colloidal materials or mixtures of them can be used too e.g., colloidal albumin, zein, casein, a cellulose derivative such as carboxymethyl cellulose, a synthetic hydrophilic colloid such as polyvinyl alcohol, poly-N-vinyl pyrrolidone, etc.
- colloidal albumin colloidal albumin
- zein casein
- casein a cellulose derivative
- a synthetic hydrophilic colloid such as polyvinyl alcohol, poly-N-vinyl pyrrolidone, etc.
- the ethyl acetate was substantially removed as described in Examples 1 and 2 and the aqueous dispersion of color coupler in water formed was admixed by gentle stirring with a conventional red-sensitized gelatino silver halide emulsion ready for coating.
- the dispersion was then admixed by gentle stirring with a conventional green-sensitized gelatino silver halide emulsion ready for coating.
- the dispersion formed was then admixed by gentle stirring with a conventional red-sensitized gelatino silver halide emulsion ready for coating.
- EXAMPLE 6 Five g of the colorless coupling compound (competing coupler) corresponding to the following structural formula were dissolved at 60 C in ml of ethyl acetate. The solution formed was dispersed at 55 C by means ofa high speed stirrer in a mixture of 40 ml of distilled water and 7.5 ml of a 10 percent aqueous solution of the wetting agent of Example 1. The ethyl acetate was removed by evaporation under reduced pressure and the dispersion obtained diluted with distilled water to make 50 ml.
- the dispersion in water of colorless coupling compound was then admixed with an aqueous gelatin coating composition for forming an intermediate layer between the red-sensitized and green-sensitized emulsion layers of a negative photographic multilayer color material.
- This multilayer material comprises in order on a support a red-sensitized silver halide emulsion layer comprising a color coupler for cyan, an intermediate layer comprising a colorless coupling compound, a green-sensitized silver halide emulsion layer comprising a color coupler for magenta, a yellow filter layer comprising colloidal silver and a spectrally unsensitized blue-sensitive silver halide emulsion layer comprising a color coupler for yellow.
- EXAMPLE 7 Five g of the colorless coupling compound corresponding to the following structural formula were dissolved at 60 C in 15 ml of ethyl acetate. While still hot, the solution formed was dispersed by means of a high speed stirrer in a mixture of 40 ml of distilled water and 7.5 ml of a 10 percent aqueous solution of the wetting agent of Example l which was heated to 55 C. The ethyl acetate was removed by evaporation under reduced pressure and the dispersion left diluted with distilled water to make 50 ml.
- the dispersion in water of the above colorless coupling compound was then admixed with a red-sensitized silver halide emulsion comprising a color coupler for cyan.
- This emulsion was coated on a support and then overcoated with a gelatin intermediate layer, a green-sensitized silver halide emulsion layer comprising a color coupler for magenta, a yellow filter layer comprising colloidal silver and a spectrally unsensitized blue-sensitive silver halide emulsion layer comprising a color coupler for yellow, thus forming a negative photographic multilayer color material.
- Method of incorporating a substantially water-insoluble organic solvent-soluble photographic ingredient into a hydrophilic colloid coating composition for forming a water-permeable colloid layer of a light-sensitive silver halide material which comprises the steps of dissolving said ingredient in at least one substantially water-immiscible organic solvent for said ingredient, admixing the organic solvent solution with water in the presence of a dispersing agent and in the absence of a hydrophilic colloid, removing from said admixture substantially all of each such organic solvent forming thereby a dispersion of said ingredient in said water, and incorporating the dispersion thus formed in said hydrophilic colloid coating composition.
- the said ingredient is a color coupler, a mask-former or a competing coupler containing a long straight-chain or branched-chain aliphatic group having from five to 20 C-atoms which renders the said ingredient fast to diffusion in the said hydrophilic colloid coating composition.
