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
  • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
  • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
  • G03C7/407—Development processes or agents therefor
  • G03C7/413—Developers
  • G03C7/4136—Developers p-Phenylenediamine or derivatives thereof

Definitions

• This invention relates to photography, and more particularly, photographic developers for use in reversal processing of photographic color films and papers.
• mul-ti-layer photographic elements used for color photography, there are usually three selectively sensitive emulsion layers coated on one side of a photographic support.
• the uppermost layer is generally bluesensitive
• the next layer generally comprises a yellow filter
• the next layer is generally green-sensitive.
• the emulsion layer adjacent to the support is generally red-sensitive.
• the yellow filter layer located between the blueand green-sensitive layers serves to absorb the blue radiation which may be transmitted through the blue-sensitive layer to the underlying layers, which are sensitive to the blue region of the spectrum, in addition to the red or green regions of the spectrum.
• multilayer photographic elements contain additional silver halide emulsion layers or other interlayers for specialized purposes.
• Multi-layer materials of the type which can be used in the present invention have been previously described in the prior art, such as Mannes et al. US. Patent 2,252,718, issued August 19, 1941.
• Color materials of the type employed in the present invention include those which are intended primarily for reversal color processes, in which the exposed material is given a conventional black-and-white negative development, followed by a reversal exposure, or exposures, and finally color development.
• the color materials useful in our invention include those having a silver halide emulsion containing the color-forming materials or couplers in the emulsion, as well as color materials which are intended for processing in a color developer which contains the color couplers.
• an object of our invention to provide improved developers for reversal color photography. Another object is to provide a method of removing aldehydes whose presence is not desired in the developers used for processing reversal color materials. Other objects will become apparent from a consideration of the following examples and description.
• balancing developing agents serve two functions, in general. First, such balancing developers act as antioxidants and they frequently react with oxidized color developer through a cross-oxidation reaction, which regenerates the desired color developer. Secondly, such balancing developing agents react directly with the exposed silver halide as an auxiliary developer. The desired photographic effects of these balancing developing agents in the cyan color developer are (1) scooped out red toe, (2) increased red speed, (3) the overall red contrast increases and (4) ice the inherent high definition of the cyan color developer is not appreciably reduced.
• balancing developing agents which fill the above requirements do have adverse effects in the reversal color developers customarily employed, in that they frequently react with the silver halide to produce oxidized balancing developers and metallic silver.
• these balancing developing agents can react with oxidized color developing agent generating a Schiifs base, which latter ingredient undergoes rather rapid hydrolysis in the strongly alkaline color developers to produce free aldehyde.
• Balancing developing agents which are particularly useful, but which have the objectionable property of forming Schiifs bases, include compounds embraced by the following general formula:
• R represents an aralkyl group, such as benzyl, which may or may not contain additional substituents, such as hydroxyl, amino, nitro, chloro, bromo, alkyl (e.g., methyl, ethyl, etc.), etc., and R represents a p-hydroxyphenyl group which can be further substituted by lower alkyl groups, such as methyl, ethyl, etc. Balancing developing agents which are particularly useful and are embraced by Formula I above, include the following:
• R represents a monocyclic aryl group of the benzene series, such as phenyl, hydroxyphenyl, chlorophenyl, aminophenyl, sulfophenyl (including alkali metal salts thereof, such as sodium and potassium), tolyl, ethylphenyl, etc.
• a primary amine which has a hydroxyl, carbonyl, or amino (substituted or not) group attached to the primary amine radical, in the color developer.
