US2368287A - Photographic element and method of making it - Google Patents
Photographic element and method of making it Download PDFInfo
- Publication number
- US2368287A US2368287A US452334A US45233442A US2368287A US 2368287 A US2368287 A US 2368287A US 452334 A US452334 A US 452334A US 45233442 A US45233442 A US 45233442A US 2368287 A US2368287 A US 2368287A
- Authority
- US
- United States
- Prior art keywords
- active
- colloid
- layer
- anion
- wetting
- 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
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- 238000004519 manufacturing process Methods 0.000 title description 13
- 239000010410 layer Substances 0.000 description 78
- 239000000084 colloidal system Substances 0.000 description 51
- 239000000080 wetting agent Substances 0.000 description 44
- 108010010803 Gelatin Proteins 0.000 description 34
- 239000008273 gelatin Substances 0.000 description 34
- 229920000159 gelatin Polymers 0.000 description 34
- 235000019322 gelatine Nutrition 0.000 description 34
- 235000011852 gelatine desserts Nutrition 0.000 description 34
- 239000000839 emulsion Substances 0.000 description 22
- 239000000243 solution Substances 0.000 description 21
- 239000003795 chemical substances by application Substances 0.000 description 18
- 239000000463 material Substances 0.000 description 18
- 238000009736 wetting Methods 0.000 description 18
- 238000000576 coating method Methods 0.000 description 17
- 239000000203 mixture Substances 0.000 description 16
- 239000011248 coating agent Substances 0.000 description 15
- 239000006185 dispersion Substances 0.000 description 15
- 239000007864 aqueous solution Substances 0.000 description 12
- 239000013543 active substance Substances 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 8
- 239000008199 coating composition Substances 0.000 description 8
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 8
- -1 silver halide Chemical class 0.000 description 7
- LFYSWCFSJAZQJJ-UHFFFAOYSA-L 1-dodecylpyridin-1-ium;sulfate Chemical compound [O-]S([O-])(=O)=O.CCCCCCCCCCCC[N+]1=CC=CC=C1.CCCCCCCCCCCC[N+]1=CC=CC=C1 LFYSWCFSJAZQJJ-UHFFFAOYSA-L 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- QBKSIHCSDPPLJI-UHFFFAOYSA-N 2-[bis(2-hydroxyethyl)amino]tetradecan-1-ol;sulfuric acid Chemical compound OS(O)(=O)=O.CCCCCCCCCCCCC(CO)N(CCO)CCO QBKSIHCSDPPLJI-UHFFFAOYSA-N 0.000 description 4
- 150000001450 anions Chemical class 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 125000000129 anionic group Chemical group 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 230000015271 coagulation Effects 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 235000015110 jellies Nutrition 0.000 description 2
- 239000008274 jelly Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- IZWPGJFSBABFGL-GMFCBQQYSA-M sodium;2-[methyl-[(z)-octadec-9-enoyl]amino]ethanesulfonate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC(=O)N(C)CCS([O-])(=O)=O IZWPGJFSBABFGL-GMFCBQQYSA-M 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- HOWPBSZGWVQFNS-UHFFFAOYSA-N 3,4-dibutyl-2-phenylphenol Chemical compound CCCCC1=CC=C(O)C(C=2C=CC=CC=2)=C1CCCC HOWPBSZGWVQFNS-UHFFFAOYSA-N 0.000 description 1
- 229920001817 Agar Polymers 0.000 description 1
- 102000009027 Albumins Human genes 0.000 description 1
- 108010088751 Albumins Proteins 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 241000206672 Gelidium Species 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 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 1
- MZVQCMJNVPIDEA-UHFFFAOYSA-N [CH2]CN(CC)CC Chemical group [CH2]CN(CC)CC MZVQCMJNVPIDEA-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 235000010419 agar Nutrition 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- RGCKGOZRHPZPFP-UHFFFAOYSA-N alizarin Chemical compound C1=CC=C2C(=O)C3=C(O)C(O)=CC=C3C(=O)C2=C1 RGCKGOZRHPZPFP-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000003868 ammonium compounds Chemical class 0.000 description 1
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 1
- 229910001864 baryta Inorganic materials 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical class OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 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
- 239000004359 castor oil Substances 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- DVBJBNKEBPCGSY-UHFFFAOYSA-M cetylpyridinium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+]1=CC=CC=C1 DVBJBNKEBPCGSY-UHFFFAOYSA-M 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 125000003438 dodecyl 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])C([H])([H])C([H])([H])* 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000012259 ether extract Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000000913 palmityl 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])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
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 239000001397 quillaja saponaria molina bark Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 150000003839 salts Chemical group 0.000 description 1
- 229930182490 saponin Natural products 0.000 description 1
- 150000007949 saponins Chemical class 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- XOAAWQZATWQOTB-UHFFFAOYSA-N taurine Chemical class NCCS(O)(=O)=O XOAAWQZATWQOTB-UHFFFAOYSA-N 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
- G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
- G03C1/38—Dispersants; Agents facilitating spreading
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31725—Of polyamide
- Y10T428/31728—Next to second layer of polyamide
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31725—Of polyamide
- Y10T428/31768—Natural source-type polyamide [e.g., casein, gelatin, etc.]
