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
  • G03C8/24—Photosensitive materials characterised by the image-receiving section
  • G03C8/243—Toners for the silver image
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
  • Y10S430/166—Toner containing

Definitions

• This invention relates to an improved photographic silver complex diffusion transfer process for obtaining dif fuion transfer images possessing a densely black image tone and a developer and a photographic material used for said process.
• a light-sensitive silver halide emulsion layer which is coated on a basesheet such as paper or plastic film is imagewise exposed and thereupon pressed into contact with an image-receiving layer which is coated with colloidal dispersion of a heavy metal or metal sulfide immersed in a hydrophillic binder such as gelatin or polyvinyl-alcohol, in the presence of a developing agent and a complexing agent for silver halide.
• the exposed silver halide grains are developed to metallic silver images and do not undergo any further change, while the unexposed part of the light-sensitive lay er is complexed with a complexing agent such as a thiosulfate, a sulfite or an organic amine which is present either in the developer or in the image-receiving layer, where it is converted into metallic silver image by means of colloidal metallic particles which act as developing nuclei during development. In such a way, a positive image of the original appears in the image receiving layer after separating the latter from the light-sensitive layer.
• a complexing agent such as a thiosulfate, a sulfite or an organic amine
• R represents a hydrogen atom or one of lower alkyl, aryl and aralkyl groups and R represents a lower alkyl group.
• Substances of B series are N-acyl derivatives of A.
• the typical derivatives of A series include 4-amino-3-methyl-1,2,4-triazoline-5-thione, 4-amino-3-ethy1-1,2,4-triazoline-S-thione, 4-amino-3-propyl-1,2,4-triazoline-S-thione, 4-amino-3-butyl-1,2,4-triazoline-5-thione, 4-amino-3-p-tolyl-1 ,2,4-triazoline- -thione,
• the typical derivatives of B series include 4-acetamide-1,2,4-triazoline-5-thione, 4-acetamide-3-methyl-1,2,4-triazoline-5-thione, 4-acetamide-3-ethyll,2,4-triazoline-5-thione, 4-acetamide-3-propyl-1,2,4-triazoline-S-thione, 4-acetamide-3-butyl-1,2,4-triazoline-S-thione, 4-ethylamide-3-methyl-1,2,4-triazoline-5-thione, 4-ethylamide-3-ethyll ,2,4-triazoline-5-thione, 4-ethylamide-3-propyl-1,2,4-triazoline-5-thione, 3-methyl-4-pyropylamide- 1,2,4-triaZoline-5-thione, 3-ethyl-4-propylamide-1,2,4-triazoline-5-thione, 4-butylamide-3-methyl1,2,4-triazoline-5-thione, 4-
• the required concentration of the toner Widely varies according to various factors involved in the system, such as temperature, contents of thiosulfate in the developer, etc. as mentioned above, but probably lies in a range between 0.01 to g./l. in the developer and 0.01 to 0.1 g./m. in the image-receiving layer or the light-sensitive layer, as a total sum of the agents used alone or in combination with similar compounds.
• Compounds of this invention are soluble in an aqueous alkaline solution and are very stable in a solution of caustic alkalin.
• the properties are suitable to be added in a developer of the silver complex diffusion transfer system.
• the elfects are not influenced very much by the temperature of developer, but it is favourable to carry out the development at a temperature between C. and 35 C., considering the rate of diffusion of the silver complexes in the layer.
• 4-acetamido-3-ethyl 1,2,4 triazoline-S-thione for example, can be prepared as follows: 106 grams of thiocarbohydrazide and 222 grams of propionic acid are mixed and heated for 9 hours at a temperature of 140 to 150 C. to yield 86 grams (60% of the theoretical amount) 4-amino-3-ethyl-1,2,4-triazoline 5 thione (M.P. 149- 150 C.), whereupon 72 grams of the latter compound is dissolved in 100 ml. acetic anhydride and the solution is heated for 3 hours at a temperature of to C., then cooled and resulting crystals are dissolved in an aqueous solution of sodium hydroxide. Acidification of the alkaline solution to a pH value 5 by adding hydrochloric acid gives 35 grams of colourless crystals (M.P. 202-203 C.). Other derivatives can also be prepared in a similar manner with ease.
• EXAMPLE 1 A light-sensitive material was prepared by coating a paper support with a silver chloride-gelatin emulsion of low sensitivity.
• An image-receiving material was prepared by coating a paper support with a suspension from the following coating composition:
• Coating weights of the suspension was adjusted to about 40 to 60 g./sq.m. And after drying precoating, a protective coating of 1.5% solution of sodium carboxymethylcellulose in water (about 30 g./m. was applied over the coating.
• a light-sensitive paper was exposed image-Wise, while being in contact with an original to be reproduced, whereupon it was passed together with the above image-receiving material through a developing bath of the following composition:
• EXAMPLE 2 The table below shows the colour-ratio, defined as the ratio of the reflection density measured at 400 m to that at 700 m of a transferred image on an image-receiving material obtained by the diffusion transfer process using developers which consist of almost the same components described in Example 1 and using various toning agent of 4-amino-1,2,4 triazoline-S-thione derivatives.
