US2527260A - Gelatino-silver halide emulsions having low setting temperatures and method of coating same - Google Patents
Gelatino-silver halide emulsions having low setting temperatures and method of coating same Download PDFInfo
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- US2527260A US2527260A US601926A US60192645A US2527260A US 2527260 A US2527260 A US 2527260A US 601926 A US601926 A US 601926A US 60192645 A US60192645 A US 60192645A US 2527260 A US2527260 A US 2527260A
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- emulsion
- gelatin
- silver halide
- gelatino
- coating
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- 239000000839 emulsion Substances 0.000 title claims description 64
- 229910052709 silver Inorganic materials 0.000 title claims description 21
- 239000004332 silver Substances 0.000 title claims description 21
- 239000011248 coating agent Substances 0.000 title description 18
- 238000000576 coating method Methods 0.000 title description 18
- 238000000034 method Methods 0.000 title description 13
- 108010010803 Gelatin Proteins 0.000 claims description 29
- 229920000159 gelatin Polymers 0.000 claims description 29
- 239000008273 gelatin Substances 0.000 claims description 29
- 235000019322 gelatine Nutrition 0.000 claims description 29
- 235000011852 gelatine desserts Nutrition 0.000 claims description 29
- -1 SILVER HALIDE Chemical class 0.000 claims description 25
- 239000007788 liquid Substances 0.000 claims description 14
- 239000002609 medium Substances 0.000 claims description 10
- 239000000344 soap Substances 0.000 claims description 9
- 239000012736 aqueous medium Substances 0.000 claims description 8
- 150000001450 anions Chemical class 0.000 claims description 6
- 239000000080 wetting agent Substances 0.000 description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- 238000005507 spraying Methods 0.000 description 11
- 125000000129 anionic group Chemical group 0.000 description 10
- 230000002209 hydrophobic effect Effects 0.000 description 10
- 150000003839 salts Chemical class 0.000 description 10
- 235000019441 ethanol Nutrition 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 5
- 239000007921 spray Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 150000004820 halides Chemical class 0.000 description 3
- 235000011149 sulphuric acid Nutrition 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 239000001117 sulphuric acid Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-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
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- RZUBARUFLYGOGC-MTHOTQAESA-L acid fuchsin Chemical compound [Na+].[Na+].[O-]S(=O)(=O)C1=C(N)C(C)=CC(C(=C\2C=C(C(=[NH2+])C=C/2)S([O-])(=O)=O)\C=2C=C(C(N)=CC=2)S([O-])(=O)=O)=C1 RZUBARUFLYGOGC-MTHOTQAESA-L 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000005521 carbonamide group Chemical group 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- MOTZDAYCYVMXPC-UHFFFAOYSA-N dodecyl hydrogen sulfate Chemical class CCCCCCCCCCCCOS(O)(=O)=O MOTZDAYCYVMXPC-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000005661 hydrophobic surface Effects 0.000 description 1
- 235000020778 linoleic acid Nutrition 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid group Chemical group C(CCCCCCC\C=C/CCCCCCCC)(=O)O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 150000002943 palmitic acids Chemical class 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
- CMPJBAKWGLWSNB-UHFFFAOYSA-N phenyl 2-hydroxybenzenesulfonate Chemical class OC1=CC=CC=C1S(=O)(=O)OC1=CC=CC=C1 CMPJBAKWGLWSNB-UHFFFAOYSA-N 0.000 description 1
- 229920000223 polyglycerol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical class OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 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
- G03C1/74—Applying photosensitive compositions to the base; Drying processes therefor
-
- 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
Definitions
- This invention relates to -photographic ma- -terials and particularly to the coating of sheets and other articles with photographic emulsions.
- flat sheet "material such as glass plates, film and. paper can usually be coated with photographic emulsions without difliculty by well known coating techniques in which a layer of emulsionis'applied from a roll r or the like, to
- the above difficulties are overcome by. employing as the .ernulsion tobe sprayed 'a gelatino silver halide emulsion which contains a substantial proportion of an anionic wetting agent and a substantial proportion of a water-miscible organic liquid.
- the emulsion contains from 2 to 8 Claims.
- the proportions of Wetting agent and organic liquid included in the gelatino silver halide emulsion are such "that the final emulsion has a setting temperature lower than that of a gelatino silver halide emul- 'sion. of similar character and gelatin content 7 which, does not contain the wetting. agent or organic liquid.