• Typical amines which can be used in the form of their free base, or more conveniently in the form of their acid addition salts (e.g., hydrochloride, sulfate, phosphate, etc.) include semicarbazide, hydrazine, carbohydrazide, hydroxylamine, etc.
• the amines useful in practicing our invention can be utilized in various concentrations, depending upon the concentration of balancing developer used, the concentration of color developer, etc. In general, we have found that from'about 0.1 to about 5.0 grams per liter of amine are satisfactory for the purposes of our invention. It is apparent that small amounts of amine can be used in those cases where the amine has some undesired developing or solvent action of its own toward silver halide, such "as is the case for hydrazine and its salts. In the case of those amines which have little or no developing or solvent action of their own toward silver halide, larger amounts can be easily tolerated without having any adverse effects upon the color development.
• the most advantageous concentration can be determined by developing a series of test strips of silver halide emulsions wherein the concentration of the amine, as well as the concentration of the developing agent, is varied.
• the usual addenda can be employed in the developers, such 'as strongly alkaline agents (e.g., sodium carbonate, potassium carbonate, sodium hydroxide, etc.), restraining agents, such as potassium bromide or iodide, stain preventatives and antioxidants, such as alkali metal sulfites, etc.
• Our invention is primarily directed to the development .of the ordinarily employed gelatino-silver-halide developing-out emulsions, e.g., gelatino-silver-chloride, -chlorobromide, -chloroiodide, -chlorobromiodide, -bromide and .-bromiodide developing-out emulsions. While the results in the following examples were obtained using gelatinosilver-bromiodide emulsions, excellent results can also be obtained using other silver halide emulsions.
• gelatino-silver-halide developing-out emulsions e.g., gelatino-silver-chloride, -chlorobromide, -chloroiodide, -chlorobromiodide, -bromide and .-bromiodide developing-out emulsions. While the results in the
• Photographic silver halide emulsions useful in our invention can also contain such addenda as chemical sensitizers, e.g., sulfur sensitizers (e.g., allyl thiocarbamide, thiourea, allyl isothiocyanate, cystine, etc.), various gold compounds (e.g., potassium chloroaurate, auric trichloride, etc.) (see U.S.
• the advantages of our invention are particularly outstanding in reversal color photographic processes wherein the color-forming compounds, or couplers, are incorporated in the color developing baths.
• the advantages of our invention are also outstanding in reversal color processes where a color film containing couplers in the emulsions (or alternatively in the color developers) has been given a hardening treatment in a bath prior to development (color or black-and-white) so that development can be performed at a higher temperature and in a shorter period of time.
• Such hardening prebaths generally contain an aldehyde hardener, such as formaldehyde or succinaldehyde.
• one of the above-identified amines can also be incorporated in a black-and-white or color negative developer to avoid the undesirable effects of the free aldehyde.
• the free aldehyde has alparticularly undesirable efiect in development of the color image in that it spontaneously reacts with the coupler (e.g., magenta or yellow) by an irreversible reaction, thereby causing a loss of color density.
• the pH ofthe developers useful in our process can be varied, depending upon the particular material which is to be processed therein.
• Typical. color-forming compounds or, couplers which are. useful in color. photography, according to our invention include the following:
• Couplers which are useful in photographic silver halide emulsion layers include couplers 65-77 in column 5 of US. Patent 2,956,876.
• Other couplers suitable for use in the emulsions of our invention include those described in Spence and Carroll U.S. Patent 2,640,776, issued June 2, 1953; Weissberger et al. U.S. Patent 2,407,210, issued September 3, 1946, and Weissberger et al. US. Patent 2,474,293, issued June 28, 1949.
• color-forming developers which can be especially useful in our invention include aromatic primary amines containing an amino (substituted or not) or hydroxyl substituent. Phenylenediamines and substituted derivatives thereof containing a primary amino group have been found to provide excellent results in our invention when employed in combination with a balancing developing agent and at least one amine of the type indicated above.
