US3340059A - Diffusion transfer process for producing silver-free azo dye images - Google Patents

Diffusion transfer process for producing silver-free azo dye images Download PDF

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Publication number
US3340059A
US3340059A US311980A US31198063A US3340059A US 3340059 A US3340059 A US 3340059A US 311980 A US311980 A US 311980A US 31198063 A US31198063 A US 31198063A US 3340059 A US3340059 A US 3340059A
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US
United States
Prior art keywords
image
silver
solution
coupling
film
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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US311980A
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English (en)
Inventor
Boes Otto
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
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Publication of US3340059A publication Critical patent/US3340059A/en
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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
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
    • G03C5/50—Reversal development; Contact processes
    • 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
    • G03C8/08—Photosensitive materials characterised by the image-forming section the substances transferred by diffusion consisting of organic compounds

Definitions

  • This invention pertains to a novel process for producing silver-free images from photographic silver images by image-true contact transfer of a compound to an image acceptor film containing a reagent suitable for coupling.
  • An object of this invention is to provide new imageforming processes.
  • a related object is to provide new processes for forming and transferring images.
  • a further object is to provide such processes which are simple and dependable. Still further objects will be apparent from the following description of the invention.
  • a photographic silver image is treated with a solution of a diazonium compound in the presence of a substance having catalytic activity and the diazonium compound is transferred, true to the image, to an image acceptor film which is placed in intimate contact with the original silver image.
  • the process of image formation takes the following course:
  • the diazonium compound solution In treating the silver image, e.g., a developed silver image in an original photographic silver halide emulsion layer, with a diazonium compound solution, the latter, under the catalytic influence of suitable additives, is decomposed at points containing image silver, with formation of noncoupling degradation products. At points free from image silver, on the other hand, in the reverse areas or non-developed areas of the layer the diazonium compound is retained unchanged.
  • an image acceptor element e.g., paper or film
  • the image acceptor element There is then formed in the image acceptor element, by coupling the diazonium compound with a reagent which is present in that film, an azo dye image with gradation opposite to that of the original, i.e., if the start is made with an ordinary photographic negative, then a positive image is obtained after the transfer, whereas when a positive is used as the original a negative image is obtained by diffusion.
  • Chloride, thiocyanate, bromide and iodide ions have been found particularly suitable for use as additives which effect the catalytic decomposition of the diazo compound by the image silver, the catalytic activity of the specified ions being in ascending order as listed. In practice, this rising activity results in an apparent increase in speed and contrast. Thus, when iodide ions are used, the apparent speed is higher and the pictures exhibit high contrast, whereas when chloride ions are used relatively lower speed and contrast are obtained.
  • the choice of a suitable catalyst for each case depends on the character of the original as well as on the requirements imposed on the finished picture, and can be easily decided from case to case by one skilled in the art.
  • Suitable compounds that will provide the ions referred to above include sodium and potassium chloride, bromide, iodide and thiocyanate which are illustrated in the examples. Mixtures of two or more of these compounds can be used. Other useful compounds are: the corresponding magnesium, calcium, strontium and barium salts and mixtures of two or more of the foregoing salts.
  • the catalytically active substances may be added to the diazonium solution singly or in combination.
  • Practically all coupling reagents and diazonium salts which are capable of azo coupling are suitable for carrying out the processes, so that a very wide selection of dyes is avail; able.
  • Usable compounds are listed, for example, in the following tables:
  • a gelatin film for example, may be used as thep act-V ceptor layer, which contains a reagent capable of azo coupling and may be applied to any desired film base, e.g., paper, a cellulose ester or the like.
  • a reagent capable of azo coupling may be applied to any desired film base, e.g., paper, a cellulose ester or the like.
  • other water-permeable colloid binding agents and film-forming materials may be used instead of gelatin as the vehicle ii such as polyvinyl alcohol, polyvinyl acetate, polyvinyl 'acetals,'polyesters, etcr
  • the reagents are incorporated in the film by methods known in the art,in which connection it has been found advisable to use the reagents in a diifusion-r'esistingjorm. It is desirable to coat the surface of the acceptor film containing the reagent capable of azo coupling with a thin protective layer of a waterpermeable
  • the process according to this invention is characterized "by a number of advantages; Thus, it is possible tomake one or more copies in-a veryshort'time from a silver.-
  • Copies may be made-in ordinary: daylight, so his not necessary to provide a dark room.
  • Therequisite processingtime for making a copy is relatively short, since in A gelatin solution containing, per liter, 6 g. of dye coupling agent No. 4 of Table I is coated in the customary manner on a transparent film base. This material serves as the acceptor film.
  • a normal negative silver image is treated 30 seconds in a solution having the following composition:
  • the clinging treatment solution is stripped from the silver image and the negative is pressed on the acceptor film with a squeegee. After seconds the acceptor film is stripped away from the silver image. It contains a yellow positive transparency of the black-and-white negative. The negative is washed with water and dried. It is practically unchanged. If the dye coupling agent in the acceptor film is replaced by one of the coupling agents listed in Table I, then, by otherwise identical processing, positive images are obtained in the colors stated in the table. When coupling agents 1820 are used, then the acceptor film, after stripping from the silver image, is given an additional treatment of 1 minute in 1% sodium carbonate solution to force formation of the dye.
  • Example 2 Water liter" 1 Diazonium compound g 10 Potassium bromide -g 25 Sodium acetate g 25 Glacial acetic acid ml 2 N-methyloleyltaurine g 0.2
  • Example 3 The same original is employed as in Example 2.
  • the acceptor film is prepared as follows: A gelatin solution is coated on an ordinary paper base; each liter of solution containing 6 g. of dye coupling agent No. 16 of Table I. A top-coat is coated on this gelatin film from a solution of the following composition:
  • a stock solution, to which another catalyst is added for each image, is used as the treatment bath.
  • Example 4 An ordinary silver image on photographic paper is used as the original. It is treated for 20 seconds with the following solution:
  • a screen negative on ordinary lithographic film is used as the original.
  • a gelatin film on a transparent base, the dye coupling agent being compound No. 16 of Table I, is used as acceptor film.
  • the treatment solution has the following composition:
  • Processing is as usual, with bath time 20 seconds and contact time 15 seconds between original and acceptor film. A red positive screen image is obtained.
  • Example 6 The same original is used as in Examples 2 and 3, with the acceptor film described in Example 5.
  • the requisite treatment solution is prepared as follows:
  • Solution A 2.9 g. of the amine corresponding to diazonium compound No. 18 of Table II is dissolved in 20 ml. of 5% hydrochloric acid and diazotized in the usual Way by adding a solution of 0.7 g. sodium nitrite in 5 ml. water. The resulting diazonium salt solution is adjusted to pH 6 by adding 10% sodium hydroxide solution and is then made up to 50 ml. with water.
  • the original is treated 30 seconds with this solution and, after removing excess solution, the wet surface is brought into contact with the acceptor film for 20.seconds.
  • the original is stripped oif and the acceptor film is immediatedried.
  • a blue positive image is obtained.
  • the correspond- .ing ready A-solutions were also obtained from the diazonium salts listed in Table II as Nos. 1517 and 19, by diazotizing the amines. They were introduced as treatment-baths after adding the same B-solutions with the same material and same processing. This gave positive images inthe colors stated in Table II. After treatment of the acceptor film with sodium carbonate solution was not necessary with these diazonium salts.
  • An'advantage of the present invention is that it provides a'simple'and practical process for forming azo dye images in a separate element.
  • Another advantage of the invention is that it is possible to prepare one or several prints from an original copy containing silver within the shortest time and without any printing exposure being. necessary.
  • a further advantage is that production of the prints may take place in normal daylight, so that a dark room is unnecessary.
  • Still further advantage of the invention is that a single treating bath only is required, so that prints can be made in a relatively short time, usually about one minute.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
US311980A 1963-02-27 1963-09-27 Diffusion transfer process for producing silver-free azo dye images Expired - Lifetime US3340059A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DEA42450A DE1171268B (de) 1963-02-27 1963-02-27 Verfahren zur Herstellung von silberfreien negativen Abbildungen von photographischen Silberbildern

