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

Definitions

• One object of this invention is to provide colored diffusion transfer images having enhanced stability in sunlight, and also to provide processes for obtaining su'ch improved stability.
• the invention accordingly comprises 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.
• the processes are preferably carried out by disposing the dye developer in the photosensitive element prior to exposure, and causing it to be solubilized therefrom by an alkaline processing liquid which isapplied between the superposed photosensitive element and image-receiving element.
• the exposed silver halide is reduced to metallic silver and the portions of the dye developer, which are oxidized as a result of the silver development, are substantially immobilized in exposed areas.
• At least a portion of the unreacted dye developer is imbibed on a superposed image-receiving layer to create thereon the positive dye image.
• the positive dye image is preferably viewed by stripping the photosensitive element from the image-receiving layer.
• the image-receiving elements used in such processes generally comprise an opaque or transparent support coated with an image-receiving layer of a dyeable material which is permeable to the alkaline aqueous processing solution.
• a dyeable material which is permeable to the alkaline aqueous processing solution.
• film-forming materials such as polyvinyl alcohol, gelatin and nylons, such as N-methoxymethyl polyhexamethylene adipamide, have been used as the dyeable materials.
• the color fastness of the colored photographic images produced in such processes upon prolonged exposure to sunlight, ultraviolet light, etc., often leaves something to be desired.
• the image-receiving layer on which the image is formed comprises at least in part polyvinyl alcohol, polyvinyl alcohol copolymers or derivatives of polyvinyl alcohol having unreacted hydroxyl groups
• the color fastness of the images may be substantially enhanced by treating said images, subse- Patented Mar. 8, 1966 ice quent to their formation, with a boron compound which in an aqueous solution forms a borate ion.
• the boron compound may conveniently be applied to the colored image by immersion, swabbing, coating, spraying, flowing, etc.
• the solution may also comprise a film-forming polymer, such, for example, as gelatin, polyvinyl alcohol, etc., which will serve as a protective surface coating for the image.
• the solution may comprise other stabilizing agents such, for example, as ultraviolet absorbers, etc.
• the boron compounds are applied from aqueous solutions.
• such aqueous solutions may contain organic solvents such, for example, as methanol, acetone, etc.
• the solution providing the borate ion also includes a saccharide, e.g., fructose or anhydroennaheptitol.
• said solution may also contain a film material, e.g., polyvinyl alcohol.
• the inclusion of the di-ortho tolyl guanidine salt of dicatechol borate has been found to enhance the stabilizing effect of the borate ion, particularly when used with aqueous boric acid or with aqueous boric acid containing anhydroennaheptitol and polyvinyl alcohol.
• borate ions are sometimes used to reduce the water-sensitivity of the image-receiving layers prior to the use of the elements in diffusion transfer processes. Such prior use of the borate ions has no notice able effect on the stability of the images which are formed thereon and should be distinguished from the processes of the present invention wherein the borate ions are used subsequent to the formation of the image.
• the dye developers may also be defined as compounds which contain in the same molecule both the chromophoric system of a dye and also a silver halide developing function.
• a silver halide developing function is meant a grouping adapted to develop exposed silver halide.
• a preferred silver halide developing function is a hydroquinonyl group.
• Other suitable developing functions are o-dihydroxyphenyl radicals.
• the developing function includes a benzenoid developing function. Examples of representative dye developers are given in my previously mentioned application, Serial No. 748,421. Additional useful dye developers are described in the following copending U.S. applications:
• the stabilizers of this invention areboron compounds which in water form a borate ion.
• orthoboric acid HgBOa (boric acid)
• metaboric acid HBO tetraboric acid H B O perboric acid HBO the alkali metal and other water-soluble salts of said acids e.g., borax, Na B O potassium borate K BO sodium perborate NaBO and boric acid esters, e.g., an ester of boric acid and ethylene glycol.
• the processes of this invention are especially effective in stabilizing dye developer transfer images which are produced on image-receiving layers comprising polyvinyl alcohol, copolymers of polyvinyl alcohol and derivatives of polyvinyl alcohol having free hydroxyl groups.