- the proportion of organic liquid which must be added is usually greater than that which would cause precipitation of the gelatin of the emulsion in the absence of an anionic wetting agent.
- Ethyl alcohol is particularly suitable as the organic liquid but other watermiscible organic liquids may be employed, e. g.
- acetone and dioxane A mixture of organic liquids maybe employed. Although, in generaLit is desirable that the emulsion should set rapidly on the sprayed surface, where this is unnecessary or undesirable an organic liquid having a rate of evaporation similar to that of water may be used.
- the quantity of organic liquid employed will I depend in each case on the characteristics of the emulsion used and on the nature and proportion of wetting agent present. Preferably it should be sufiicient to reduce the viscosity of the emulsion to a minimum without causing precipitation of the gelatin of the emulsion.
- anionic wetting agents which may be employed there may be mentioned:
- Soluble salts of long-chain-alkyl carboxylic acids e. g. soluble salts of fatty acids containing eight or more carbon atoms as, for example, oleic, ricinoleic, linoleic, stearic and palmitic acids.
- Soluble salts of sulphated higher fatty alcohols e. g. soluble salts of fatty alcohol sulphates of which the alkyl group contains at least eight carbon atoms, as for example, the soluble salts of lauryl hydrogen sulphate and oleyl hydrogen sulphate.
- Soluble salts of alkylated aromatic sulphonic acids e. .g. soluble salts of alkyl benzene sulphonic acids, of alkyl naphthalene sulphonic acids and of alkylated hydroxy diphenylsulphonic acids.
- the soluble salts may be formed from alkali metals, .e. g. sodium and potassium, from ammonia or from amines, e. g. triethanolamine and cyclohexylamine.
- the free acids may also be employed, where these are sufiiciently soluble.
- wetting agent in the surface to be coated.
- the wetting agent may be incorporated in the substance of the article to be ';coated or applied to its surface in aqueous or non-aqueous solution by flowing, dipping, brush- Ling, beading or spraying.
- the wetting agent for this purpose maybe anionic, cationic or nonionic.
- a subcoat useful where the surface to be coated is hydrophobic, e. g. is a surface of cellulose nitrate or :methyl methacrylate polymer, may consist of .a hydrophobic dispersion of gelatin in an organic solvent medium.
- wetting agents suitable for addition "to such a sub-coat solution is limited to those free from basic radicles such as sodium, ammonium or cetyl trimetliylam- Y monium, which tend to fiocculate the gelatin.
- Suitable wetting agents are, therefore, non-ionic agents such a; polyglycerol higher fatty acid esters or long-chain-alkyl sulphuric acids such :as l-methyl 'tridecyl sulphuric acid.
- non-ionic agents such as a; polyglycerol higher fatty acid esters or long-chain-alkyl sulphuric acids such :as l-methyl 'tridecyl sulphuric acid.
- This difliculty may be overcome by including in the emulsion to be sprayed a dy or pigment which absorbs strongly in the light which the safe-light filter transmits, so that the emulsion appears grey or black when viewed by the safe-light. It is of advantage to employ for this purpose a dye or pigment which is destroyed or dissolved away, or the colour of which is discharged during the usual hotographic processing operations.
- Example 7 The emulsion is heated to F. to melt it, the wetting agent 'is mixed in and the alcohol thenadded. The resulting emulsion is cooled to I "about 65 F. for use.
- Example 2 'Cc. Gelatino silver halide emulsion containing 8% gelatin 1,000 50% solution of 'triethanolamine dodecyl sulphate Acetone 500
- Example 3 To 1000 cc. of an emulsion prepared as in EX- ample 1 there is added 20 cc. of .a 5%solution of Ink Blue, where the emulsion is to be sprayed in a yellow safelig'ht, or 20 cc. of a 5% solution of Acid Magenta, ,where the emulsion is to be sprayed in a green safelight. These dyes are readily removed during the normal development of the sprayed emulsions.
- the following example illustrates a suitable sub-coat solution for use where the surface to be coated is hydrophobic.