- Y10T428/31772—Next to cellulosic
- Y10T428/31775—Paper
Definitions
- This invention relates to surface-active materials which serve as wetting, dispersing and emulsifying agents and particularly to the use of such materials in the production and treatment of materials containing colloid layers such as photographic" films, plates, papers, baryta coated papers and similar materials.
- anion-active or anionic and kationactive or "kationic agents are referred to as anion-active or anionic and kationactive or "kationic agents respectively.
- the complex wetting agents may be isolated by mixing together the anionic and kationic agents, preferably in substantially chemically equivalent proportions. and isolating the complex formed which contains both an act ve anion and an active kation by mechanical means if it is relatively insoluble in the reaction soluti n. e. g. by centrifuging or b extraction with an organic solvent, e. g. ethyl ether.
- the wetting operation is effected in the presence of a combination of anion-active and kation-active wettin agents.
- com binat om of anion-active and kation-active wetting agents is intended to include both mixtures of the a ents and the isolated complex wetting agents referred to above.
- wetting agents may be present in the layer whose surface it is desired to wet (and this is preferred) or in the wetting fluid, or one of the said wetting agents may be present in said surface and the other in said fluid.
- the combinations of wetting agents characteristic of this invention are of particular value in the production and treatment of photographic materials.
- a support e. g. of cellulose nitrate, cellulose acetate, glass or paper is provided on one or both surfaces with one or more superposed layers of photographic emulsion, usually gelatinosilver halide emulsion, and such layenor layers may be present with other layers of colloid material acting as substrata, intermediate layers, fllterlayers, antihalation or backing layers or supercoating layers.
- a support of cellulose derivative film ma be provided with a substratum layer having a basis of gelatin, or of a mixtureof gelatin and a cellulose derivative,
- a gelatino silver halide emulsion layer may be coated on the substratum layer.
- a plurality of emulsion layers may be coated on the support and such emulsion layers may be coated in direct contact with one another or may be separated by plain or coloured gelatin layers as desired.
- the outermost emulsion layer in a photographic element may be supercoated with a. further colloid layer in order I to prevent damage to the emulsion surface.
- the coating layers employed may be water-insoluble, it' is far more frequent that the coating layers are of watersoluble or water-dispersible colloids, such as gelatin. It will be appreciated, therefore, that it is a matter of considerable importance in the manufacture of photographic elements where the support or any colloid layer already present is to be provided with a superposed layer of another colloid by coating it with an aqueous dispersion of such colloid that the support or colloid layer already present should be readily wetted by aqueous solutions. Only in this way can it be ensured that the superposed coatin may be readily formed as a uniform continuous layer. Furthermore, it is a matter of considerable importance in' the proces ing t ea ment of photographic films, plates and papers, e. g., with developing and fixing baths, that the elements should be readily wetted by aqueous solutions.
- the invention further provides photographic elements in which the outermost layer contains a combination of anion active and kation-active wetting agents and which are therefore very readily wetted by aqueous processing solutions.
- the degree of wetting obtained by the combination of wetting agents of this invention is greater than that obtainable by either of the two agents separately in comparable concentration.
- concentration of the anionactive and kation-active agents required to give a marked increase in wettability may be as low as 1 part of each compound in 100,000 parts of aqueous colloid dispersion compared with one part in 5,000 parts of aqueous colloid dispersion for the separate wetting agents.
- Anion-active wetting agents which may be employed are, for example, aliphatic alcohol sulphates, aliphatic sulphonates, aromatic sulphonates, sulphonated taurine derivatives, soaps and sulphonated castor oils.
- aliphatic alcohol sulphates aliphatic sulphonates
- aromatic sulphonates aromatic sulphonates
- sulphonated taurine derivatives soaps and sulphonated castor oils.
- dodecyl triethanolamine sulphate dodecyl sodium sulphate
- Turkey red oils and the materials sold under the trade names Igepon T (believed to be the sodium salt of oleyl amino ethane sulphonic acid), Aresklene 375 (believed to be the sodium salt of dibutyl phenyl phenol disulphonic acid), Lissapol C (believed to be a sulphated fatty alcohol) and Santomerse D (believed to be an alkylated aryl sulphonate).
- Kation-active wetting agents which may be employed are, for example, alkyl-, aryland aralkyl-substituted ammonium compounds and quaternary salts of heterocyclic nitrogen compounds. Specific examples are dodecyl pyridinium sulphate, hexadecyl pyridinium bromide and the materials sold under the trade names Fixanol (believed to be a quaternary ammonium compound) and Sapamine MS (believed to be a diethyl aminoethyl long-chain alkyl amide ester).
- Fixanol (believed to be a quaternary ammonium compound)
- Sapamine MS believed to be a diethyl aminoethyl long-chain alkyl amide ester.
- One or more anion-active agents may be used in' combination with one or more kation-active agents, if desired.