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- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
- Colloid Chemistry (AREA)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB1476369 | 1969-03-20 |
Publications (1)
Publication Number | Publication Date |
---|---|
US3658546A true US3658546A (en) | 1972-04-25 |
Family
ID=10047061
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US21470A Expired - Lifetime US3658546A (en) | 1969-03-20 | 1970-03-20 | Method of incorporating photographic ingredients into photographic colloid compositions |
Country Status (8)
Country | Link |
---|---|
US (1) | US3658546A (da) |
JP (1) | JPS498330B1 (da) |
BE (1) | BE747589A (da) |
CA (1) | CA933406A (da) |
CH (1) | CH527439A (da) |
DE (1) | DE2013419C3 (da) |
FR (1) | FR2039738A5 (da) |
GB (1) | GB1297947A (da) |
Cited By (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3837863A (en) * | 1971-06-18 | 1974-09-24 | Konishiroku Photo Ind | Process for preparing light-sensitive silver halide photographic materials |
US3912515A (en) * | 1972-12-28 | 1975-10-14 | Konishiroku Photo Ind | Silver halide photosensitive material |
US3912517A (en) * | 1973-03-19 | 1975-10-14 | Agfa Gevaert A Naamloze Vennoo | Method of incorporating photographic ingredients into hydrophilic colloids |
US4388403A (en) * | 1980-09-30 | 1983-06-14 | Agfa-Gevaert Aktiengesellschaft | Process for the preparation of dispersions of hydrophobic substances in water |
US4957857A (en) * | 1988-12-23 | 1990-09-18 | Eastman Kodak Company | Stabilization of precipitated dispersions of hydrophobic couplers |
US4990431A (en) * | 1989-01-17 | 1991-02-05 | Eastman Kodak Company | Methods of forming stable dispersions of photographic materials |
US5015564A (en) * | 1988-12-23 | 1991-05-14 | Eastman Kodak Company | Stabilizatin of precipitated dispersions of hydrophobic couplers, surfactants and polymers |
US5087554A (en) * | 1990-06-27 | 1992-02-11 | Eastman Kodak Company | Stabilization of precipitated dispersions of hydrophobic couplers |
US5089380A (en) * | 1989-10-02 | 1992-02-18 | Eastman Kodak Company | Methods of preparation of precipitated coupler dispersions with increased photographic activity |
US5104776A (en) * | 1989-11-29 | 1992-04-14 | Eastman Kodak Company | Increased photographic activity precipitated coupler dispersions prepared by coprecipitation with liquid carboxylic acids |
US5158863A (en) * | 1989-01-17 | 1992-10-27 | Eastman Kodak Company | Methods of forming stable dispersions of photographic materials |
US5256527A (en) * | 1990-06-27 | 1993-10-26 | Eastman Kodak Company | Stabilization of precipitated dispersions of hydrophobic couplers |
US5616446A (en) * | 1994-09-29 | 1997-04-01 | Konica Corporation | Silver halide photographic light-sensitive material |
EP0774687A1 (en) | 1995-10-30 | 1997-05-21 | Konica Corporation | Solid processing composition and method for processing silver halide photographic light-sensitive material |
US6468727B2 (en) * | 2000-02-05 | 2002-10-22 | Eastman Kodak Company | Nonionic oligomeric surfactants and their use as dispersants and stabilizers |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2353262A (en) * | 1942-11-24 | 1944-07-11 | Eastman Kodak Co | Preventing crystallization of couplers |
US2835579A (en) * | 1955-08-31 | 1958-05-20 | Eastman Kodak Co | N-alkyl and acylphenol coupler solvents for color photography |
US3050394A (en) * | 1959-09-30 | 1962-08-21 | Gen Aniline & Film Corp | Method of incorporating color couplers in hydrophlic colloids |
US3255012A (en) * | 1960-08-20 | 1966-06-07 | Agfa Ag | Sensitized color photographic emulsions and processes containing color couplers |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3092495A (en) * | 1960-06-09 | 1963-06-04 | Gen Aniline & Film Corp | Lower alkyl lactate coupler solvents |