• the imagetone is generally represented by the colour-ratio, and the image-tone was brown or brownish black when the colourratio was larger than two, and it was neutral black or blue-black when it was smaller than two on the contrary.
• EXAMPLE 4 The coating solution for the protective layer of the image-receiving material described in the Example 3 was further added to 5 ml. of 1% solution of Z-methyl-S-mercapto-1,3,4-triazol, a well known toning agent, in ethanol, and the amount of 1% solution of 4-propion-amido-3- methyl-1,2,4-triazoline-5-thione in ethanol was reduced to 2 ml.
• the combination of two or more toning agents leads to a wide latitude for the processing conditions such as temperature, and also serves to the reduction of the cost of material.
• EXAMPLE 3 0.01 gram l-phenyl-S-mercapto-1,2,3,4-tetrazole and 0.01 gram mercapto-benzothiazole were added per litre of the emulsion described in the Example 1. They are well known stabilizing agents.
• An image-receiving material was also prepared by coating a paper support with a suspension of the coating composition described in the Example 1 (coating weight: 40 to 60 g./m.
• silver-chloro-bromide gelatin emulsion of which about a half amount of gelatin was displaced by the same amount of carboxy-methyl-starch and also added with 0.02 g./l. of benzotriazole as stabilizer, was coated on the inter-layer and finally 2% solution of carboxy methyl-starch was over coated as a protective layer.
• the photosensitive material thus produced was particularly suitable for retrievals of the drawings for industrial design or architecture from a micro-filmed positive, and also suitable for obtaining inter-diapositives of medium size from original drawings by direct cameracopying.
• the sensitive material was processed for 30 sec. to 1 min. in the transfer-developer of the following composition;
• a negative image was produced in an upper light-sensitive layer and a positive image was transferred into the lower image-receiving layer by diffusiontransfer process at the same time, then the material was transferred to the washing bath, where the upper layer was dispersed into water by means of the inter-layer which may be easily disintegrated into solution, and there left a final positive image on the film base in a very short time.
• EXAMPLE 6 60 m1. of 1% solution of 4-amino-3-propyl-1,2,4-triazoline-S-thione in ethanol plus 40 ml. of 1% solution of 4-acetamido-3-methyl-1,2,4-triazoline-5-thione in ethanol were advantageously added to the coating solution for the image-receiving layer described in the Example 5, instead of being added into the developer. In contrast with this, benztriazole was added into the developer instead of being added into the photo sensitive emulsion, but the latter case was disadvantageous, considering the stability of the photo sensitive materials.
• EXAMPLE 7 0.07 g. of 4-acetamide-3-ethy1-1,2,4-triazoline-5-thione per 1 l. of emulsion was contained in the sensitive layer of Example 1. The same image-receiving material as in Example was prepared. A positive densely black image was immediately formed on the image-receiving material using the usual developing solution for the silver complex diffusion transfer process.
• EXAMPLE 8 A sensitive material was prepared by coating the support paper of 90 g./m. with gelatino-silver halide emulsion in such a way that 1.30 g. of silver chloride was present per 1 m? of the sensitive material. A sensitive sheet was produced by coating the following solution on said emulsion layer at the rate of 1 l./ 10 m2.
• PAM75 (trade name for polyacrylamide having a medium viscosity and produced by American Cyanamide Company)l g.
• the image-receiving material was produced by coating the following solution on a support paper of 80 g./m. at the rate of 35 g./m.
• a positive densely black image was immediately formed on the image-receiving material using the treating solution of Example 3 as the developing solution.
• R is a member selected from the group consisting of hydrogen, lower alkyl, aryl and aralkyl, and
• X is a member selected from the group consisting of NH and NHCOR wherein R is a lower alkyl group, said process immediately producing a densely black transfer image.
• 4-amino- 1,2,4-triazoline-5-thione derivatives used are selected from the group consisting of 4-amino-3-ethyl-1,2,4-triazoline-5- thioue, 4-amino 3 propyl-1,2,4-triazoline-5-thione, 4- ethylamide 3 methyl-1,2,4-triazoline-S-thione, 4-ethylamide-3-ethyl-1,2,4-triazoline-5-thione and 4-ethylamide- 3-propyl-1,2,4-triazoline-5-thione.
• a developer for immediately producing diffusion transfer images comprising a silver halide solvent and at least one developing agent
• said developer contains at least one 4-amino-1,2,4-triazoline-5-thione derivative of the general formula:
• R is a member selected from the group consisting of hydrogen, lower alkyl, aryl and aralkyl,
• X is a member selected from the group consisting of NH and NHCOR wherein R is a lower alkyl group, wherein said transfer images possess a densely black image tone.
• a silver complex diffusion transferring material containing at least one of the derivatives according to claim 3 in a sensitive layer or a layer adjacent thereto.

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

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Cited By (2)

• 1968
  • 1968-03-11 US US711880A patent/US3576629A/en not_active Expired - Lifetime
  • 1968-03-13 GB GB02287/68A patent/GB1204931A/en not_active Expired
  • 1968-03-26 BE BE712789D patent/BE712789A/xx not_active IP Right Cessation

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