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
  • G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
  • G03C8/02—Photosensitive materials characterised by the image-forming section
  • G03C8/04—Photosensitive materials characterised by the image-forming section the substances transferred by diffusion consisting of inorganic or organo-metallic compounds derived from photosensitive noble metals
  • G03C8/06—Silver salt diffusion transfer

Definitions

• the present invention relates to the application of 3-hydroxy-propylene sulphite for preventing the yellow ing of photographic images produced according to the silver complex diffusion transfer process and to an imagereceiving material containing said 3-hydroxy-propylene sulphite.
• the lightsensitive silver halide emulsion material is image-wise exposed and then brought into contact with the imagereceiving material during the development and diffusion transfer.
• the image-receiving material still contains a part of the chemical substances applied in the development and diffusion transfer such as developing agent, alkali, sodium sulphite and sodium thiosulphate.
• the developing agents commonly used for example hydroquinone and p-monomethylamino phenol hemisulphate, show the disadvantage of being rapidly oxidised when exposed to the air in alkaline medium so that in the white parts of the transfer copies yellow to brown coloured products are formed during storage of said copies.
• the present invention provides a photographic silver complex diffusion transfer process according to which an image of an original is produced with improved stability and pictorial quality as to yellowing by development of an image-wise exposed light-sensitive silver halide emulsion layer and diffusion of the undeveloped complexed silver halide from the emulsion layer to an image-receiving material that comprises 3-hydroxy-propylene sulphite where the complexed silver halide is converted in the presence of development nuclei in a silver containing image.
• the present invention further provides an image-receiving material for use in a silver complex diffusion transfer process which image-receiving material comprises as anti yellowing agent 3-hydroxy-propylene sulphite.
• the 3-hydroxy-propylene sulphite of use according to the present invention may for instance be prepared from glycerol and thionyl chloride according to one of the following procedures.
• the crude product may be distilled through a short vigreux column, at a pressure of about 1 mm.
• the main fraction boils at 126/1 mm.
• the crude product may be distilled through a short vigreux column, at a pressure of about 1 mm.
• the main fraction boils at 126/ 1 mm.
• 3-hydroxy-propylene sulphite as described above by reaction of glycerol with thionyl chloride
• the 3-hydroxy-propylene sulphite can be incorporated, in a manner commonly used in photographic processes, into any desired layer of the image-receiving material. For instance it can be incorporated into the support, into a baryta-layer, into an intermediate layer arranged between the image-receiving layer and the support, into the image-receiving layer itself and into a water-permeable top layer coated over the image-receiving layer.
• the 3- hydroxyapropylene sulphite may be applied to the composing layers of the image-receiving material in any suitable manner, as for example, by dipping the layer under consideration in a suitable solution of the 3-hydroxypropylene sulphite, by spreading or otherwise applying such solution over the surface of the layer, or by incorporating the 3-hydroxy-propylene sulphite into the coatin g composition of the said layer.
• the 3 hydroxy-propylene sulphite may be incorporated into the! imagereceiving material in an amount comprised preferably between 0.25 and 4 cc. per sq. m. of material.
• composition of the treating solution in the diffusion transfer process according -to the present invention may be that of the common processing solutions for the silver complex diffusion transfer process that contain the ingredients beneficial or essential to the development and the: diffusion transfer for instance developing substance(s) such as hydroquinone, monomethyl-p-aminophenol sulphate, p-aminophenol, a 3-pyrazolidinone compound such as 1-phenyl-3-pyrazolidinone, complexing agent(s) for the non-developed silver halide such as sodium thiosulphate, sodium thiocyanate and ammonia, alkali, potassium bromide, sodium sulphite, a calcium sequestering compound, black toning agent e.g. l-phenyl-S-mercaptotetrazole or similar products such as those described in British Patents 561,875 and 695,905 etc.
• developing substance(s) such as hydroquinone, monomethyl-p-aminophenol sulphate, p-aminophenol,
• the treating solution must not necessarily contain all of the above ingredients; many of them may be present in the image-receiving material and/or in the light-sensitive material.
• the developing substances may be incorporated into the image-receiving material and/ or into the light-sensitive material so that the treating solution can be restricted for instance to an alkaline aqueous liquid which is free of developing agents.
• the imagereceiving material incorporates hydroquinone and the light-sensitive material comprises a 3-pyrazolidinone derivative may be referred to the French patent specification 1,362,792 and to its patent of Addition 84,190.
• the treating liquid basic compounds can be used such as sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonium hydroxide, sodium carbonate, sodium phosphate, etc.
• the amount of anhydrous salt used varies from 50 to 200 g. per litre but in the case of a compound which imparts a high degree of alkalinity for instance sodium hydroxide an amount of from 5 to g. will suffice.
• One of the advantages of using a treating liquid which is free of developing substance is that the liquid cannot get exhausted by aerial oxidation and consequently that it can be used for a long time before being replaced.