- a photographic emulsion comprising silver halide dispersed in a gelatin-anion soap complex made by admixing a gelatin silver halide emul-,
- a method of coating a, support with a photographic emulsion which comprises spraying the support at room temperature with a photographic emulsion comprising sliver halide dispersed in a gelatin-anion soap complex made by admixing a gelatin silver halide emulsion with an aqueous medium containing 2 to 10% on the weight of the gelatin of an anion soap, 30-70% of the weight 4.
- a method of coating a hydrophobic support with a photographic emulsion which comprises applying to the support a hydrophobic dispersion of gelatin in an organic solvent medium containing a non-ionic Wetting agent, allowing such coating to set and thereafter spraying at room temperature with a photographic emulsion comprising silver halide dispersed in gelatin in an aqueous medium containing a substantial proportion of an anionic wetting agent and a substantial proportion of a water-miscible organic liquid, the proportions being such that the emulsion has a setting temperature lower than that of an emulsion of similar strength in an aqueous medium containing no wetting agent or organic solvent.
- a method of coating a hydrophobic support with a photographic emulsion which comprises applying to the support a hydrophobic dispersion of gelatin in an organic solvent medium containing a non-ionic wetting agent, allowing such coating to set and thereafter spraying at room temperature with a photographic emulsion comprising silver halide dispersed in gelatin in an aqueous medium containing a substantial proportion of an anionicwetting agent, 30-70% of the weight of the medium being water-miscible organic liquid the proportions being such that the emulsion has a setting temperature lower than coating to set and thereafter spraying at room temperature with a photographic emulsion comprising silver halide dispersed in gelatin in an aqueous medium containing 2 to 25% on the weight of the gelatin of an anionic wetting agent, 30-70% of the weight of the medium being watermiscibleorganic liquid.
- a method of coating a hydrophobic support with a photographic emulsion which comprises applying to the support a hydrophobic dispersion of gelatin in an organic solvent medium containing a non-ionic wetting agent, allowing such coating to set and thereafter spraying at room temperature with a photographic emulsion comprising silver halide dispersed in gelatin in an aqueous medium containing 2 to 10% on the weight of the gelatin of an anionic wetting agent, 30-70% of the weight of the medium being ethyl alcohol.
- a method of coating a support with a photographic emulsion whichcomprises spraying the support at room temperature with a photographic emulsion made by dispersing silver halides in a gelatin-anion soap complex obtained by adding to an aqueous gelatin silver halide emulsion 2 to 10% by weight, based on the gelatin, of an anion soap and adding to the emulsion 30 to by weight of such emulsion of ethyl alcohol.
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- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Description
i atenteci Oct. 24, 1950 UNITED STATES PAT T OFFICE l GELATINO-SILVER HALIDE EMULSAIONS HAVING LOW SETTING TEMPERA- TUBES AND METHOD OF COATING SAME I John Alfred Henry Hart and-Edward William Lee, Ilford, ,England, assignors to Ilford Limited,
Ilford, England, a British company NoDravving. Application June 27, 1945, Serial a No. 601,926. In Great Britain July 19, 1944 This invention relates to -photographic ma- -terials and particularly to the coating of sheets and other articles with photographic emulsions. Although flat sheet "material such as glass plates, film and. paper can usually be coated with photographic emulsions without difliculty by well known coating techniques in which a layer of emulsionis'applied from a roll r or the like, to
the surface of the plate,'film or pa er; there are certain cases in which this technique is not very convenient and it is useless if the surface of the material to be coated is irregular.
An alternative method of coating is to spray :the photographicemulsion on to thearticle to be coated, withthe aidofa compressed-air-operated spray gun. This method is. particularly {suitable where the surface to be coated is irre ular, but may also be used to coat flat surfaces. However, the method is not without certain difliculties. V
Thus an ordinary gelatino silver halide emulsion tends to set in'the spray gun unless the gun I is specially heated. A diificulty which arises when freliefs or vertical surfaces are to be coated, is
that a normal gela'tinosilver halide emulsion does .not set quickly enough onthe sprayed surface so that the emulsion flows after coating and thus Y gives rise to an irregular coating thickness.
Another difficulty is that when the surface to be coated is hydrophobic the sprayed emulsion wets the surface only slowly, again resulting in an uneven coating. As the spraying proceeds the spray wets the already coated droplets more readily than it wets the hydrophobic surface, so
that there is a tendency for the spraying to result ;in larger and larger droplets-forming on the sprayed surface. These eventually fuse together, "but at this stage the coating is usually undesirably thick. If the emulsion sets beforethe fusion of the drops the non-uniformityof thecoating persists. g
, According to the present invention, the above difficulties are overcome by. employing as the .ernulsion tobe sprayed 'a gelatino silver halide emulsion which contains a substantial proportion of an anionic wetting agent and a substantial proportion of a water-miscible organic liquid.
