US3368896A - Image-receiving material for the production of photographic images by the silver salt diffusion process - Google Patents

Image-receiving material for the production of photographic images by the silver salt diffusion process Download PDF

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Publication number
US3368896A
US3368896A US290603A US29060363A US3368896A US 3368896 A US3368896 A US 3368896A US 290603 A US290603 A US 290603A US 29060363 A US29060363 A US 29060363A US 3368896 A US3368896 A US 3368896A
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Prior art keywords
image
layer
layers
photographic images
production
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US290603A
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English (en)
Inventor
Riebel Alexander
Ulrich Hans
Himmelmann Wolfgang
Britz Karl-Heinz
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AFGA AG
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AFGA AG
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    • 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
    • G03C8/24—Photosensitive materials characterised by the image-receiving section
    • G03C8/26—Image-receiving layers
    • G03C8/28—Image-receiving layers containing development nuclei or compounds forming such nuclei
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment

Definitions

  • the invention relates to an image-receiving material for the production of photographic images by the silver salt diffusion process.
  • a light-sensitive silver halide emulsion layer negative layer
  • a layer of a suitable image-receiving material positive layer
  • unexposed silver halide is dissolved from the negative layer, diffuses into the positive layer and is transformed into a silver image at the development nuclei present in the latter layer.
  • the facility with which the two layers may be separated depends substantially on the choice of the coating media for the negative and positive layers. For example, if gelatine is used for both layers, they adhere very firmly one to another and they must quickly be separated one from another, whereas addition of a cellulose ester enables the layers to be separated more easily and after a much longer period of contact.
  • Other substances which substantially facilitate the separation of the layers after the diffusion are known from British Patent No. 687,751, according to which a variety of materials, including polyamides, polyesters, polyvinyl alcohol, polyvinyl acetates and polyvinyl pyrrolidones can be employed.
  • British Patent No. 856,792 describes transfer foils with a transparent support, and image-receiving layers which contain, as binder, mixtures of alkylvinyl ether maleic anhydride copolymers with hydrophobic resins, such as cellulose derivatives. These layers have the disadvantage, however, that separate processing steps are necessary to produce the water-absorption capacity.
  • the moist image-receiving lay ers after the image has been produced and after separation from the light-sensitive material, are alkaline because they contain developer residues. As a result the white portions of the image show a tendency to yellow discoloration on keeping. Finally, the proteins develop tensile forces when completely dried and these forces result in curling of the papers.
  • imagereceiving layers that contain a hydrophilic film-forming protein, such as gelatine or casein, are considerably improved if they have incorporated therein in dispersed form a copolymer of alkyl vinyl ethers and maleic anhydride, the anhydride groups of which have been transformed, into semi-ester and semi-amide groups by reaction with lower aliphatic alcohols and monoalkanolamines.
  • a hydrophilic film-forming protein such as gelatine or casein
  • the layers according to the invention show a neutral reaction rapidlyely after the separation. As a result, yellowing of the material is largely prevented.
  • the new image-receiving layers also show far less tendency to curl, presumably because addition of the copolymer in the form of a dispersion reduces the tension forces of the colloids in the hydrophilic layer.
  • a further advantage of the new image-receiving layers is the more rapid drying, which is a result of the relatively small proportion of hydrophilic colloid per unit area.
  • copolymers from which are made the additives used according to the invention, are obtained in a manner known per so by copolymerising maleic anhydride with alkyl vinyl ethers.
  • alkyl vinyl ethers there are advantageously used the vinyl ethers of lower aliphatic, monohydric saturated alcohols having 1 to 5 carbon atoms, more especially nbutyl vinyl ether or isobutyl vinylether.
  • the copolymers advantageously contain the said components in approximately equimolar quantities, and generally have molecular weights from 800 to 3000.
  • these copolymers may be reacted, at elevated temperatures in alcoholic solution, with an alcohol and a monoalkanolamine whereby the anhydride groups are partially or completely transformed into semi-ester and semi-amide groups.
  • Suitable alcohols are monohydric, aliphatic, saturated alcohols with 1 to 3 carbon atoms, more especially methanol and suitable monoalkanolamines are such in which the alkanol group contains 2 to 4 carbon atoms.
  • Monoethanolamine is advantageously used as the alkanolamine.
  • the alkanolamines are generally applied in quantities of 0.1 to 5% by weight, calculated on the copolymer.
  • the reaction may be carried out in a 120% solution of the copolymer in the aforementioned alcohols at temperatures of 50-120" (1., preferably at the reflux temperature of the solutions.
  • the reaction products ob tained are insoluble in Water and are soluble in dilute alkalis and in aliphatic alcohols, such as methanol, propanol and butanol. Since the reaction products, in the form of their solutions in aliphatic alcohols, have a higher viscosity than corresponding material which has been produced exclusively with the use of the aforementioned alcohols, it is probable that the reaction leads to a crosslinking by the moneothanolamine or at least to a substantial increase in the molecular weight of the copolymers.