- wetting power of the com- "binations of anion-active and kation-active agents of this invention increases progressively as the amounts of such agents are brought more closely to the point of chemical equivalence and that in the neighbourhood of this point the wetting power is increased to a surprisingly high degree, a phenomenon which is believed to be due to the formation of the complex type of wetting agent referred to above.
- agents are being used to effect the wetting of colloid layers they may be adsorbed by or may react with the colloid layer or layers, or materials contained in such layers. It is to be understood that in such a case the term chemical equivalence" refers to the free agents unadsorbed and uncombined with such other materials.
- the anion-active and kation-active wetting agents may both be incorporated in the support or colloid layer already present (as the case may be), both in the colloid dispersion which is being applied, or one in the support or colloid layer already present (as the case may be) and one in the colloid dispersion.
- both the anion-active and kationactive wetting agents should be present in the support or layer to which the colloid dispersion is to be applied.
- the colloid layer to which the dispersion of colloid is applied may be a dried layer or may be in the form of a set jelly from which surplus solvent has not been removed.
- a mixture of anion-active and kation-active wetting agents may be present in an underlayer of colloid, e. g. a sensitive gelatino photographic emulsion to which it is desired to apply a colloid layer or a further gelatino photographic emulsion in liquid form
- this mixture of wetting agents may also with advantage be present in the outermost colloid layer or layers of the final photographic element in which case a considerable advance in ease of wetting by photographic processing solutions is obtained.
- any excess of one over the other should 'be in favour of the anion-active agent since an excess of Ration-active agent in some cases tends to affeet the properties of the light-sensitive emulsions deleteriously.
- the mixture of agents is added to a light-sensitive colloid emull 'may be usefully employed in connection with other water-dispersible colloid layers, e. g. agaragar, casein, albumin, alginates and synthetic water-dispersible colloids.
- the combinations of wetting agents are unaffected by ethyl alcohol and other agents commonly present in photographic layers, such as the alums used as hardens agents.
- wetting power of the combinations of wetting agents was assessed by the maximum speed at which it proved'possible to apply successfully a coating of colloid in the presence of the combination of wetting agents, in a continuous coating operation.
- Example I A layer' of gelatin is applied to a support by coating the support with a solution of the following composition at 95 F.:
- Example III It was established by direct titration of the Example III To a photographic gelatino silver bromide emulsion was added 25 cc. of a 0.5% aqueous so.- lution of dodecyl pyridinium sulphate per litre of the emulsion. The treated emulsion was divided into a .number of portions and to each portion one of a range of quantities of 0.5% aqueous solution of sodium dodecyl sulphate was added. The several emulsions so prepared were coated upon glass, the layers obtained were set to jelly at room temperature and coatings of anaqueous 2.2% solution of gelatin were applied to them. 'It was found that in all cases the ge1a-,
- Example V 63.2 cos. of a 5% aqueous solution of dodecyl pyridinium sulphate were thoroughly mixed with 86.6 cos. of a 5% aqueous solution of a proprietary wetting agent known to contain sodium dodecyl sulphate a the active ingredient, these relative quantities being found by prior test to give maximum coagulation.
- the reaction mixture consisted of a semi-gelatinous cloudy mixture and thiswas centrifuged for about 6 hours.
- the product thus separated consisted of a curdlike substance which contained about 30% of solid matter which was recovered as a wax-like substance
- the product was freely soluble in ethyl alcohol and in benzene though it is to be noted that sodium dodecyl sulphate is insoluble in ethyl alcohol and that neither sodium dodecyl sulphate nor dodecyl pyridinium sulphate is appreciably soluble in benzene.
- CnHuN- Photographic film base carrying a layer 01' gelatin was coated with a light-sensitive emulsion to which had been added a 5% solution in ethyl alcohol of the complex wetting agent prepared as above, 1 cc. of the solution being added (a commercial wetting agent of the anion-active class; the word Santomerse being a registered trade-mark) or with the sodium salt of oleyl amino ethane sulphonic acid (sold under the name Igepon T, the word Igepon being a registered trade-mark).
- Example VI 100 cos. of a 20% aqueous solution oi! a proprietary wetting agent containing hexadecyi Dyridinium bromide was mixed with 74 cc. of a 20% aqueous solution of a proprietary wetting agent of the alkylated benzene sulphonate class, these quantities being found by test to give maximum coagulation.
- the coagulated product was separated from the reaction solution by extractin with 500 cc. of diethyl ether and evaporating the ether extract. The product which was a waxy solid was found to be freely soluble in ethyl alcohol.
- wetting agents characteristic of this invention have been described with particular reference to the manufacture of photographic materials they may be used in other connections where a' wetting action is desired. For example, they ma be included in photographic developers or in textile treating baths.
- a process for the production of photographic materials containing colloid layers wherein a coating composition consisting essentially of an aqueous dispersion of a water-dispersible colloid is applied to a support, which comprises facilitating the coating of said composition on said sup- .port by means of a combination of anion-active coating or such composition 0n said gelatin surface by means of a combination of anion-active and kation-active wetting agents present, during the coating operation, at the common surface of said gelatin layer and said coating composition, the proportions of free anion-active and kationactive agents present being substantially chemicallyequivalent.
