US2740715A - Photographic processes for producing prints by transfer and products useful in connection therewith - Google Patents
Photographic processes for producing prints by transfer and products useful in connection therewith Download PDFInfo
- Publication number
- US2740715A US2740715A US314053A US31405352A US2740715A US 2740715 A US2740715 A US 2740715A US 314053 A US314053 A US 314053A US 31405352 A US31405352 A US 31405352A US 2740715 A US2740715 A US 2740715A
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- Prior art keywords
- silver halide
- transfer
- layer
- composition
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- Expired - Lifetime
Links
- 238000000034 method Methods 0.000 title claims description 44
- 230000008569 process Effects 0.000 title claims description 43
- 229910052709 silver Inorganic materials 0.000 claims description 85
- 239000004332 silver Substances 0.000 claims description 85
- 239000000203 mixture Substances 0.000 claims description 68
- -1 SILVER HALIDE Chemical class 0.000 claims description 51
- 239000000839 emulsion Substances 0.000 claims description 45
- 150000003839 salts Chemical class 0.000 claims description 45
- 239000007788 liquid Substances 0.000 claims description 42
- 150000001412 amines Chemical class 0.000 claims description 41
- 239000003513 alkali Substances 0.000 claims description 14
- 239000003153 chemical reaction reagent Substances 0.000 claims description 13
- 239000007795 chemical reaction product Substances 0.000 claims description 9
- 239000012466 permeate Substances 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 230000002411 adverse Effects 0.000 claims description 3
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical class [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 claims 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 42
- 239000000047 product Substances 0.000 description 34
- 239000003795 chemical substances by application Substances 0.000 description 27
- 239000000463 material Substances 0.000 description 17
- 230000001376 precipitating effect Effects 0.000 description 17
- 239000000243 solution Substances 0.000 description 15
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 14
- 230000000087 stabilizing effect Effects 0.000 description 14
- 239000002562 thickening agent Substances 0.000 description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- 239000007787 solid Substances 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000009835 boiling Methods 0.000 description 8
- 239000003381 stabilizer Substances 0.000 description 8
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 7
- 229910001864 baryta Inorganic materials 0.000 description 7
- 230000007480 spreading Effects 0.000 description 5
- 238000003892 spreading Methods 0.000 description 5
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 description 4
- 239000012670 alkaline solution Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- NLXFONFHPKEHOZ-UHFFFAOYSA-N diethylazanium;hydron;sulfate Chemical compound CCNCC.OS(O)(=O)=O NLXFONFHPKEHOZ-UHFFFAOYSA-N 0.000 description 4
- 239000000123 paper Substances 0.000 description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 3
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 2
- 239000004965 Silica aerogel Substances 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 2
- 150000003840 hydrochlorides Chemical class 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- CBPYOHALYYGNOE-UHFFFAOYSA-M potassium;3,5-dinitrobenzoate Chemical compound [K+].[O-]C(=O)C1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1 CBPYOHALYYGNOE-UHFFFAOYSA-M 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- CYXJEHCKVOQFOV-UHFFFAOYSA-N (4-amino-2-methylphenyl) hydrogen sulfate Chemical compound CC1=CC(N)=CC=C1OS(O)(=O)=O CYXJEHCKVOQFOV-UHFFFAOYSA-N 0.000 description 1
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- HDZHNYWSJFVZIO-UHFFFAOYSA-N 2,3-diaminophenol;hydrochloride Chemical compound Cl.NC1=CC=CC(O)=C1N HDZHNYWSJFVZIO-UHFFFAOYSA-N 0.000 description 1
- REFDOIWRJDGBHY-UHFFFAOYSA-N 2-bromobenzene-1,4-diol Chemical compound OC1=CC=C(O)C(Br)=C1 REFDOIWRJDGBHY-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- 239000001828 Gelatine Substances 0.000 description 1
- 229920000084 Gum arabic Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- WRUZLCLJULHLEY-UHFFFAOYSA-N N-(p-hydroxyphenyl)glycine Chemical compound OC(=O)CNC1=CC=C(O)C=C1 WRUZLCLJULHLEY-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 241000978776 Senegalia senegal Species 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000000205 acacia gum Substances 0.000 description 1