• Typical of such colorforming developers are the sulfonarnido substituted pphenylenediamines disclosed in Weissberger US. Patent 2,548,574, issued April 10, 1951, the substituted p-phenylenediamines disclosed in Weissberger et al. US. Patent 2,566,271, issued August 28, 1951.
• the first developer i.e., black-and-white negative developer, employed in the process of our invention is generally a rapid developer of the MQ type, i.e., a combination of hydroquinone and Elon developer (p-N-methylaminophenol).
• MQ a rapid developer of the MQ type
• Elon developer p-N-methylaminophenol
• Other black-and-white developers such as hydroquinone alone, pyrazolidone developers (e.g., 1- phenyl 3 pyrazolidone, 4,4-dimethyl-1-phenyl-3-pyrazolidone, etc.) can also be used.
• the photographic silver halide emulsions useful in the process of our invention can be prepared according to known methods, such as those described in Hewitson and McClintock US. Patent 2,618,556, issued November 18, 1952, for example. Of course, emulsions prepared by other methods can be used to equal advantage in our invention. These emulsions can be chemically sensitized or not, as mentioned above. Additional chemical sensitizers useful in our invention comprise those disclosed in US. Patent 2,886,437, issued May 12, 1958, in the name of D. E. Piper.
• Example 1 A portion of a gelatino-silver-bromiodide emulsion which had been sensitized with a sulfur compound and a gold salt as mentioned above, was coated on a cellulose acetate support. The coating was then dried and cut into several strips. One strip of each coating was then exposed for & second to a 500-wattt, 3000 K. light source on an Eastman Type 1b sensitometer. One of the exposed 8 strips was then developed 'for 3 minutes in a "developer having the following composition:
• the strip was then washed for about 2 minutes.
• the strip was then washed for about 10 minutes in water and treated for about 12 minutes in a silver bleach bath having the following composition:
• Example 2 A multi-layer photographic element of the type described in Mannes et al. US. Patent 2,252,718, issued August 19, 1941, was exposed to an original multi-colored scene and developed for about 3 /2 minutes at 80 F. in a developer having the following composition:
• Quadrofos g 0.6 Sodium sulfite g 12.0 p-N-methylaminophenol sulfate g 5.0 Sodium hydroxide g. 1.0 Hydroquinone g 2.0 Sodium sulfite g 6.0 Sodium carbonate g 35.0 Potassium iodide (0.1% solution) rnl 10.0 Sodium bromide g 3.0 Sodium thiocyanate g 1.75
• the photographic element was then spray washed with water for about /2 minute and given an exposure to red illumination of 1100 ft. candle seconds.
• the exposed material was then developed in a cyan developer having the following formula:
• the photographic element was then washed for about /2 minute with water and exposed to blue light of 300 ft. candle seconds intensity and developed in a yellow color developer containing a phenylenediamine color-developing agent, such as 4-amino-N,N-diethylaniline hydrochloride and a yellow coupler, such as Coupler No. 47 from column 4 of US. Patent 2,956,876.
• a phenylenediamine color-developing agent such as 4-amino-N,N-diethylaniline hydrochloride and a yellow coupler, such as Coupler No. 47 from column 4 of US. Patent 2,956,876.
• the photographic element was then washed and fogged chemically by treatment with a sodium borohydride solution, as described in Henn et al. US. application Serial No. 699,478, filed November 29, 1957 (now US. Patent 2,984,567, issued May 16, 1961).
• magenta color developer containing a color developing agent, such as 4-amino-N,N-diethyl- 3-methylaniline hydrochloride and a magenta coupler, such as Coupler No. 30 in column 4 of US. Patent 2,956,876.
• a color developing agent such as 4-amino-N,N-diethyl- 3-methylaniline hydrochloride
• magenta coupler such as Coupler No. 30 in column 4 of US. Patent 2,956,876.
• the amines of our invention are also useful when incorporated into the first or negative developer in a reversal color process. While this first developer produces a black-and-white image, the function of the amine is the same as in the color developer in that it acts as a scavenger of any aldehyde which carries over into the first developer from the prebath containing an aliphatic aldehyde, such as formaldehyde or succinaldehyde.