- a process for the production of photographic materials containing gelatin layers wherein a coating composition consisting essentially of an aqueous dispersion of gelatin is applied to the gelatin surface of a support already carrying a gelatin layer, which comprises facilitating the coating of such composition on said gelatin surface by means of a combination of anion-active and kation-active wetting agents present in said gelatin layer, the proportions of free anion-active and kation-active agents present being substantially chemically equivalent.
- a process for the production of photographic materials containing gelatin layers wherein a coating composition consisting essentially of an aqueous dispersion of gelatin is applied to a gelatino light-sensitive emulsion layer which comprises facilitating the coating of such composition on said emulsion layer by means of a combination of anion-active and kation-active wetting agents present in said emulsion layer, the proportions of free anion-active and kationactive agents present being substantially chemically equivalent.
- a photographic element containing a support and at least one layer of a water-dispersible colloid, said layer having in intimate contact therewith a combination of anion-active and kation-active wetting agents in substantially chemically equivalent proportions.
- a photographic element containing a support and at least two superposed layersof waterdispersible colloid, said superposed layers containing, when considered together, a combination proportions of free anion-active and kation-ac- V tive agents present being substantially chemically equivalent.
- a process for the production of photographic materials containing colloid layers wherein a coating composition consisting essentially of an aqueous dispersion of a water-dispersible colloid is applied to the surface of a support which already carries a coating of a set water-dispersible colloid, which comprises facilitating the coating of such composition on said surface by means of a combination of anion-active and kation-active wetting agents present, during the coating operation, at the common surface of said set waterdispersible colloid and said coating composition, the proportions of free anion-active and kationactive agents present being substantially chemically equivalent.
- a process for the production of photographic materials containing gelatin layers wherein a coating composition consisting essentially of an aqueous dispersion of gelatin is applied to the gelatin surface of a support already carrying a gelatin layer, which comprises facilitating the of anion-active and kation-active wetting agents in substantially chemically equivalent proportions.
- a photographic element containing a sup port and at least two superposed layers of water-- dispersible colloid, the layer adjacent the support containing a combination of anion-active and kation-active wetting agents in substantially chemically equivalent proportions.
- a photographic element containing a support and at least two superposed layers of waterdispersibie colloid wherein the colloid consists essentially of gelatin, said superposed layers containing, when considered together, a combination of anion-active andkation-active wetting agents in substantially chemically equivalent proportions.
- a photographic element containing a support and at least two superposed layers of waterdispersible colloid wherein the colloid consists essentially of gelatin, the layer adjacent to the support containin a combination of anion-active and kation-active wetting agents in substantially chemically equivalent proportions.
- a photographic element containing a support and an outer layer of a water-dispersible colloid, said outer layer containing a combination of anion-active and'kation-active wetting agents in substantially chemically equivalent proportions.
- a photographic element comprising a suptherewith a combination of an anion-active wetport and at least one layer of a water-disnersisble 5 ting agent and hexadecyl pyridlnium bromide in colloid, said layer having in intimate contact substantially chemically equivalent proportions. therewith a small amount of a combination of s dodecyl triethanolamlne sulphate and a kation- LEONARD VINCENT CHILTON. active wetting agent in substantially chemically equivalent proportions. 10
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- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Physics & Mathematics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Optical Filters (AREA)
- Colloid Chemistry (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
Description
Patented Jan. 30, 1945 PHOTOGRAPHIC ELEMENT AND METHOIi OF MAKING IT Leonard' Vincent Chilton, Ilford, England, assignor to Iliord Limited, Iliord, England, a company of Great Britain No Drawing. Application July .25, 1942, Serial No. 452,334. In Great Britain August 28, 1941 14 Claims.
This invention relates to surface-active materials which serve as wetting, dispersing and emulsifying agents and particularly to the use of such materials in the production and treatment of materials containing colloid layers such as photographic" films, plates, papers, baryta coated papers and similar materials.
In recent years there have been produced large numbers of organic surface-activ compounds. Such compounds normally ionise in aqueous solution and according to Whether the wetting function is due to the anion or the kation are referred to as anion-active or anionic and kationactive or "kationic agents respectively.
It has now been discovered, and this forms the basis of the presentinvention, that when anionactive and kation-active substances are employed in combination the resulting wetting power is very much greater than is obtained by the use of either of such substances separately in comparable concentration. Anion-active and kation-active substances when mixed in aqueous solution react together to produce a relatively insoluble complex of which both the anion and the kation are. surface-active and it is believed that the remarkable increase in wetting obtained by'th use of a combination of such wetting agents is due to the formation of this complex, since if the complex so formed is isolated and used as a-wetting agent it exerts a wetting power comparable to that exerted by the mixture of anion-active and kation-active agents from which it was isolated.
'The complex wetting agents may be isolated by mixing together the anionic and kationic agents, preferably in substantially chemically equivalent proportions. and isolating the complex formed which contains both an act ve anion and an active kation by mechanical means if it is relatively insoluble in the reaction soluti n. e. g. by centrifuging or b extraction with an organic solvent, e. g. ethyl ether.