- 235000010489 acacia gum Nutrition 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000002535 acidifier Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- LHQLJMJLROMYRN-UHFFFAOYSA-L cadmium acetate Chemical compound [Cd+2].CC([O-])=O.CC([O-])=O LHQLJMJLROMYRN-UHFFFAOYSA-L 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 229920003090 carboxymethyl hydroxyethyl cellulose Polymers 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
- AJPXTSMULZANCB-UHFFFAOYSA-N chlorohydroquinone Chemical compound OC1=CC=C(O)C(Cl)=C1 AJPXTSMULZANCB-UHFFFAOYSA-N 0.000 description 1
- 150000001860 citric acid derivatives Chemical class 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 229940043279 diisopropylamine Drugs 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 229940046892 lead acetate Drugs 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- NQMRYBIKMRVZLB-UHFFFAOYSA-N methylamine hydrochloride Chemical compound [Cl-].[NH3+]C NQMRYBIKMRVZLB-UHFFFAOYSA-N 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- QDDJFNCPALBLEO-UHFFFAOYSA-N n-ethylethanamine;nitric acid Chemical compound O[N+]([O-])=O.CCNCC QDDJFNCPALBLEO-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000136 polysorbate Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000010424 printmaking Methods 0.000 description 1
- 150000003346 selenoethers Chemical class 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 150000003892 tartrate salts Chemical class 0.000 description 1
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical class CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 description 1
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 230000004304 visual acuity Effects 0.000 description 1
Images
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03D—APPARATUS FOR PROCESSING EXPOSED PHOTOGRAPHIC MATERIALS; ACCESSORIES THEREFOR
- G03D9/00—Diffusion development apparatus
- G03D9/02—Diffusion development apparatus using rupturable ampoules of liquid
Definitions
- This invention relates to photographic products and processes and more particularly to transfer processes which involve the development of a latent image in a silver halide emulsion and the transfer of components rom said emulsion to another layer to effect the formation of a print of said latent image in said other layer, and to products useful in the performance of said transfer processes.
- the processing composition either contains the developing agent prior to its distribution or dissolves such an agent after it is distributed, and, in either event, the processing composition renders the developing agent effective for developing the silver halide emulsion.
- it When using most developing agents, it must be relatively highly alkaline to perform this function. A highly alkaline environment is thus proucked in the print-receiving layer, and this environment, if permitted to exist, sometimes introduces several sources of instability which adversely affect the pictorial quality of the print with the passage of time.
- a principal source of this instability is the oxidation of the unexhausted residue developer which may stain the highlights of the print-receiving layer. The occurrence of this instability is reduced to negligible proportions if the alkalinity of the print-receiving layer can be effectively lowered within a relatively short time after the formation of the transfer print therein.
- lt is accordingly one object of the present invention to provide an improved process for forming prints, by transfer, wherein a developing composition of relatively high alkalinity may be used during the print formation but which gives afinished transfer print whose ultimate alkalinity is low enough to substantially eliminate .the possibility of the aforementioned print instability.
- This object is achieved by providing, preferably on or adjacent to the surfaces of the elements permeated by the processing liquid, compounds which will react with the by droxyl ions of an alkaline solution to produce a volatile reaction product which itself is alkaline.
- the processing composition remains alkaline despite the formation of the said reaction product.
- the volatile reaction product becomes free to evaporate from the positive print, thereby effectively reducing the alkalinity of the positive'print. It is more convenient to have the alkali element 10 and a present initially in the composition in a nonvolatile condition and to avoid any volatilization of the alkaline component until after the final print is obtained and both these desirable objectives are achieved by the aforementioned arrangement.
- One class of stabilizing agents comprehended by the present invention are the salts of the volatile amines and particularly of amines which are aliphatic and whose one normal solution has a pH in excess of 10.