Preferably the emulsion contains from 2 to 8 Claims.
thereby to increase the viscosity of the emulsion.
The further addition of a water-miscible organicliquid, however, causes a reduction in the viscosity of the emulsion and also a reduction in the temperature at which the emulsion sets.
In accordance with this invention the proportions of Wetting agent and organic liquid included in the gelatino silver halide emulsion are such "that the final emulsion has a setting temperature lower than that of a gelatino silver halide emul- 'sion. of similar character and gelatin content 7 which, does not contain the wetting. agent or organic liquid. The proportion of organic liquid which must be added is usually greater than that which would cause precipitation of the gelatin of the emulsion in the absence of an anionic wetting agent.
Thus emulsions which have been found very ferred) the emulsion sets very much more quickly than does an ordinary gelatinosilver halide emulsion. This is probably due to a combination of causes. Thus evaporation of the volatile solvent in the airblast from the spray gun causes rapid chilling of the emulsion, a rapid increase in the concentration ofthe gelatin and an increase in the relative proportion of water in the remaining 7 .-solvent mixture causing an increase; in the vis- 25% of an anionic wettingagent (based on the ;Weight of the gelatin); {The effectof adding an anionic wetting agent to-a gelatino,- silver halide emulsion is to cause the formation ofa gelatin/wetting agent complex (compare co-pending United States application Serial No. 600,844, filed June 21, 1945, nowrU, S. ratent 2, 3%) and cosity of the emulsion.
Ethyl alcohol, referred to above, is particularly suitable as the organic liquid but other watermiscible organic liquids may be employed, e. g.
methyl alcohol, isopropyl alcohol, methyl acetate,
acetone and dioxane. A mixture of organic liquids maybe employed. Although, in generaLit is desirable that the emulsion should set rapidly on the sprayed surface, where this is unnecessary or undesirable an organic liquid having a rate of evaporation similar to that of water may be used.
, ;Thus an emulsion containing dioxane sets less rapidly after spraying than does one which contains ethyl alcohol. 7
The quantity of organic liquid employed will I depend in each case on the characteristics of the emulsion used and on the nature and proportion of wetting agent present. Preferably it should be sufiicient to reduce the viscosity of the emulsion to a minimum without causing precipitation of the gelatin of the emulsion.
As examples of anionic wetting agents which may be employed there may be mentioned:
(a) Soluble salts of long-chain-alkyl carboxylic acids, e. g. soluble salts of fatty acids containing eight or more carbon atoms as, for example, oleic, ricinoleic, linoleic, stearic and palmitic acids.
(b) Soluble salts of long-.chain-alkyl sulphonic acids.
Soluble salts of sulphated higher fatty alcohols, e. g. soluble salts of fatty alcohol sulphates of which the alkyl group contains at least eight carbon atoms, as for example, the soluble salts of lauryl hydrogen sulphate and oleyl hydrogen sulphate.
:(d) Soluble salts of sulphated secondary alcohols containing at least eight carbon atoms in the chain.
(e) Soluble salts of alkylated aromatic sulphonic acids, e. .g. soluble salts of alkyl benzene sulphonic acids, of alkyl naphthalene sulphonic acids and of alkylated hydroxy diphenylsulphonic acids.
(7) isolubleisalts of lon'g-chain-alkyl esters of sulphated succinic acid.
The soluble salts may be formed from alkali metals, .e. g. sodium and potassium, from ammonia or from amines, e. g. triethanolamine and cyclohexylamine. The free acids may also be employed, where these are sufiiciently soluble.
' The compounds may contain amino residues in the anion of the soap :as, for example, in the sodium salt of oleyl amino ethane sulphonic acid which contains a carbonamide group =Very many anionic wetting agents are commercially marketed as detergents and these com- .mercial products may conveniently be employed in the process of this invention.