According to the present invent on. therefore. in a process wherein a surface is desired to be wetted, the wetting operation is effected in the presence of a combination of anion-active and kation-active wettin agents.
The expression com binat om of anion-active and kation-active wetting agents is intended to include both mixtures of the a ents and the isolated complex wetting agents referred to above.
The combination of wetting agents may be present in the layer whose surface it is desired to wet (and this is preferred) or in the wetting fluid, or one of the said wetting agents may be present in said surface and the other in said fluid.
As already indicated, the combinations of wetting agents characteristic of this invention are of particular value in the production and treatment of photographic materials.
In the production of photographic films, plates and papers, a support, e. g. of cellulose nitrate, cellulose acetate, glass or paper is provided on one or both surfaces with one or more superposed layers of photographic emulsion, usually gelatinosilver halide emulsion, and such layenor layers may be present with other layers of colloid material acting as substrata, intermediate layers, fllterlayers, antihalation or backing layers or supercoating layers. For example, a support of cellulose derivative film ma be provided with a substratum layer having a basis of gelatin, or of a mixtureof gelatin and a cellulose derivative,
and a gelatino silver halide emulsion layer may be coated on the substratum layer. In the case of photographic elements to be used for multicolour photography a plurality of emulsion layers may be coated on the support and such emulsion layers may be coated in direct contact with one another or may be separated by plain or coloured gelatin layers as desired. Further, the outermost emulsion layer in a photographic element may be supercoated with a. further colloid layer in order I to prevent damage to the emulsion surface.
Although for some purposes the coating layers employed may be water-insoluble, it' is far more frequent that the coating layers are of watersoluble or water-dispersible colloids, such as gelatin. It will be appreciated, therefore, that it is a matter of considerable importance in the manufacture of photographic elements where the support or any colloid layer already present is to be provided with a superposed layer of another colloid by coating it with an aqueous dispersion of such colloid that the support or colloid layer already present should be readily wetted by aqueous solutions. Only in this way can it be ensured that the superposed coatin may be readily formed as a uniform continuous layer. Furthermore, it is a matter of considerable importance in' the proces ing t ea ment of photographic films, plates and papers, e. g., with developing and fixing baths, that the elements should be readily wetted by aqueous solutions.
In order to facilitate such wetting, it is well known to include saponin or an anion-active wetting agent such as a sulphonated oil or soap, or both, as ingredients of the colloid layers.
According, therefore, to a further feature of this invention, in the production of .materials containing colloid layers and particularly photographic films, plates, papers, colour filters and similar products, wherein coating compositions consisting essentially of dispersions of colloids are applied to film, plate, paper or other supports or to set or dried colloid layers already present on such supports, there is present either in the colloid dispersion or in the support or colloid layer to which it is to be applied,or in both, taken together or separately, a combination of anion-active and kation-active wetting agents.
The invention further provides photographic elements in which the outermost layer contains a combination of anion active and kation-active wetting agents and which are therefore very readily wetted by aqueous processing solutions.
The degree of wetting obtained by the combination of wetting agents of this invention is greater than that obtainable by either of the two agents separately in comparable concentration. Where the agents are used in the coating of colloid layers the concentration of the anionactive and kation-active agents required to give a marked increase in wettability may be as low as 1 part of each compound in 100,000 parts of aqueous colloid dispersion compared with one part in 5,000 parts of aqueous colloid dispersion for the separate wetting agents.
If the ratio of anion-active to kation-active agent is substantially maintained the ease of wetting increases progressively as the concentrations of the two components are raised.
Anion-active wetting agents which may be employed are, for example, aliphatic alcohol sulphates, aliphatic sulphonates, aromatic sulphonates, sulphonated taurine derivatives, soaps and sulphonated castor oils. As specific examples there may be mentioned dodecyl triethanolamine sulphate, dodecyl sodium sulphate,
Turkey red oils and the materials sold under the trade names Igepon T (believed to be the sodium salt of oleyl amino ethane sulphonic acid), Aresklene 375 (believed to be the sodium salt of dibutyl phenyl phenol disulphonic acid), Lissapol C (believed to be a sulphated fatty alcohol) and Santomerse D (believed to be an alkylated aryl sulphonate).
Kation-active wetting agents which may be employed are, for example, alkyl-, aryland aralkyl-substituted ammonium compounds and quaternary salts of heterocyclic nitrogen compounds. Specific examples are dodecyl pyridinium sulphate, hexadecyl pyridinium bromide and the materials sold under the trade names Fixanol (believed to be a quaternary ammonium compound) and Sapamine MS (believed to be a diethyl aminoethyl long-chain alkyl amide ester). One or more anion-active agents may be used in' combination with one or more kation-active agents, if desired.
It is found that the wetting power of the com- "binations of anion-active and kation-active agents of this invention increases progressively as the amounts of such agents are brought more closely to the point of chemical equivalence and that in the neighbourhood of this point the wetting power is increased to a surprisingly high degree, a phenomenon which is believed to be due to the formation of the complex type of wetting agent referred to above. Apart from chemical combination between the agents, it is possible that either or both may be adsorbed by or may react with the materials which are being wetted.