- the salts of the more volatile amines i. e., amines having a boiling point of the order of C. or less, are of course preferred, and examples of such amines whose salts are satisfactory are diethylamine, triethylamine, diisopropylamine, allylamine and ethylamine.
- hydrochlorides, sulfates, nitrates, oxalates, citrates and tartrates of these amines may be satisfactorily employed, and preferred species of salts are diethylamine hydrochloride, diethylamine sulfate, and diethylamine nitrate.
- the invention accordingly comprises the product possessing the features, properties and the relation of components, and the process involving the several steps and the relation and order of one or more of such steps with respect to each of the others, which are exemplified in the following detailed disclosure, and the scope of the application of which will be indicated in the claims.
- Figurel is a diagrammatic, enlarged, sectional view illustrating the association of elements during one stage of the performance of one form of the novel transfer process of the invention, the thicknesses of the variousmaterlals being exaggerated and not necessarily in correct relative proportion;
- Fig. 2 is a perspective view, with parts broken away, of one form of print-receiving element upon which containers of. the processing agent are so positioned as to be capable of distributing their contents between the surface of the print-receiving element and a photosensitive element.
- the present invention comprehends improved processes and products of the type whereby a positive print may be obtained in a single step by suitably treating a silver halide emulsion containing a latent image with a uniformly applied layer of processing liquid.
- the processing composition is in a viscous condition and is spread in a liquid film 14 (Fig. 1) between the photosensitive print-receiving element 12.
- the photosensitive element as shown, comprises a support 10a and a silver halide emulsion 10b and the print-receiving element is preferably of a type suitable for receiving silver transfer prints and comprises a support 12a upon which is mounted a silver precipitating layer 16.
- the liquid composition develops the latent image in the emulsion and forms a soluble silver complex with undeveloped silver halide.
- This soluble silver complea is at least in part transported in the direction of print-receiving element 12 and the silver thereof is largely precipitated in the silver precipitating layer 16 to form a positive image in silver.
- novel stabilizing agents comprehended by the present invention are carried by one or both of elements 10 and 12, being dispersed in the portions of said elements which are permeated by the liquid of the processing composition.
- the support 12a of element 12 is permeable to the processing composition and is not separated from the silver precipitating layer 16 by an impermeable subcoat, it is preferable to have the stabilizing salts dispersed throughout the thickness of said support 12a.
- the stabilizing salts may be carried by a subcoat provided beneath silver precipitating layer 16.
- the stabilizing agent may also be dispersed throughout the emulsion layer 10b or carried in a permeable subcoat located between said emulsion layer and its support.
- the stabilizing agent When provided in the photosensitive element either in layer 10b or in an adjacent layer, consideration should be given to the possible effect of the stabilizing agent upon the sensitivity of the emulsion.
- the amine sulfates are preferred to the corresponding hydrochlorides, especially when layer 10b is one of the relatively fast silver halide negative type emulsions.
- a sufficient excess of the stabilizing salt is preferably provided to assure reaction with the entire hydroxyl content of the processing composition.
- adsorbent preferably siliceous, material, such, for example, as silica aerogel.
- siliceous material such as silica aerogel.
- the processing composition is preferably viscous and has dispersed therein, usually in solution, a sufficient amount of solid film-forming thickening agent for imparting thereto its desired viscosity.
- a sufficient amount of solid film-forming thickening agent for imparting thereto its desired viscosity.
- element 12 a compound such, for example, as the salt of a volatile amine which reacts with the hydroxyl groups in the processing composition to form the volatile amine.
- a compound such, for example, as the salt of a volatile amine which reacts with the hydroxyl groups in the processing composition to form the volatile amine.
- the latter is sufficiently alkaline to maintain the alkalinity of the processing composition at its desired high level so long as the concentration of the amine is not reduced.
- the volatlity of the amine the latter will evaporate when thesetceiving element is stripped from the photosensitive element, thereby substantially reducing the alkalinity of the print receiving element.