  • T he modified copolymers according to the invention are generally added in quantities from 5 to 200%, advantageously 10 to by weight, calculated on the weight of the film-forming protein.
  • the modified copolymers are first of all dissolved inan organic solvent such as butanol, together with a difiicultlyvolatile, oily dispersion auxiliary, such as a phthalicacid ester, and the solution obtained is dispersed, by means of a high-speed turbo-stirrer, in an aqueous solution of the protein.
  • a copolymer suitable for use in the present invention may be produced as follows:
  • the precipitated polymer is collccted, roughly comminutcd, dried in vacuo at 35 to 50 C., and ground.
  • n-butyl-vinyl other there may also be used methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether or isobutyl vinyl ether in equimolecular quantities.
  • polymeric hardeners which are superior to the known monomeric hardeners such as formaldehyde, are added to the layers.
  • Concerned here more especially are bisulphite compounds of polyacrolein which have been described in British Patent No. 797,459 and which may be applied according to the prescription given in Belgian Patent No. 624,108.
  • Oxidation products of carbohydrates are also suitable, for example the so-called dialdehyde starches which are described in British Patent No. 891,221 and also polyvinyl alcohol maleates, which are known from British Patent No. 822,061.
  • a transfer material with particularly advantageous properties is obtained if the polymeric hardener is added both to the baryta-coating layer and to the image-receiving layer, hydrophobic film-forming products being used as binding agent for the barytacoating layer.
  • Suitable as dialdehyde starch is, for example, the product marketed by Messrs. Miles Lab. Co. under the trade name Sunistar. It is used in an aqueous sodium acetate solution.
  • development nuclei for the transfer layer can be used as development nuclei for the transfer layer, for example colloidal silver or gold, thiourea, and the colloidal sulphides or selenides of silver, gold, lead, mercury, tin, zinc or copper.
  • the development nuclei can be added to the casting solution as colloidal solutions or can be produced in the prepared layer by known processes.
  • the nuclei are advantageously used in quantities from 0.001 to 1 g. per litre of casting solution.
  • compounds which influence the image tone such as mercaptobenzthiazolcs, mercaptotetrazoles or hydroxymercaptotriazines, as well as developer substances such as hydroquinone and silver halide solvents such as alkali or alkaline earth thiosulphates can be added to the positive layer.
  • Example 1 A solution of l g. of a 1:1 copolymer of maleic anhydride and n-butyl-vinyl ether, which is prepared and reacted in the manner described above, in a mixture of 5 ml. of n-butanol and 1 ml. of dibutyl phthalate, is run into 170 ml. of a 6% gelatine solution, which contains 0.003 g. of silver sulphide in colloidal form and 6 g. of sodium thiosulphate, using a high-speed turbo-stirrer with high speeds of revolution and strong shearing forces, so that a uniform emulsion is obtained. 1 ml. of a 10% solution of a bisulphite compound of polyacrolein is added 4- to this mixture. The casting solution thus prepared is cast in known manner onto ordinary or baryta-coatcd paper and dried.
  • the positive material is guided, in contact with an exposed silver halide emulsion layer (negative layer) prepared in the usual manner, through one of the known continuous-developing apparatuses, which contains the following developer solution:
  • Example 2 The process described in Example 1 is followed, using 6 g. of ccpolymer dissolved in 30 ml. of n'butanol and 6 ml. of dibutyl phthalate, emulsified into a gclatine solution. After development, the positive layer and negative layer can still satisfactorily be separated one from another after a contact time of 5 minutes. In addition, the resistance to yellowing of the prepared copy is substantially improved over a copy not containing the additive.
  • Example 3 A solution of l g. of copolymer in a mixture of 5 ml. of n-butanol and 1 ml. of dibutyl phthalate is emulsified, in ml. of a 6% aqueous neutral casein solution with additions of development nuclei and silver halide solvents as in Example 1.
  • the hardening, as well as the casting and processing, is carried out according to Example 1. An image of good density is obtained on the positive layer.
  • the positive and negative layers can still satisfactorily be separated after a contact time of 2 minutes.
  • Example 4 The process of Example 3 was followed but with 6 g. of copolymer dissolved in 30 ml. of n-butanol and 6 mi. of dibutyl phthalate. A hardener of the type described in Example 1 is also added. The contact time between positive and negative layers can thereby be extended to 5 minutes.
  • Example 5 A baryta coating, the binding agent of which consists of a hydrophobic, synthetic resin, for example of copolymers of acrylic acid esters, and which contains barium sulphate in normal concentrations is applied to a paper web.
  • the baryta coating can contain also the usual additives such as white toners and wetting agents.
  • As hardener bisulphite compounds of polyacrolein, such as those described in Example I, are added to the baryta coating. From 500 to 1000 ml. of an aqueous 10% hardener solution are used to 30 litres of baryta casting solution which contains from 10 to 20% of binding agents.
  • Example 1 The image-receiving layer described in Example 1 is applied to the dried baryta coating, the paper is processed photographically in the same manner and a positive image of excellent quality is obtained. Satisfactory separation of the negative and positive materials is possible even after relatively long contact times.
  • the transfer material described above is characterised by an excellent bonding, more especially between the baryta coating and the transfer layer.