For example, where the agents are being used to effect the wetting of colloid layers they may be adsorbed by or may react with the colloid layer or layers, or materials contained in such layers. It is to be understood that in such a case the term chemical equivalence" refers to the free agents unadsorbed and uncombined with such other materials.
In the coating of a support or colloid layer carried thereby with a dispersion of a colloid, the anion-active and kation-active wetting agents may both be incorporated in the support or colloid layer already present (as the case may be), both in the colloid dispersion which is being applied, or one in the support or colloid layer already present (as the case may be) and one in the colloid dispersion. However, it is generally preferable that both the anion-active and kationactive wetting agents should be present in the support or layer to which the colloid dispersion is to be applied. The colloid layer to which the dispersion of colloid is applied may be a dried layer or may be in the form of a set jelly from which surplus solvent has not been removed.
Whereas, as indicated above, a mixture of anion-active and kation-active wetting agents may be present in an underlayer of colloid, e. g. a sensitive gelatino photographic emulsion to which it is desired to apply a colloid layer or a further gelatino photographic emulsion in liquid form, this mixture of wetting agents may also with advantage be present in the outermost colloid layer or layers of the final photographic element in which case a considerable advance in ease of wetting by photographic processing solutions is obtained.
Where a mixture of anion-active and kationactiveagents is employed in the production of photographic materials carrying light sensitive emulsions, it is generally desirable that if the agents are not present in equivalent proportions, any excess of one over the other should 'be in favour of the anion-active agent since an excess of Ration-active agent in some cases tends to affeet the properties of the light-sensitive emulsions deleteriously. Moreover, if the mixture of agents is added to a light-sensitive colloid emull 'may be usefully employed in connection with other water-dispersible colloid layers, e. g. agaragar, casein, albumin, alginates and synthetic water-dispersible colloids. The combinations of wetting agents are unaffected by ethyl alcohol and other agents commonly present in photographic layers, such as the alums used as hardens agents.
The following examples illustrate the invention but are not to be regarded as limiting it in any way:
In these examples the wetting power of the combinations of wetting agents was assessed by the maximum speed at which it proved'possible to apply successfully a coating of colloid in the presence of the combination of wetting agents, in a continuous coating operation.
Example I A layer' of gelatin is applied to a support by coating the support with a solution of the following composition at 95 F.:
Fixanol grams 0.2 Dodecyl triethanolamine sulphate do 0.2 Gelatin do 80.0 Water to litre 1 The resulting layer is ,then set at 60 F. A
supercoating solution of the following composition is then applied:
Gelatin grams 40 Water to "litre 1 To a 6% solution of gelatin were added 10 cc. of a 0.5% aqueous solution of dodecyl pyridinium sulphate per litre of the gelatin solution. The
solution was divided into a number of portions and to each portion one of a range of quantities of 0.5% aqueous solution of sodium dodecyl sulphate was added. The several solutions so prepared were coated upon strips of photographic film base, set at room temperature and supercoated with a 4% solution of gelatin containing no wetting agent. The supercoating solution spread smoothly on all the gelatin subcoats, but with the greatest facility upon that in which the addition of sodium dodecyl sulphate was at the rate of 5 cc. of 0.5% aqueous solution per litre.
It was established by direct titration of the Example III To a photographic gelatino silver bromide emulsion was added 25 cc. of a 0.5% aqueous so.- lution of dodecyl pyridinium sulphate per litre of the emulsion. The treated emulsion was divided into a .number of portions and to each portion one of a range of quantities of 0.5% aqueous solution of sodium dodecyl sulphate was added. The several emulsions so prepared were coated upon glass, the layers obtained were set to jelly at room temperature and coatings of anaqueous 2.2% solution of gelatin were applied to them. 'It was found that in all cases the ge1a-,
tin solution readily wetted the underlying emulsion coatings, a maximum wetting effect being obtained when the quantity of sodium dodecyl sulphate solution employed was 5 cc. per litre of emulsion.
By the titration method mentioned in Example II 25 cc. of the dodecyl pyridinium sulphate solution were found to be chemically equivalent to 12.5 cos. of the sodium dodecyl sulphate solution. The difference (between 5 cc. and 12.5 cc.) is probably dueto adsorption of wetting agent to constituents of the emulsion.
Ea'ample IV 'A layer of gelatin was appliedto a support by coating the support with a solution of the following composition at F.:
Dodecyl triethanolamine sulphate -gms 0.2 Gelatin do 80.0 Water' to litre 1 The resulting layer was then set at 70 F. A supercoating solution of the following composition was then applied:
Fixanol grams 0.2 Gelatin do 40.0 Water to litre 1 In this example the. anionic and kationic wetting agents were present separately and it was found that the supercoating solution spread smoothly and evenly on the underlying gelatin layer. v
A similar result was obtained by employing Fixanol in the under layer of gelatin and dodecyl triethanolamine sulphate in the supercoating layer, in the same amounts.