- this stabilizing agent can be contained in the support for the print-receiving element, or in the emulsion layer, or in a separate layer provided either as a subcoat or overcoat for emulsion layer 10b or silver precipitating layer 16.
- liquid layer 14 may be obtained by spreading the processing composition, for example, in a manner disclosed in my said copending ap plication Serial No. 7795.
- the processing composition contains, in addition to the alkali, the silver halide developer and the material for forming the soluble silver complex with the undeveloped silver halide, i. e., a silver halide fixer. These materials are preferably in aqueous solution.
- the silver halide developer and/or the silver halide fixer may be, in part or wholly, added to the processing composition as or after it is spread between elements 10 or 12, said reagents being so located in or adjacent the surface of one or both of said elements as to be dissolved by or otherwise interacted with the liquid composition when the latter contacts said surface.
- the liquid processing composition may be provided for spreading as a layer 14 between elements 10 and 12 by being discharged from an elongated rupturable container 20 which, as shown in Fig. 2, has a length at least equal to the transverse dimension of the area of photosensitive element 10 to which the liquid processing agent is to be applied
- Individual containers may be manually or mechanically fed between the print-receiving and the photosensitive elements by mechanism of the type shown in my Patents Nos. 2,435,718 and 2,543,180.
- One or more containers 20 may also be attached to one of elements 10 or 12 and, in Fig. 2, two such containers are shown secured to the print-receiving surface of element 12, being spaced apart, lengthwise of said element, a distance equal at least to the length of a single frame of the photosensitive element 10.
- the container 20 is preferably inexpensive and disposable and so constructed as to be capable of retaining the liquid processing agent or composition therein for relatively long periods of time without vapor loss or oxidation.
- a suitable container of this type is formed from a single multilayer sheet of material comprising three laminae.
- the inner lamiua which provides the inner surface of the container, is formed of a material which is chemically inert to the reagents in the processing agent and which is impervious to the liquid of the agent.
- One material suitable for this purpose is polyethylene.
- the intermediate lamina is preferably impervious to the vapor of the processing agent and is formed, for example, of a metallic foil such as lead, aluminum or silver foil.
- the outer or backing lamina is formed of a strong, deformable, relatively, inexpensive sheet material such as a kraft paper.
- the container 20 is preferably formed by taking the single sheet of three-ply material and folding the same medially at 22, and thereafter securing the end marginal portions 24 and the longitudinal portions 26 of the two folded faces to one another, providing a central space or cavity 28 for containing the processing liquid.
- the seal provided at the longitudinal portions 26 is preferably weaker than the end seals, providing a liquid-discharging lip which substantially parallels the long dimension of the container.
- Photosensitive element maybe any of the commer cially available photosensitive silver halide films, the term films being understood to include paper-backed emulsions.
- the products of the present invention are particularly useful in improving the results obtained when the transfer process is carried out with one of the highspeed photosensitive silver halide emulsions such as the emulsion of the relatively high-speed orthochromatic films, e. g., Eastman Kodak Verichrome film, having an A S A speed rating of 0200 and an A S A exposure index rating in the daylight of 50, and the extremely high-speed panchromatic emulsions, e. g., Eastman Kodak Super XX Pan having an A S A speed rating of 0400 and an A S A exposure index rating in the daylight of 100, and Ansco Triple S Pan.
- the highspeed photosensitive silver halide emulsions such as the emulsion of the relatively high-speed orthochromatic films, e. g., Eastman Kodak Verichrome film, having an A S
- Element 12 may be formed by applying to a suitable support 12a, for example of baryta paper, a coating of a suspension or sol of the silica containing the silver precipitating agent. This sol is permitted to dry and provides layer 16.
- the suspension of silica may be obtained by dispersing the silica, for example, in water, and then adding the silver precipitating agent either directly or by introducing into the sol salts whose reaction product is the precipitating agent.