.If it is desired to ensure that the droplets of emulsion reaching the article to be sprayed should flow out to a uniform film immediately they arrive on the surface of the article, it is preferred to incorporate a wetting agent in the surface to be coated. The wetting agent may be incorporated in the substance of the article to be ';coated or applied to its surface in aqueous or non-aqueous solution by flowing, dipping, brush- Ling, beading or spraying. The wetting agent for this purpose maybe anionic, cationic or nonionic. :Sometimes it is desirabl 'to apply a preliminary coat (a' sub-coat) to the article to be sprayed in order to improve adhesion between-the article and the sprayed emulsion andthe wetting agent may be included in such sub-coat. A subcoat useful where the surface to be coated is hydrophobic, e. g. is a surface of cellulose nitrate or :methyl methacrylate polymer, may consist of .a hydrophobic dispersion of gelatin in an organic solvent medium. The choice of wetting agents suitable for addition "to such a sub-coat solution is limited to those free from basic radicles such as sodium, ammonium or cetyl trimetliylam- Y monium, which tend to fiocculate the gelatin.
Suitable wetting agents are, therefore, non-ionic agents such a; polyglycerol higher fatty acid esters or long-chain-alkyl sulphuric acids such :as l-methyl 'tridecyl sulphuric acid. When a .gelatino silver halide emulsion is sprayed :on to a white or light-coloured surface it is often difficult, using the usual photographic safe-lights, to see whether the emulsion is being sprayed uniformly, due to the low contrast between the sprayed emulsion and the surface which is being sprayed. This difliculty may be overcome by including in the emulsion to be sprayed a dy or pigment which absorbs strongly in the light which the safe-light filter transmits, so that the emulsion appears grey or black when viewed by the safe-light. It is of advantage to employ for this purpose a dye or pigment which is destroyed or dissolved away, or the colour of which is discharged during the usual hotographic processing operations.
The following examples of emulsions suitable for spraying serve to illustrate the invention:
ExampZeI Cc. Gelatino .silver halide emulsion containing gelatin 1,000 20% solution of sodium salt of l-methyl tridecyl. sulphuric acid 50 :Ethyl alcohol 1,000
7 The emulsion is heated to F. to melt it, the wetting agent 'is mixed in and the alcohol thenadded. The resulting emulsion is cooled to I "about 65 F. for use. Example 2 'Cc. Gelatino silver halide emulsion containing 8% gelatin 1,000 50% solution of 'triethanolamine dodecyl sulphate Acetone 500 Example 3 To 1000 cc. of an emulsion prepared as in EX- ample 1 there is added 20 cc. of .a 5%solution of Ink Blue, where the emulsion is to be sprayed in a yellow safelig'ht, or 20 cc. of a 5% solution of Acid Magenta, ,where the emulsion is to be sprayed in a green safelight. These dyes are readily removed during the normal development of the sprayed emulsions.
The following example illustrates a suitable sub-coat solution for use where the surface to be coated is hydrophobic.
Example 4 Gelatin -gr rm 10 .Salicyclic acid do 2.5 Rolyglycerol ester do 2.5 Water cubic centimeterm- 30 "Methyl alcohol do 1,000 Acetone do .l,000
25% :on the weight of the gelatin of an anion lsoa-p, 30 .70% :ofethe weight of the medium 'being water-miscible organic liquid.
2. A photographic emulsion comprising silver halide dispersed in a gelatin-anion soap complex made by admixing a gelatin silver halide emul-,
sion with an aqueous medium containing 2 to on the weight of the gelatin of an anion soap, -70% of the weight of the medium being ethyl alcohol.
3. A method of coating a, support with a photographic emulsion which comprises spraying the support at room temperature with a photographic emulsion comprising sliver halide dispersed in a gelatin-anion soap complex made by admixing a gelatin silver halide emulsion with an aqueous medium containing 2 to 10% on the weight of the gelatin of an anion soap, 30-70% of the weight 4. A method of coating a hydrophobic support with a photographic emulsion which comprises applying to the support a hydrophobic dispersion of gelatin in an organic solvent medium containing a non-ionic Wetting agent, allowing such coating to set and thereafter spraying at room temperature with a photographic emulsion comprising silver halide dispersed in gelatin in an aqueous medium containing a substantial proportion of an anionic wetting agent and a substantial proportion of a water-miscible organic liquid, the proportions being such that the emulsion has a setting temperature lower than that of an emulsion of similar strength in an aqueous medium containing no wetting agent or organic solvent.