Example V 63.2 cos. of a 5% aqueous solution of dodecyl pyridinium sulphate were thoroughly mixed with 86.6 cos. of a 5% aqueous solution of a proprietary wetting agent known to contain sodium dodecyl sulphate a the active ingredient, these relative quantities being found by prior test to give maximum coagulation. The reaction mixture consisted of a semi-gelatinous cloudy mixture and thiswas centrifuged for about 6 hours. The product thus separated consisted of a curdlike substance which contained about 30% of solid matter which was recovered as a wax-like substance The product was freely soluble in ethyl alcohol and in benzene though it is to be noted that sodium dodecyl sulphate is insoluble in ethyl alcohol and that neither sodium dodecyl sulphate nor dodecyl pyridinium sulphate is appreciably soluble in benzene.
It is believed that the reaction proceeds according to the equation:
CnHuN- Photographic film base carrying a layer 01' gelatin was coated with a light-sensitive emulsion to which had been added a 5% solution in ethyl alcohol of the complex wetting agent prepared as above, 1 cc. of the solution being added (a commercial wetting agent of the anion-active class; the word Santomerse being a registered trade-mark) or with the sodium salt of oleyl amino ethane sulphonic acid (sold under the name Igepon T, the word Igepon being a registered trade-mark).
Example VI 100 cos. of a 20% aqueous solution oi! a proprietary wetting agent containing hexadecyi Dyridinium bromide was mixed with 74 cc. of a 20% aqueous solution of a proprietary wetting agent of the alkylated benzene sulphonate class, these quantities being found by test to give maximum coagulation. The coagulated product was separated from the reaction solution by extractin with 500 cc. of diethyl ether and evaporating the ether extract. The product which was a waxy solid was found to be freely soluble in ethyl alcohol. I
The complex prepared as above was used as in Example V and gave similar satisfactory results.
Although the uses of the combination of wetting agents characteristic of this invention have been described with particular reference to the manufacture of photographic materials they may be used in other connections where a' wetting action is desired. For example, they ma be included in photographic developers or in textile treating baths.
WhatI claim is:
1. A process for the production of photographic materials containing colloid layers wherein a coating composition consisting essentially of an aqueous dispersion of a water-dispersible colloid is applied to a support, which comprises facilitating the coating of said composition on said sup- .port by means of a combination of anion-active coating or such composition 0n said gelatin surface by means of a combination of anion-active and kation-active wetting agents present, during the coating operation, at the common surface of said gelatin layer and said coating composition, the proportions of free anion-active and kationactive agents present being substantially chemicallyequivalent.
4. A process for the production of photographic materials containing gelatin layers wherein a coating composition consisting essentially of an aqueous dispersion of gelatin is applied to the gelatin surface of a support already carrying a gelatin layer, which comprises facilitating the coating of such composition on said gelatin surface by means of a combination of anion-active and kation-active wetting agents present in said gelatin layer, the proportions of free anion-active and kation-active agents present being substantially chemically equivalent.
5. A process for the production of photographic materials containing gelatin layers wherein a coating composition consisting essentially of an aqueous dispersion of gelatin is applied to a gelatino light-sensitive emulsion layer which comprises facilitating the coating of such composition on said emulsion layer by means of a combination of anion-active and kation-active wetting agents present in said emulsion layer, the proportions of free anion-active and kationactive agents present being substantially chemically equivalent.
6. A photographic element containing a support and at least one layer of a water-dispersible colloid, said layer having in intimate contact therewith a combination of anion-active and kation-active wetting agents in substantially chemically equivalent proportions.
'7. A photographic element containing a support and at least two superposed layersof waterdispersible colloid, said superposed layers containing, when considered together, a combination proportions of free anion-active and kation-ac- V tive agents present being substantially chemically equivalent.
2. A process for the production of photographic materials containing colloid layers wherein a coating composition consisting essentially of an aqueous dispersion of a water-dispersible colloid is applied to the surface of a support which already carries a coating of a set water-dispersible colloid, which comprises facilitating the coating of such composition on said surface by means of a combination of anion-active and kation-active wetting agents present, during the coating operation, at the common surface of said set waterdispersible colloid and said coating composition, the proportions of free anion-active and kationactive agents present being substantially chemically equivalent.
3. A process for the production of photographic materials containing gelatin layers wherein a coating composition consisting essentially of an aqueous dispersion of gelatin is applied to the gelatin surface of a support already carrying a gelatin layer, which comprises facilitating the of anion-active and kation-active wetting agents in substantially chemically equivalent proportions.
8. A photographic element containing a sup port and at least two superposed layers of water-- dispersible colloid, the layer adjacent the support containing a combination of anion-active and kation-active wetting agents in substantially chemically equivalent proportions.
9. A photographic element containing a support and at least two superposed layers of waterdispersibie colloid wherein the colloid consists essentially of gelatin, said superposed layers containing, when considered together, a combination of anion-active andkation-active wetting agents in substantially chemically equivalent proportions.