- the sol may also be applied to the sheet without the silver precipitating agent, and the sheet with the layer of silica thereon may then be dipped in a solution or mixture of the silver precipitating agent to deposit the latter in said layer.
- preferred stabilizing salts are the aliphatic salts of volatile amines.
- the alkaline reaction productof the reaction between the said stabilizing salts and the hydroxyl groups in the processing composition give a slightly lower alkalinity than the alkalinity obtained from the material which introduces said hydroxyl groups into the alkaline solution.
- the aliphatic amines while sufficiently alkaline to maintain operative a developer composition, possess a slightly lower alkalinity than the alkalinity, for example, of the hydroxides of the alkali metals and the alkali earths.
- the stabilizing salt may be provided in a subcoat which is between layer 16 and support 12a and which is sufiiciently thick to carry an adequate quantity of said stabilizing salt to obtain the desired result. It is possible, of course, to locate some of the stabilizing salt'in the permeable portion of the photosensitive element and remainder in the print-receiving element, in which event-a subeoat for the stabilizing agent may be substantially thinner than if the print-receiving element carried all of the stabilizing salts.
- Example 1 A processing composition is prepared by mixing together the following ingredients:
- a print-receiving element 12 baryta-coated surface of a mixture comprising:
- Silica aerogel "grams-.. 800 60% water solution of gum arabic ..cc 135 /2 solution of sodium sulfide cc 3,200 Cadmium acetate grams 19 Lead acetate do 25 Water cc 13,400
- the processing composition is spread in a layer of approximately .O02-.003 inch in thickness between the treated baryta surface of element 12 and the photosensitive silver halide emulsion 10b of photosensitive element 10.
- Emulsion 10b is a relatively high speed orthochromatic emulsion like the emulsion of Eastman Kodak Verichrome film and has been exposed to predetermined subject matter so that it contains a latent image of this subject matter, and support for said emulsion is a white paper.
- the lamination formed by the spreading of the processing agent in a layer 14 between elements 10 and 12 is kept intact for approximately one-half to one and one-half minutes, preferably one minute, and at the end of this time, element 12 is stripped from element 10.
- Element 12 when so stripped, carries a positive print in silver of the subject matter of the latent image of. emulsion 10b. in this form of the process, the film of sodium carboxymethyl cellulose contained in the layer 14 of the processing composition adheres to the surface of element 12 and solidifies to form a film thereon.
- the hydroxyl ions of the processing composition are converted to the volatile alkaline amine during the processing, and so much of this amine as remains in the print-receiving stratum begins to evaporate shortly after the stripping of said print-receiving element from the photosensitive element so that there is soon produced a sufficient diminution in the alkalinity of the print-receiving stratum to greatly minimize the creation of stains and other sources of instability.
- the film-forming material in the processing agent which imparts the desired viscosity to the latter may be any of the high molecular weight polymers which are stable to alkalies and which are soluble in aqueous alkaline solutions.
- the film-forming material in the processing agent which imparts the desired viscosity to the latter may be any of the high molecular weight polymers which are stable to alkalies and which are soluble in aqueous alkaline solutions.
- plastics such other plastics as hydroxyethyl cellulose, carboxy methyl-hydroxyethyl cellulose, polyvinyl alcohol and the sodium salts of polymethacrylic acid and polyacrylic acid may be used. It is desirable that the plastic be contained in the agent in sufiicient quantities to impart to the composition a viscosity in excess of 1000 centipoises at a temperature of approximately 24 C. Preferably the viscosities of the processing agent are of the order of 1,000 to 200.000 centipoises at a temperature of approximately 24 C.
- Other developing agents may be used, for example one of the following: paminophenol hydrochloride; bromohydroquinone; chlorohydroquinone; diaminophenol hydrochloride; toluhydroquinone; monomethyl-p-aminophenol sulfate; a mixture consisting by weight of one-half hydroquinone and one-half p-hydrorzyphenylaminoacetic acid; and a mixture consisting by weight of one-fourth hydroquinone and three-fourths p-hydroxyphenylaminoacetic acid.