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Laminated Bodies (AREA)
US290603A 1962-07-28 1963-06-26 Image-receiving material for the production of photographic images by the silver salt diffusion process Expired - Lifetime US3368896A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DEA40836A DE1156651B (de) 1962-07-28 1962-07-28 Bildempfangsmaterial fuer die Erzeugung photographischer Bilder nach dem Silbersalzdiffusionsverfahren

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US3368896A true US3368896A (en) 1968-02-13

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BE (1) BE635438A (en))
CH (1) CH450161A (en))
DE (1) DE1156651B (en))
GB (1) GB1001380A (en))

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2558857A (en) * 1947-02-08 1951-07-03 Polaroid Corp Photographic developer element
US2607762A (en) * 1948-12-07 1952-08-19 Monsanto Chemicals Dry process manufacture of watersoluble derivatives of styrenemaleic anhydride type heteropolymers
DE1083051B (de) * 1958-10-04 1960-06-09 Degussa Verfahren zur Herstellung von Verbundpolymeren des Polyacroleins
GB856792A (en) * 1958-05-07 1960-12-21 Gen Aniline & Film Corp Receiving sheet for use in photographic silver transfer process
US3017377A (en) * 1955-03-08 1962-01-16 Sherwin Williams Co Extender composition for textile printing pastes containing reaction product of monoethanolamine solution and the co-polymer of unhydrolyzed methyl vinyl ether and maleic anhydride

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2558857A (en) * 1947-02-08 1951-07-03 Polaroid Corp Photographic developer element
US2607762A (en) * 1948-12-07 1952-08-19 Monsanto Chemicals Dry process manufacture of watersoluble derivatives of styrenemaleic anhydride type heteropolymers
US3017377A (en) * 1955-03-08 1962-01-16 Sherwin Williams Co Extender composition for textile printing pastes containing reaction product of monoethanolamine solution and the co-polymer of unhydrolyzed methyl vinyl ether and maleic anhydride
GB856792A (en) * 1958-05-07 1960-12-21 Gen Aniline & Film Corp Receiving sheet for use in photographic silver transfer process
DE1083051B (de) * 1958-10-04 1960-06-09 Degussa Verfahren zur Herstellung von Verbundpolymeren des Polyacroleins

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GB1001380A (en) 1965-08-18
DE1156651B (de) 1963-10-31
CH450161A (de) 1968-01-15
BE635438A (en))

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