10. A photographic element containing a support and at least two superposed layers of waterdispersible colloid wherein the colloid consists essentially of gelatin, the layer adjacent to the support containin a combination of anion-active and kation-active wetting agents in substantially chemically equivalent proportions.
11. A photographic element containing a support and an outer layer of a water-dispersible colloid, said outer layer containing a combination of anion-active and'kation-active wetting agents in substantially chemically equivalent proportions.
12. A photographic element containing a support, andan outer layer consisting essentially of assess? 5 tion of anion-active and kation-active wetting 143A photographic element comprising a supagents in substantially chemically equivalent proport and at least one layer of a water-dispersible portions. colloid, said layer having in intimate contact 13. A photographic element comprising a suptherewith a combination of an anion-active wetport and at least one layer of a water-disnersisble 5 ting agent and hexadecyl pyridlnium bromide in colloid, said layer having in intimate contact substantially chemically equivalent proportions. therewith a small amount of a combination of s dodecyl triethanolamlne sulphate and a kation- LEONARD VINCENT CHILTON. active wetting agent in substantially chemically equivalent proportions. 10
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB10969/41A GB551633A (en) | 1941-08-28 | 1941-08-28 | Improvements in and relating to the production of materials containing colloid layers |
Publications (1)
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US2368287A true US2368287A (en) | 1945-01-30 |
Family
ID=9977648
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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US452334A Expired - Lifetime US2368287A (en) | 1941-08-28 | 1942-07-25 | Photographic element and method of making it |
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GB (1) | GB551633A (en) |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2490760A (en) * | 1946-04-15 | 1949-12-06 | Eastman Kodak Co | Water spot prevention in photographic film |
US2556540A (en) * | 1946-04-15 | 1951-06-12 | Eastman Kodak Co | Water spot prevention in photographic film |
US2739891A (en) * | 1953-07-17 | 1956-03-27 | Eastman Kodak Co | Method of preparing photographic products |
US2756146A (en) * | 1954-07-28 | 1956-07-24 | Levy Marilyn | Sensitizer for photothermographic substances |
US2835582A (en) * | 1954-02-03 | 1958-05-20 | Eastman Kodak Co | Gelatin-polymeric hydrosol mixtures and photographic articles prepared therefrom |
US2835609A (en) * | 1954-06-24 | 1958-05-20 | Eastman Kodak Co | Method for coating cellulose ester films |
US2970907A (en) * | 1956-04-20 | 1961-02-07 | Gen Aniline & Film Corp | Physical properties of photographic papers |
US3018178A (en) * | 1956-10-29 | 1962-01-23 | Benjamin R Harriman | Coating photographic material |
US3317344A (en) * | 1963-09-27 | 1967-05-02 | Gen Aniline & Film Corp | Antistatic photographic film |
US3793032A (en) * | 1970-06-04 | 1974-02-19 | Agfa Gevaert Nv | Coating aids for film-forming coating compositions |
WO2006111712A2 (en) * | 2005-04-20 | 2006-10-26 | The Queen's University Of Belfast | Ionic liquids and uses thereof |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2140572B (en) * | 1983-05-26 | 1986-06-18 | Kodak Ltd | Photographic dispersions |
-
1941
- 1941-08-28 GB GB10969/41A patent/GB551633A/en not_active Expired
-
1942
- 1942-07-25 US US452334A patent/US2368287A/en not_active Expired - Lifetime
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2490760A (en) * | 1946-04-15 | 1949-12-06 | Eastman Kodak Co | Water spot prevention in photographic film |
US2556540A (en) * | 1946-04-15 | 1951-06-12 | Eastman Kodak Co | Water spot prevention in photographic film |
US2739891A (en) * | 1953-07-17 | 1956-03-27 | Eastman Kodak Co | Method of preparing photographic products |
US2835582A (en) * | 1954-02-03 | 1958-05-20 | Eastman Kodak Co | Gelatin-polymeric hydrosol mixtures and photographic articles prepared therefrom |
US2835609A (en) * | 1954-06-24 | 1958-05-20 | Eastman Kodak Co | Method for coating cellulose ester films |
US2756146A (en) * | 1954-07-28 | 1956-07-24 | Levy Marilyn | Sensitizer for photothermographic substances |
US2970907A (en) * | 1956-04-20 | 1961-02-07 | Gen Aniline & Film Corp | Physical properties of photographic papers |
US3018178A (en) * | 1956-10-29 | 1962-01-23 | Benjamin R Harriman | Coating photographic material |
US3317344A (en) * | 1963-09-27 | 1967-05-02 | Gen Aniline & Film Corp | Antistatic photographic film |
US3793032A (en) * | 1970-06-04 | 1974-02-19 | Agfa Gevaert Nv | Coating aids for film-forming coating compositions |
WO2006111712A2 (en) * | 2005-04-20 | 2006-10-26 | The Queen's University Of Belfast | Ionic liquids and uses thereof |
WO2006111712A3 (en) * | 2005-04-20 | 2007-01-04 | Bp Plc | Ionic liquids and uses thereof |
Also Published As
Publication number | Publication date |
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GB551633A (en) | 1943-03-03 |
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