- Such other complexforming substances as sodium thiocyanate, ammonium thiocyanate and ammonia may be employed.
- Support 12a of element 12 may consist of gelatine, cellophane, polyvinyl alcohol, sodium alginate, and cellulose ethers such as methyl cellulose and their derivatives such as hydroxyethyl cellulose.
- stabilizing salts such for example as diethylamine hydrochloride or methylamine hydrochloride, may be used in essentially the same quantity as the diethylamine sulfate of this example.
- Example 2 The residual film of carboxymethyl cellulose may be stripped with the photosensitive element instead of with the print-receiving element by providing a stripping layer on the surface of the print-receiving element. This is accomplished by roll-coating on the processedpurposeceiving element of Fig. 1 a 5% aqueous solution of polyvinyl alcohol in a layer whose thickness is of the order of .001 inch. An equivalent amount of hydroxyethyl cellulose or polymethacrylic acid may be substituted for the polyvinyl alcohol of this example.
- the silver precipitating agents which aid in the reduction and precipitation of the metallic silver of the positive print may be contained in the developer composition.
- One example of a composition which can be usefully employed in this manner to thereby avoid the need for a special silver precipitating layer upon the print-receiving element is the following:
- This composition is spread, as in Example 1, between a photosensitive emulsion of the Vcrichrome type and the baryta-coated surface of a plain baryta sheet. At he end of approximately a minute, the baryta sheet is stripped from the emulsion and carries with it the solid residue of the spread composition. This solid residue provides the print-receiving stratum. The silver precipitate which produces the positive is formed largely in this stratum and gives a positive print of good quality, high resolving power and excellent stability.
- an emulsion so constituted is the following:
- Example 4 A photosensitive silver halide element comprising a paper base and a Verichrome type emulsion is dipped into a 5% aqueous solution of diethylamine sulfate for five minutes. This photosensitive element is thereafter used in conjunction with a print-receiving element which is formed in the same manner as the print-receiving element of Example 1 except that the last dipping operation involving diethylarnine sulfate is omitted. These two sheets are processed, as described in Example 1, with the processing composition of that example to give a transfer print of good quality and stability.
- a photographic process for forming, by transfer, a print of a latent image contained in the silver halide emulsion of a photosensitive element wherein a single application of liquid to said element is effective to give a finished print of improved stability which process comprises the steps of bringing an alkaline processing composition containing a relatively nonvolatile alkali into contact with the photosensitive element so as to permeate said emulsion with the liquid of said composition; providing another element in superposed relation with the photosensitive element so that the said composition is confined between the outer surfaces of said elements, said processing composition, upon permeation of said silver halide emulsion, containing reagents for developing said latent image and for forming a transfer print thereof in a print-receiving stratum of the superposed assembly formed by said elements and said layer of liquid, said reagents including a silver halide developer which is characterized by its propensity for oxidizing in an alkaline environment and for adversely affecting the transfer print when so oxidized in the print-
- the salt for reacting with the hydroxyl content of the processing composition is a salt of an aliphatic amine.
- the processing composition contains a thickening agent and is spread be tween said elements and, when so spread, tends to form a solid layer of said thickening agent, said layer of thickening agent providing the print-receiving stratum.
- the processing composition contains a thickening agent and is spread between said elements and, when so spread, tends to form a layer of the thickening agent, said layer of thickening agent adhering to the photosensitive element when the latter is stripped from the other element and a surface :portionrof said other element providing the print'reeeiving stratum.
- a photographic process for forming, by transfer, a positive print of a latent image contained in the silver halide emulsion of a photosensitive element wherein a single applicationof liquid to said element is effective to give a'finished print of improved stability comprises the steps of bringing a relatively uniform layerwise distribution of an alkaline processing composition containing a relatively nonvolatile alkali into contact with the photosensitive element so as to permeate said emulsion with the liquid of said composition; providing a print-receiving element in superposed relation with the photosensitive element so that the layerwise distribution of the processing composition is essentially confined to said superposed elements, said processing composition containing, after permeation of said silver halide emulsion, all of the reagents, including a silver halide developer, for developing the latent image in the silver halide emulsion and for forming a positive print of the Subject matter of said latent image upon said35ceiviug element, said developer being characterized by its propensity for oxidizing
- the salt for reacting with the hydroxyl content of the processing composition is a salt of a volatile, aliphatic amine, and the reaction product is the amine.