• the image-receiving material according to the invention may consist of a support which is impregnated with a substance or substances, such as for example development nuclei, for bringing about the formation of a visible image from the diffusing silver halide complex, and/or a compound or compounds capable of forming such a substance in situ.
• the image-receiving material comprises a paper or other flexible support that is coated with one or more additional layers.
• One of these layers may be the image-receiving layer of nucleicontaining layer that comprises such substances(s) for bringing about the formation of a visible image from the diffusing silver halide complex, and/or such compound(s) capable of forming such substance(s) in situ.
• Such an image-receiving layer can suitably be prepared from colloid binding agents such as gelatin, mixtures of gelatin and sodium alginate, gelatin and carboxymethyl cellulose, polyvinyl alcohol, partially saponified polyvinyl acetate, cellulose acetate or hydrated colloidal silica wherein the development nuclei are incorporated.
• colloid binding agents such as gelatin, mixtures of gelatin and sodium alginate, gelatin and carboxymethyl cellulose, polyvinyl alcohol, partially saponified polyvinyl acetate, cellulose acetate or hydrated colloidal silica wherein the development nuclei are incorporated.
• an image-receiving material which contains no substance(s) for bringing about the formation of a visible image from the diffusing silver halide complex, the said substance(s) being present in the treating solution.
• Such silver halide diffusion transfer process has been described more detailedly in the British patent application 1,001, 8 and in the French patent specification 84,127( which is a patent of addition to the French patent specification 1,321,724), wherein it is carried out with a light-sensitive material bearing a water-permeable colloid layer on top of the light-sensitive layer.
• Examples of development nuclei for complexed silver halide which are suitable for being used according to the invention are sulphides, selenides, polysulphides, polyselenides, thioureas, mercaptans, stannous halides, heavy metals or their salts and fogged silver halide.
• Sulphides of heavy metals such as antimony, bismuth, cadmium, .cobalt, lead, nickel and silver are also suitable.
• the heavy metals silver gold, platinum, palladium and mercury are to be mentioned, preferably in colloidal form. The noble metals among them are the most active.
• the image-receiving material may also comprise in at least one of its layers other ingredients for the diffusion transfer process such as sodium sulphite, a complexing agent for silver halide such as sodium thiosulphate and black-toning agents. It is particularly interesting to have present in the image-receiving material for-instance in the nuclei-containing layer, a quantity of hydroquinone and occasionally at least one compound selected from the group consisting of alkali met abisulphites such as potassium metab-isulphite, water-soluble inorganic bisulphites and water-soluble aldehyde bisulphites. An image-receiving material containing hydroquinone and the said bisulphites is described in the British patent application 1,000, 115.
• the hydroquinone is suitably present in an amount of from 0.1 to 5 g. per sq. m. and the water-soluble bisulphite in an amount of from 0.2 to 2 g. per sq. m.
• the image-receiving layer can also be applied to the same support as the silver halide emulsion layer, for instance as described in the British patent application 1,006,292.
• the multilayer material described in said patent application comprises a light-sensitive silver halide emulsion layer, an underlying image-receiving layer and between these two layers at least one intervening layer, which consists of or comprises a starch ether.
• the silver halide emulsion layer can be detached from the starch ether intermediate layer by bringing the imagewise exposed and developed multilayer material in a rinsing bath at room temperature or even at lower temperature whereby the emulsion detaches as a coherent membrane or by other methods such as stripping off after contact with a sheet of paper.
• the light-sensitive material suitable for use in the silver complex diffusion transfer process according to the present invention may be any material comprising a lightsensitive silver halide emulsion layer, the exposed silver halide of which is sufficiently rapidly developed and the non-exposed silver halide of which is sufficiently rapidly complexed for allowing the formation of a diffusion transfer image.
• a lightsensitive silver halide emulsion layer Preferably gelatino silver chloride emulsions are used, which may contain amounts of silver bromide or silver iodide and to which other ingredients may be added in order to obtain the desired emulsion characteristics.
• the light-sensitive silver halide emulsion layer may be hardened in a usual way by a suitable hardening agent such as formaldehyde.
• the silver halide emulsion layer contains per sq. m. of light-sensitive material an amount of sil-ver halide equivalent to from 0.2 g. to 2 g. of silver nitrate.
• the light-sensitive silver halide emulsion layer of the light-sensitive material may be coated over with a top layer of a water-permeable colloid.
• Such light-sensitive materials are described e.g. in the British patent specification 1,001,558, in the above French patent of addition 84,127 and in French patent specification 84,190, referred to above.
• Suitable water-permeable colloids are among others: methyl cellulose, hydroxyethyl cellulose, hydroxyethyl starch, hydroxypropyl starch, sodium alginate, propylene glycol ester of alginic acid, gum tragacanth, starch, poly(vinylalcohol), poly(acrylic acid), poly(acrylamide), poly(v-inyl pyrrolidinone), poly(oxyethylene), copoly(methyl vinyl ether/maleic acid), etc.