-
1969
- 1969-03-20 GB GB1476369A patent/GB1297947A/en not_active Expired
-
1970
- 1970-03-11 CA CA077138A patent/CA933406A/en not_active Expired
- 1970-03-18 JP JP45023476A patent/JPS498330B1/ja active Pending
- 1970-03-18 CH CH405070A patent/CH527439A/de not_active IP Right Cessation
- 1970-03-19 FR FR7009986A patent/FR2039738A5/fr not_active Expired
- 1970-03-19 BE BE747589D patent/BE747589A/xx unknown
- 1970-03-20 DE DE2013419A patent/DE2013419C3/de not_active Expired
- 1970-03-20 US US21470A patent/US3658546A/en not_active Expired - Lifetime
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2353262A (en) * | 1942-11-24 | 1944-07-11 | Eastman Kodak Co | Preventing crystallization of couplers |
US2835579A (en) * | 1955-08-31 | 1958-05-20 | Eastman Kodak Co | N-alkyl and acylphenol coupler solvents for color photography |
US3050394A (en) * | 1959-09-30 | 1962-08-21 | Gen Aniline & Film Corp | Method of incorporating color couplers in hydrophlic colloids |
US3255012A (en) * | 1960-08-20 | 1966-06-07 | Agfa Ag | Sensitized color photographic emulsions and processes containing color couplers |
Cited By (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3837863A (en) * | 1971-06-18 | 1974-09-24 | Konishiroku Photo Ind | Process for preparing light-sensitive silver halide photographic materials |
US3912515A (en) * | 1972-12-28 | 1975-10-14 | Konishiroku Photo Ind | Silver halide photosensitive material |
US3912517A (en) * | 1973-03-19 | 1975-10-14 | Agfa Gevaert A Naamloze Vennoo | Method of incorporating photographic ingredients into hydrophilic colloids |
US4388403A (en) * | 1980-09-30 | 1983-06-14 | Agfa-Gevaert Aktiengesellschaft | Process for the preparation of dispersions of hydrophobic substances in water |
US5015564A (en) * | 1988-12-23 | 1991-05-14 | Eastman Kodak Company | Stabilizatin of precipitated dispersions of hydrophobic couplers, surfactants and polymers |
US4957857A (en) * | 1988-12-23 | 1990-09-18 | Eastman Kodak Company | Stabilization of precipitated dispersions of hydrophobic couplers |
US4990431A (en) * | 1989-01-17 | 1991-02-05 | Eastman Kodak Company | Methods of forming stable dispersions of photographic materials |
US5158863A (en) * | 1989-01-17 | 1992-10-27 | Eastman Kodak Company | Methods of forming stable dispersions of photographic materials |
US5089380A (en) * | 1989-10-02 | 1992-02-18 | Eastman Kodak Company | Methods of preparation of precipitated coupler dispersions with increased photographic activity |
US5104776A (en) * | 1989-11-29 | 1992-04-14 | Eastman Kodak Company | Increased photographic activity precipitated coupler dispersions prepared by coprecipitation with liquid carboxylic acids |
US5087554A (en) * | 1990-06-27 | 1992-02-11 | Eastman Kodak Company | Stabilization of precipitated dispersions of hydrophobic couplers |
US5256527A (en) * | 1990-06-27 | 1993-10-26 | Eastman Kodak Company | Stabilization of precipitated dispersions of hydrophobic couplers |
US5616446A (en) * | 1994-09-29 | 1997-04-01 | Konica Corporation | Silver halide photographic light-sensitive material |
EP0774687A1 (en) | 1995-10-30 | 1997-05-21 | Konica Corporation | Solid processing composition and method for processing silver halide photographic light-sensitive material |
US6468727B2 (en) * | 2000-02-05 | 2002-10-22 | Eastman Kodak Company | Nonionic oligomeric surfactants and their use as dispersants and stabilizers |
Also Published As
Publication number | Publication date |
---|---|
BE747589A (fr) | 1970-09-21 |
FR2039738A5 (da) | 1971-01-15 |
CA933406A (en) | 1973-09-11 |
DE2013419B2 (de) | 1980-12-04 |
GB1297947A (da) | 1972-11-29 |
CH527439A (de) | 1972-08-31 |
JPS498330B1 (da) | 1974-02-26 |
DE2013419C3 (de) | 1981-08-27 |
DE2013419A1 (de) | 1970-10-01 |
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