- a photographic process for forming by transfer a positive print of a latent image contained in the silver halide emulsion of a photosensitive element wherein a single application of liquid to said element is eifective to give a finished print sufficiently stable to require no subsequent stabilizing treatments for ordinary use which process comprises the steps of spreading in a layer between the photosensitive element and another element a processing liquid which includes, in solution, a silver halide developer characterized by its propensity for oxidizing in an alkaline environment to produce stain, a silver halide solvent, at film-forming thickening agent and, as its principal alkali, a relatively nonvolatile hydroxide; reacting the hydroxyl content of said composition with a salt of a volatile, organic amine to form an amine whose one normal solution has a pH in excess of 10 and whose boiling point is lower than approximately 175 C.; developing the latent image in said emulsion and forming a positive print in silver in a print-receiving stratum provided by one of
- a photographic product comprising, in combination, a photosensitive .silver halide layer, another layer, and a container carrying an alkaline processing liquid comprising a relatively nonvolatile hydroxide as its alkali, means holding said layers and said container together so that said container is capable of releasing its-contents to permeate superposed portions of said layers, said product containing reagents, including a silver halide developer, which are rendered operable upon the releaseof said content: to develop a latent image in said photosensitive layer and to form in a stratum of :said product other than said photosensitive layer a transfer print of said latent image, at least one ofsaid layers carrying, in the portions thereof adapted to he permeated by said liquid, a salt of a volatile, organic amine capable of reacting with said hydroxide to give a volatile, organic amine.
- the product of claim 12 wherein the salt is a salt of an organic amine having a pH in excess of 10 in one normal solution and having a boiling point lower than approximately C.
- processing liquid in the container comprises a thickening agent capable of providing the print-receiving stratum when the container contents are released.
- a photographic product comprising, in combination, a photosensitive silver halide layer, another layer, and a container carrying an alkaline processing liquid comprising a relatively nonvolatile alkali, means holding said layers and said container together so that said container is capable of releasing its contents to permeate superposed portions of said layers, said product containing reagents, including a silver halide developer, which are rendered operable upon the release of said contents to develop a latent image in said photosensitive layer and to form in a stratum of said product other than said photosensitive layer a transfer print of said latent image, at least one of said layers carrying, in the portions thereof adapted to be permeated by said liquid, a salt of an organic amine capable of reacting with the hydroxyl content of said liquid to form a volatile, organic amine.
- a photographic product for use in the formation of transfer prints comprising a rupturahle containing means holding a photographic processing liquid and a sheet support upon which said containing means is mounted, said sheet support providing an image-receiving area adjacent said containing means onto which said liquid is spreadable in a thin layer directly from said containing means, said liquid being highly alkaline and comprising as its principal alkal-imparting component a relatively nonvolatile alkali, said support carrying, distributed over said image-receiving area, a salt of an organic amine capable of reacting with the hydroxyl content of the liquid in said containing means to form a volatile, organic amine.
- liquid in the containing means includes at least one substance from the class consisting of the silver halide developers and the silver halide solvents.
- a photographic product capable of forming transfer prints in conjunction with a photosensitive silver halide element, said product comprising a rupturable containing means holding a liquid and a sheet support upon which said containing means is mounted, said sheet support providing an image-receiving area adjacent said containing means and onto which said liquid is spreadable in a thin layer directly from said containing means, said product carrying all of the reagents, including a stain-forming silver halide developer and an alkali, for forming a transfer print of a latent image in a silver halide emul sion, said reagents being so located in relation to said image-receiving area that the spreading of said liquid over said area disperses the silver halide developer and the other reagents throughout said area in adequate quantity to form a transfer print of a latent image in an area of a contiguous silver halide element equivalent to said image-receiving area, said support carrying, distributed over said image-receiving layer and in addition to said image-
- the salt is a salt of an amine having a pH in excess of 10 in one normal solution and having a boiling point lower than approximately 175 C.