• a typical first developer for use in a reversal color process which can be used in our invention is as follows:
• hydroxylamine sulfate instead of hydroxylamine sulfate, other amines, such as carbohydrazide, 1.0 g./liter, or any of the other aboveidentified amines can be used. Since only a black-andwhite image is produced in the first developer, it is obvious that the amount of amine stabilizer used is not nearly as important as in the case of the color developers.
• a photographic developer for producing a color image comprising an aqueous alkaline solution of a pphenylene-diamine photographic developing agent, a p- N-aralkylaminophenol, and a compound selected from the class consisting of (A) a primary amine selected from the class consisting of hydroxylarnine, semicarbazide, hydrazine, carbohydrazide, biuret, aminoguanidine, methylsemicarbazide and water-soluble salts of said compounds, and (B) Girards reagent.
• a photographic developer for producing a color image comprising an aqueous alkaline solution of a pphenylene-diamine photographic developing agent, a balancing developing agent selected from those represented by the following general formula:
• R represents an aralkyl group and R represents a p-hydroxyphenyl group, and a compound selected from the class consisting of hydroxylamine and a water-soluble salt thereof.
• a photographic developer for color photography comprising an aqueous alkaline solution of a p-phenylenediamine photographic developing agent, a balancing developing agent selected from those represented by the following general formula:
• R represents an aralkyl group and R represents a p-hydroxyphenyl group, and semicarbazide.
• a photographic developer for color photography comprising an aqueous alkaline solution of a p-phenylenediamine photographic developing agent, a balancing developing agent selected from those represented by the following general formula:
• R represents an aralkyl group and R represents a p-hydroxyphenyl group, and carbohydrazide.
• a photographic developer for color photography comprising an aqueous alkaline solution of a p-phenylenediamine photographic developing agent, a balancing developing agent selected from those represented by the following general formula:
• R represents an aralkyl group and R represents a p-hydroxyphenyl group, and a compound selected from the class consisting of hydrazine and a water-soluble salt thereof.
• R represents an aralkyl group and R represents and (B) Girards reagent.
• R represents an aralkyl group and R represents a p-hydroxyphenyl group and a compound selected from the class consisting of hydroxylamine and a water-soluble salt theerof.
• R-NHR wherein R represents an aralkyl group and R represents a p-hydroxyphenyl group, and semicarbazide,
• R represents an aralkyl group and R represents a p-hydroxyphenyl group, and carbohydrazide.
• R represents an aralkyl group and R represents a p-hydroxyphenyl group, and a compound selected from the class consisting of hydrazine and a water-soluble salt thereof.
• a photographic developer for color photography comprising an aqueous alkaline solution of a p-phenylenediamine developing agent, a balancing developing agent selected from those represented by the following general formula:
• R-NHR wherein R represents an aralkyl group and R represents a p-hydroxyphenyl group, a compound selected from the class consisting of (A) a primary amine selected from the class consisting of hydroxylamine, semicarbazide, hy-
• a photographic developer for color photography comprising an aqueous alkaline solution of a p-phenylenediamine photographic developing agent, a p-N-aralkylaminophenol, a compound selected from the class consisting of (A) a primary amine selected from the class consisting of hydroxylamine, semicarbazide, hydrazine, carbohydrazide, biuret, aminoguanidine, methylsemicarbazide and water soluble salts of said compounds and (B) Girards reagent, and a phenolic coupler capable of coupling with the oxidation products of said p-phenylenediamine developing agent to produce a cyan image.

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

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Cited By (20)

Citations (7)

• 0
  • BE BE613239D patent/BE613239A/xx unknown
• 1961
  • 1961-02-01 US US86288A patent/US3141771A/en not_active Expired - Lifetime
  • 1961-12-20 DE DE19611422855 patent/DE1422855A1/de active Pending
• 1962
  • 1962-02-01 GB GB3824/62A patent/GB995035A/en not_active Expired

Patent Citations (7)

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