Publications (1)

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US3340059A true US3340059A (en) 1967-09-05

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US (1) US3340059A (de)
DE (1) DE1171268B (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2418480A1 (fr) * 1978-02-28 1979-09-21 Ciba Geigy Ag Procede de production d'images photographiques par diffusion-transfert du colorant et matiere photographique appropriee dans ce procede

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2271176A (en) * 1938-12-19 1942-01-27 Chromogen Inc Process for the manufacture of color photographic images
US2386167A (en) * 1943-08-28 1945-10-02 Du Pont Photographic article of manufacture
US2465760A (en) * 1947-07-02 1949-03-29 Gen Anlline & Film Corp Diazotype materials derived from aryl diazo sulfones
US2747999A (en) * 1953-03-16 1956-05-29 Eastman Kodak Co Photographic reproduction process

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2271176A (en) * 1938-12-19 1942-01-27 Chromogen Inc Process for the manufacture of color photographic images
US2386167A (en) * 1943-08-28 1945-10-02 Du Pont Photographic article of manufacture
US2465760A (en) * 1947-07-02 1949-03-29 Gen Anlline & Film Corp Diazotype materials derived from aryl diazo sulfones
US2747999A (en) * 1953-03-16 1956-05-29 Eastman Kodak Co Photographic reproduction process

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2418480A1 (fr) * 1978-02-28 1979-09-21 Ciba Geigy Ag Procede de production d'images photographiques par diffusion-transfert du colorant et matiere photographique appropriee dans ce procede
US4269928A (en) * 1978-02-28 1981-05-26 Ciba-Geigy Aktiengesellschaft Process for the production of photographic images by dye diffusion transfer and photographic material suitable in this process

Also Published As

Publication number Publication date
DE1171268B (de) 1964-05-27

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