- a print-receiving element for having transfer prints formed thereon by reducing the silver of a soluble silver complex brought into contact therewith, said element being substantially inert to light and comprising a support and a silver precipitation layer, one surface portion of said element including said layer being permeable to the ionic content of an aqueous solution of a soluble silver complex, said layer comprising a macroscopically continuous matrix of particles of a water-insoluble, inorganic, chemically inert, adsorbent, siliceous substance, said matrix having dispersed therethrough solid colloidal particles of a silver precipitation agent for aiding the reduction and the precipitation of metallic silver from silver complex ions in the presence of a developing agent, said surface portion having distributed therethrough a stabilizing agent, said stabilizing agent being a salt of an organic amine capable of reacting with the hydroxyl content of an alkaline liquid to form a volatile, organic amine.
- the salt is a salt of an amine having a pH in excess of 10 in a one normal solution and having a boiling point lower than approximately 175 C.
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- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
NL91464D NL91464C (enEXAMPLES) | 1952-10-10 | ||
US314053A US2740715A (en) | 1952-10-10 | 1952-10-10 | Photographic processes for producing prints by transfer and products useful in connection therewith |
GB27809/53A GB739027A (en) | 1952-10-10 | 1953-10-09 | Improvements in or relating to photographic product and process |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US314053A US2740715A (en) | 1952-10-10 | 1952-10-10 | Photographic processes for producing prints by transfer and products useful in connection therewith |
Publications (1)
Publication Number | Publication Date |
---|---|
US2740715A true US2740715A (en) | 1956-04-03 |
Family
ID=23218360
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US314053A Expired - Lifetime US2740715A (en) | 1952-10-10 | 1952-10-10 | Photographic processes for producing prints by transfer and products useful in connection therewith |
Country Status (3)
Country | Link |
---|---|
US (1) | US2740715A (enEXAMPLES) |
GB (1) | GB739027A (enEXAMPLES) |
NL (1) | NL91464C (enEXAMPLES) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2901350A (en) * | 1954-10-12 | 1959-08-25 | Goldhammer Jerome Stewart | Combined developers and fixers |
US2984565A (en) * | 1960-03-18 | 1961-05-16 | Polaroid Corp | Photographic process and composition |
US3362822A (en) * | 1965-08-25 | 1968-01-09 | Polaroid Corp | Film formation in silver and color diffusion transfer processes |
US3395015A (en) * | 1965-02-26 | 1968-07-30 | Geveaert Agfa N V | Silver complex diffusion transfer process using 3-hydroxy-propylene sulphite |
-
0
- NL NL91464D patent/NL91464C/xx active
-
1952
- 1952-10-10 US US314053A patent/US2740715A/en not_active Expired - Lifetime
-
1953
- 1953-10-09 GB GB27809/53A patent/GB739027A/en not_active Expired
Non-Patent Citations (1)
Title |
---|
None * |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2901350A (en) * | 1954-10-12 | 1959-08-25 | Goldhammer Jerome Stewart | Combined developers and fixers |
US2984565A (en) * | 1960-03-18 | 1961-05-16 | Polaroid Corp | Photographic process and composition |
US3395015A (en) * | 1965-02-26 | 1968-07-30 | Geveaert Agfa N V | Silver complex diffusion transfer process using 3-hydroxy-propylene sulphite |
US3362822A (en) * | 1965-08-25 | 1968-01-09 | Polaroid Corp | Film formation in silver and color diffusion transfer processes |
Also Published As
Publication number | Publication date |
---|---|
NL91464C (enEXAMPLES) | |
GB739027A (en) | 1955-10-26 |
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