• the most suitable thickness for this top layer depends inter alia on the nature of the colloid chosen and the viscosity of the used colloid solution, but in general the top layer should be only a thin layer.
• substances beneficial or essential to the process may be incorporated such as for instance developing agents, softening agents, stabilizing agents, hardening agents, black-toning agents and the like.
• both the lightsensitive and the image-receiving material may be moistened w-ith treating liquid and then brought into contact with each other. It is, however, also possible to moisten only one of the materials used, preferably the light-sensitive material, and to bring this moistened material into contact with the dry one. This latter embodiment is successfully applied especially when the light-sensitive material is coated over with a top layer of a waterpermeable colloid as described above.
• the moistening of at least one of the materials used may occur by means of wetted rollers e.g. as fully described in the French patent specification 1,407,079. In this way only one side e.g. the emulsion side of the light-sensitive material is wetted, which is a preferred embodiment.
• the image-receiving material or the pressed sandwich of light-sensitive and image-receiving materials may be subjected to heat.
• the application of heat may occur in order to accelerate the diffusion transfer and/or to facilitate the separation of the light-sensitive material from the image-receiving material.
• Example 1 gelatino silver chloride emulsion hardened in the usual way with formaldehyde is applied at 45 C. to a common paper support of 90 g./sq. m. in such a way that an amount of silver chloride equivalent to 0.7 g. of silver nitrate is present per sq. m. of lightsensitive material.
• a top layer is coated in a proportion of 1 litre per 20 sq. m. from the following composition:
• Example 3 While thoroughly stirring 5 cc. of 3-hydroxy-propylene sulphite are added to a suspension of 28 g. of barium sulphate in cc. of a 2% aqueous gelatin solution. This suspension is applied to a paper support. Then said barium sulphate layer is coated pro rata of 13 sq. m./litre with a nuclei-containing layer of the following composition:
• the image-receiving material thus obtained is dried.
• a light-sensitive material is prepared by coating a paper support of 90 g./sq. m. with a gelatino silver chloride emulsion layer in such a way that an amount of silver chloride equivalent to 1 g. of silver nitrate is present per sq. m. of light-sensitive material.
• the light-sensitive material is image-wise exposed and then together with the image-receiving material fed through a diffusion transfer processing apparatus that contains a solution of the following composition:
• Example 4 Example 3 is repeated using, however, an image-receiving material prepared in the following way.
• a nuclei-containing layer is applied from the following composition to a paper support:
• a top layer is applied from a 3% aqueous solution of carboxymethyl cellulose comprising 5 cc. of 3-hydroxy-propylene sulphite.
• the positive print obtained shows no stains after storing for a long time.
• Example 5 A paper support is impregnated with a aqueous solution of 3-hydroxy-propylene sulphite. Then a nuclei-containing layer as described in Example is applied to the paper base.
• a light-sensitive material is prepared by coating a paper support of 90 g./sq. m. with a gelatino silver chloride emulsion layer in such a way that an amount of silver chloride equivalent to 1.3 g. of silver nitrate is present per sq. m. After exposure, development and diffusion transfer as described in Example 3 a positive image is obtained that keeps its white background even after storing for a long time.
• Method for producing photographic images according to the silver complex diffusion transfer process comprising the steps of (1) image-wise exposing a light-sensitive material containing a silver halide emulsion layer,
• Method for producing photographic images according to the silver complex diffusion transfer process comprising the steps of (1) image-wise exposing a light-sensitive material containing a silver halide emulsion layer,
• Method for producing photographic images according to the silver complex diffusion transfer process comprising the steps of (1) image-wise exposing a light-sensitive material containing a silver halide emulsion layer,
• Image-receiving material for use in a method for producing photographic images according to the silver complex diffusion transfer process, wherein 3-hydroxypropylene sulphite is incorporated therein.
• Image-receiving material according to claim 7 including a support and wherein the 3-hydroxy-propylene sulphite is incorporated into the support.
• Image-receiving material according to claim 7 including a baryta-layer and wherein the 3-hydroxy-propylene sulphite is incorporated into a baryta-layer coated on the support.
• Image-receiving material according to claim 7 including an image-receiving layer and wherein the S-hydroxy-propylene sulphite is incorporated into the imagereceiving layer.

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• Chemical & Material Sciences (AREA)
• Inorganic Chemistry (AREA)
• Physics & Mathematics (AREA)
• General Physics & Mathematics (AREA)
• Photosensitive Polymer And Photoresist Processing (AREA)
• Silver Salt Photography Or Processing Solution Therefor (AREA)
• Epoxy Compounds (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

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Citations (2)

• 1965
  • 1965-02-26 GB GB8479/65A patent/GB1106763A/en not_active Expired
  • 1965-09-24 US US490082A patent/US3395015A/en not_active Expired - Lifetime
• 1966
  • 1966-02-25 DE DEA51682A patent/DE1300017B/de active Pending
  • 1966-02-25 NL NL6602509A patent/NL6602509A/xx unknown
  • 1966-02-25 CH CH276366A patent/CH472055A/de not_active IP Right Cessation
  • 1966-02-28 BE BE677090D patent/BE677090A/xx unknown

Patent Citations (2)

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