5. A method of coating a hydrophobic support with a photographic emulsion which comprises applying to the support a hydrophobic dispersion of gelatin in an organic solvent medium containing a non-ionic wetting agent, allowing such coating to set and thereafter spraying at room temperature with a photographic emulsion comprising silver halide dispersed in gelatin in an aqueous medium containing a substantial proportion of an anionicwetting agent, 30-70% of the weight of the medium being water-miscible organic liquid the proportions being such that the emulsion has a setting temperature lower than coating to set and thereafter spraying at room temperature with a photographic emulsion comprising silver halide dispersed in gelatin in an aqueous medium containing 2 to 25% on the weight of the gelatin of an anionic wetting agent, 30-70% of the weight of the medium being watermiscibleorganic liquid.
7. A method of coating a hydrophobic support with a photographic emulsion which comprises applying to the support a hydrophobic dispersion of gelatin in an organic solvent medium containing a non-ionic wetting agent, allowing such coating to set and thereafter spraying at room temperature with a photographic emulsion comprising silver halide dispersed in gelatin in an aqueous medium containing 2 to 10% on the weight of the gelatin of an anionic wetting agent, 30-70% of the weight of the medium being ethyl alcohol.
8. A method of coating a support with a photographic emulsion whichcomprises spraying the support at room temperature with a photographic emulsion made by dispersing silver halides in a gelatin-anion soap complex obtained by adding to an aqueous gelatin silver halide emulsion 2 to 10% by weight, based on the gelatin, of an anion soap and adding to the emulsion 30 to by weight of such emulsion of ethyl alcohol.
JOHN ALFRED HENRY HART. EDWARD WILLIAM LEE.
REFERENCES CITED The following references are of record in the file of this patent:
UNITED STATES PATENTS OTHER REFERENCES Wall, Photographic Emulsions, published 1929 by American Phot. Publ. Co., Boston, pp. -454.
Claims (1)
1. A PHOTOGRAPHIC EMULSION COMPRISING SILVER HALIDE DISPERSED IN A GELATIN-ANION SOAP COMPLEX MADE BY ADMIXING A GELATIN SILVER HALIDE EMULSION WITH AN AQUEOUS MEDIUM CONTAINING 2 TO 25% ON THE WEIGHT OF THE GELATIN OF AN ANION SOAP, 30-70% OF THE WEIGHT OF THE MEDIUM BEING WATER-MISCIBLE ORGANIC LIQUID.
Applications Claiming Priority (1)
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GB2527260X | 1944-07-19 |
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Publication Number | Publication Date |
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US2527260A true US2527260A (en) | 1950-10-24 |
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ID=10909202
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Application Number | Title | Priority Date | Filing Date |
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US601926A Expired - Lifetime US2527260A (en) | 1944-07-19 | 1945-06-27 | Gelatino-silver halide emulsions having low setting temperatures and method of coating same |
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Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2952559A (en) * | 1956-11-01 | 1960-09-13 | Eastman Kodak Co | Method of coating a liquid photographic emulsion on the surface of a support |
US2992108A (en) * | 1957-10-21 | 1961-07-11 | Eastman Kodak Co | Gelatin coating compositions |
US3075841A (en) * | 1956-06-19 | 1963-01-29 | Du Pont | Mordant treating process and elements containing same |
US3317344A (en) * | 1963-09-27 | 1967-05-02 | Gen Aniline & Film Corp | Antistatic photographic film |
US3421927A (en) * | 1964-09-15 | 1969-01-14 | American Cyanamid Co | Sheet polyethylene carrying a fused hydrophilic tiecoat of a polyethylene-emulsifying agent mixture and a hydrophobic organic topcoat |
US3793032A (en) * | 1970-06-04 | 1974-02-19 | Agfa Gevaert Nv | Coating aids for film-forming coating compositions |
US4370412A (en) * | 1978-09-14 | 1983-01-25 | Eastman Kodak Company | Aqueous hydrophilic colloid coating composition containing a combination of anionic surfactants |
FR2629739A1 (en) * | 1988-04-08 | 1989-10-13 | Garitat Joel | Method of applying a photographic emulsion to a smooth support-medium surface |