• the image-receiving layer need not comprise solely the above-mentioned polyvinyl alcohol polymers, but may comprise other polymers and other reagents, e.g., mordants, pH buffers, etc., which may be useful in the transfer processes. Especially useful results have been obtained, however, when said imagereceiving layers comprise a major portion of such polymers.
• poly-4-vinylpyridine poly-N-vinylpyrrolidone
• nylons such, for example, as N-methoxymethyl polyhexamethylene adipamide.
• derivatives of polyvinyl alcohol polymers which can be converted to polyvinyl alcohol through hydrolysis.
• partial esters and acetals such as partially hydrolyzed polyvinyl acetate, a partial acetal of polyvinyl alcohol and 4-pyridine carboxaldehyde and a partial acetal of polyvinyl alcohol and p-trimethylaminobenzaldehyde p-toluene sulfonate.
• the imagereceiving layer comprises copolymers of vinyl alcohol or derivatives of polyvinyl alcohol, it is desirable for best results that such copolymers and derivatives comprise a major portion of segments.
• the amount of boron compound used will vary with many factors such, for example, as the original color fastness of the dye developers, the amount of sunlight the colored image will be exposed to during its life expectancy, etc.
• the amount of stabilizer employed to provide protection may be referred to as an effective amount, i.e., an amount efiective to give the desired protection, and it will be understood that such an amount will vary with factors, such as mentioned above, and can be readily determined through color-fading tests which will hereinafter be described.
• swabbing or coating solutions containing about 1 to 2% of the boron compound will be effective in enhancing the color stability of the images.
• Example 1 A subcoated film support was coated with a methanolwater solution (1 to 9 by volume comprising):
• Example 2 A subcoated film support was coated with an aqueous coating solution comprising:
• Example 3 A subcoated film support was coated with a coating solution comprising:
• Example 4 A subcoated film support was coated with a coating solution comprising:
• a subcoated film support was coated with an aqueous coating solution comprising:
• the image-receiving elements prepared in the above examples were used in diffusion transfer processes employing multilayer photosensitive elements prepared in a manner similar to that disclosed in the above-mentioned copending application Serial No. 748,421 (now U.S. Patent No. 2,983,606).
• the photosensitive elements comprised a support carrying a red-sensitive silver halide emulsion stratum, a green-sensitive silver halide emulsion stratum and a blue-sensitive silver salide emulsion stratum; said emulsions having disposed in separate alkali-permeable layers behind them, re-
• a cyan dye developer a magenta dye developer and a yellow dye developer.
• the particular dye developers employed in the photosensitive elements were (1) 1,4 bis [or methyl 5 (2,5' di-hydroxyphenyD- ethylamino]-anthraquinone (a cyan dye developer), (2) 2 [p (2,-5 dihydroxyphenethyl) phenylazo]- 4-propoxy-l-naphthol (a magenta dye developer), and (3) 1 phenyl 3 n hexyl carboxamido 4 [p- (hydroquinonylethyl)-phenylazo]-5-pyrazolone (a yellow dye developer).
• IMAGE-RECEIVING ELEMENT OF EXAMPLE 1 IMAGE-RECEIVING ELEMENT OF EXAMPLE 2 [Percent fading] Unswabbed Swabbed 20 Hours 40 Hours 20 Hours 40 Hours Red Filter 45 67 7 9 Green Filter-.. 91 96 40 56 Blue Filter 78 85 55 64. 5
• the boron compound may be used in a latent form and placed in the image-receiving element prior to the use of such element in a diffusion transfer process. During processing, such boron compound may be rendered active by the processing solution to provide borate ions to stabilize the image.
• a latent boron compound is a hydrolyzable borate ester.
• said filmforming material comprises a mixture of polyvinyl alcohol and poly-4-vinylpyridine.
• said filmforming material comprises a mixture of polyvinyl alcohol and a partial acetal of polyvinyl alcohol and ptrimethylammonium benzaldehyde p-toluene sulfonate.
• said dye developer is selected from the group consisting of am and anthraquinone dye developers.

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• Physics & Mathematics (AREA)
• General Physics & Mathematics (AREA)
• Silver Salt Photography Or Processing Solution Therefor (AREA)

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Cited By (8)

Citations (12)

• 0
  • BE BE614693D patent/BE614693A/xx unknown
• 1961
  • 1961-03-06 US US93309A patent/US3239338A/en not_active Expired - Lifetime
• 1962
  • 1962-03-06 DE DEJ21395A patent/DE1172117B/de active Pending
  • 1962-03-06 GB GB8629/62A patent/GB946012A/en not_active Expired

Patent Citations (12)

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