US5994049A (en) * | 1997-08-28 | 1999-11-30 | Eastman Kodak Company | Water-soluble non-interactive polymers and surfactant micelles for desalting and concentrating silver halide photographic emulsions |
US6004740A (en) * | 1997-08-28 | 1999-12-21 | Eastman Kodak Company | Water-soluble non-interactive carboxyl polymers for desalting and concentrating silver halide photographic emulsions |
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US1772081A (en) * | 1927-08-27 | 1930-08-05 | Frederick W Hochstetter | Process and apparatus for treating derivatives of aqueous cellulose compounds for use in photographic and its allied arts and other useful purposes |
US1997745A (en) * | 1929-08-24 | 1935-04-16 | Renker Max | Process for the manufacture of photographic films and of carriers for the same |
US2118059A (en) * | 1935-09-20 | 1938-05-24 | Eastman Kodak Co | Antistatic photographic film |
US2142311A (en) * | 1934-03-15 | 1939-01-03 | Heidenhain Johannes | Process for the preparation of washed out reliefs |
GB537256A (en) * | 1939-09-13 | 1941-06-16 | Eastman Kodak Co | Process employing non-diffusing compounds for use in colour photography and other photographic processes |
GB556360A (en) * | 1942-01-28 | 1943-10-01 | Thomas Thorne Baker | Improvements in or relating to photographic processes |
US2349760A (en) * | 1942-06-01 | 1944-05-23 | Eastman Kodak Co | Ultraviolet-sensitive photographic element |
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Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1772081A (en) * | 1927-08-27 | 1930-08-05 | Frederick W Hochstetter | Process and apparatus for treating derivatives of aqueous cellulose compounds for use in photographic and its allied arts and other useful purposes |
US1997745A (en) * | 1929-08-24 | 1935-04-16 | Renker Max | Process for the manufacture of photographic films and of carriers for the same |
US2142311A (en) * | 1934-03-15 | 1939-01-03 | Heidenhain Johannes | Process for the preparation of washed out reliefs |
US2118059A (en) * | 1935-09-20 | 1938-05-24 | Eastman Kodak Co | Antistatic photographic film |
GB537256A (en) * | 1939-09-13 | 1941-06-16 | Eastman Kodak Co | Process employing non-diffusing compounds for use in colour photography and other photographic processes |
US2282001A (en) * | 1939-09-13 | 1942-05-05 | Eastman Kodak Co | Color-forming gelatin compound |
GB556360A (en) * | 1942-01-28 | 1943-10-01 | Thomas Thorne Baker | Improvements in or relating to photographic processes |
US2349760A (en) * | 1942-06-01 | 1944-05-23 | Eastman Kodak Co | Ultraviolet-sensitive photographic element |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3075841A (en) * | 1956-06-19 | 1963-01-29 | Du Pont | Mordant treating process and elements containing same |
US2952559A (en) * | 1956-11-01 | 1960-09-13 | Eastman Kodak Co | Method of coating a liquid photographic emulsion on the surface of a support |
US2992108A (en) * | 1957-10-21 | 1961-07-11 | Eastman Kodak Co | Gelatin coating compositions |
US3317344A (en) * | 1963-09-27 | 1967-05-02 | Gen Aniline & Film Corp | Antistatic photographic film |
US3421927A (en) * | 1964-09-15 | 1969-01-14 | American Cyanamid Co | Sheet polyethylene carrying a fused hydrophilic tiecoat of a polyethylene-emulsifying agent mixture and a hydrophobic organic topcoat |
US3793032A (en) * | 1970-06-04 | 1974-02-19 | Agfa Gevaert Nv | Coating aids for film-forming coating compositions |
US4370412A (en) * | 1978-09-14 | 1983-01-25 | Eastman Kodak Company | Aqueous hydrophilic colloid coating composition containing a combination of anionic surfactants |
FR2629739A1 (en) * | 1988-04-08 | 1989-10-13 | Garitat Joel | Method of applying a photographic emulsion to a smooth support-medium surface |
US5994049A (en) * | 1997-08-28 | 1999-11-30 | Eastman Kodak Company | Water-soluble non-interactive polymers and surfactant micelles for desalting and concentrating silver halide photographic emulsions |
US6004740A (en) * | 1997-08-28 | 1999-12-21 | Eastman Kodak Company | Water-soluble non-interactive carboxyl polymers for desalting and concentrating silver halide photographic emulsions |
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