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

• Cur-X wherein X and X each represents a p-hydroxyanilino group of which the benzene ring may further be substituted by a member selected from the class consisting of an alkyl group having from one to four carbon atoms, a hydroxyalkyl group having from one to four carbon atoms, an alkoxy group having from one to four carbon atoms and a halogen atom, and the XCH group may be located at the 0- mor p-position to the position ofthe XCH -group.
• An improved color reversal development of a multilayer, multicolor photographic element is also claimed, where the improvement comprises utilizing, in at least one color developer used in the process, a water-soluble competing developing agent as above described.
• composition for preparing a color developer solution comprising a primary aromatic amino developing agent and the water-soluble competing developing agent described above.
• the present invention relates to a developer composition for color photography, and more particularly, to a color-forming developer composition containing a novel water-soluble competing developing agent.
• reversal color photographic light-sensitive elements which are to be developed in a coupler-containing developer are, after exposure, subjected to black and white development, and then, after being subjected to a reversal exposure, are processed in a color developer which contains couplers.
• This type of element usually has multiple emulsion layers which will include three selective light-sensitive emulsion layers.
• a support will carry the following layers: a lowermost red-sensitive emulsion layer, a green-sensitive emulsion layer, a yellow filter layer, a blue-sensitive emulsion layer, and an upper protective layer (formed on the support in the order given.).
• a color-forming developer used for developing such a reversal color photographic light-sensitive element usually comprises: an alkaline aqueous solution containing a p-phenylenediamine-type developing agent which has at least one primary amino group; a color-forming coupler; and additives, such as an alkali metal sulfite, e.g., sodium sulfite, an alkali metal bromide, e.g. sodium bromide, an alkali metal iodide, etc.
• an alkali metal sulfite e.g., sodium sulfite
• an alkali metal bromide e.g. sodium bromide
• an alkali metal iodide etc.
• a phenolic or naphtholic coupler as a cyan dye former
• a pyrazolone coupler as a magenta dyeformer
• an open-chain ketomethylene coupler as a yellow dye-former.
• a competing developing agent When subjecting a reversal color photographic element to cyan development using a color-forming developer containing a color former or coupler, to suppress the formation of cyan fogs in the green-sensitive and the blue-sensitive emulsion layers, a competing developing agent is incorporated into the cyan developer.
• N-benzyl-p-aminophenol is widely used as one such "competing developing agent.” It is generally known that the competing developing agent will reduce an oxidized color developing agent to the state of the original developing agent, and will reduce an exposed silver halide into metallic silver. The competing developing agent will thus contribute to suppressing cyan contamination in the blue-sensitive emulsion layer and, in particular, in the green-sensitive emulsion layer, therefore yielding a correct red reproduction of the subject photographed. This is due to the fact that the competing developing agent and the color developing agent will both compete for reaction with the exposed silver halide.
• a competing developing agent which may be employed in photographic processing must be capable of increasing the red contrast by removing cyan contamination, and 'r'nust be capable of also increasing the sensitivity of the red-sensitive emulsion layer. Furthermore, the competing developing agent must not reduce the maximum density of the red-sensitive emulsion layer; must not reduce the high degree of clarity of the cyan color developing agent; and must not reduce the photographic properties of the emulsion without also reducing the stability of the cyan developer.
• the present invention provides an improved color developer composition
• a primary aromatic amino developing agent comprising a color-forming coupler, an alkali, and a novel water-soluble competing developing agent having the formula:
• X and X each represents a p-hydroxyanilino group of which the benzene ring may further be substituted by a member selected from the class consisting of an alkyl group having from one to four carbon atoms, a hydroxyalkyl group having from one to four carbon atoms, an alkoxy group having from one to four carbon atoms and a halogen atom, and the X'-CH -group may be located at the 0-, mor p-position to the position of the X-CH -group.
• the present invention further provides a novel color reversal development process for multilayer, multicolor photographic elements which have been exposed through an original image, the element comprising a support coated with differently sensitive silver halide emulsion layers, one of said layers being red-sensitive, one of said layer being green-sensitive and one of said layers being blue-sensitive, in which the said exposed elements given a negative black and white development, selective reexposure of said red-sensitive layer with red light, treatment of said element with a cyan color developer, selective reexposure of the said blue-sensitive layer with blue light, treatment of said element with a yellow color developer, fogging the unexposed silver halide in the green sensitive layer, treating the said element with a magenta color developer, treating said developed element in a ferricyanidebromide bleach and then in a fixing bath, to leave in'said element a color reproduction of said original image.
• the improvement in said process specifically comprises the use, in at least one of said color developers, of a water-soluble competing developing agent having the formula:
• X and X each represents a p-hydroxyanilino group of which the benzene ring may further be substituted by a member selected from the class consisting of an alkyl group having from one to four carbon atoms, a hydroxyalkyl group having from one to four carbon atoms, an alkoxy group having from one to four carbon atoms and a halogen atom, and the X-CH group may be located on the 0-, mor p-position to the position of the X-CH -group.
• the invention further comprises a composition for preparing a color developing solution, the composition comprising a primary aromatic amino developing agent and a water-soluble competing developing agent above defined.
• Another object is to provide a color developer composition containing a novel competing developing agent which will yield a highly pure red reproduction, and which will also increase the sensitivity of a red-sensitive emulsion layer.
• Still a further object is to provide a competing developing agent which will not reduce the maximum density of a red-sensitive emulsion layer, will not reduce the clarity of a cyan color developing agent and which will not reduce the photographic properties of the emulsion. such as reversal sensitivity, red purity and the red filter density-blue filter density ratio. without reducing the stability of the cyan developer.
• the aforesaid objects of the present invention are accomplished according to this invention by using certain 01, adi(hydroxyanilino)-substituted xylenes as competing developing agents in color developer solutions.
• the water-soluble competing developing agents of the present invention include those represented by the formula:
• X and X each represents a p-hydroxyanilino group, of which the benzene ring may further be substituted by an alkyl group having from one to four carbon atoms such as methyl, ethyl, propyl, butyl; a hydroxy-alkyl group having from one to four carbon atoms, such as hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl; an alkoxy group having from one to four carbon atoms such as methoxy, ethoxy, propyoxy, butoxy; or a halogen atom; and the XCI-I -group may be located on the mor p-position with respect to the position of the X-CI-I -group.
• the color developer composition of the present invention comprises, therefore: (1) a primary aromatic amino developing agent, (2) a color-forming coupler, (3) an alkali material, and (4) a water-soluble competing developing agent having the formula (I).
• the competing developing agents of this invention are used to advantage in color developer solutions for processing color photographic elements in instances where it is desirable to control color contrast, fog, etc.
• the competing developing agents of the present invention are unexpectedly better than some known competing developing agents and are valuable for use in color photographic processing.
• the competing developing agent of the present invention is used by incorporation in a cyan color developer which contains a p-phenylenediamine type color developing agent, a phenolic or naphtholic cyan color former and an alkali, excellent results are obtained.
• the diffusing tendency of the compounds into the emulsion layers of multilayer photographic elements is lowered and therefore, only the upper layers, i.e., a blue-sensitive layer and a green-sensitive layer, are effectively subjected to the black and white development, while the lowermost red-sensitive layer is hardly developed. Consequently, the use of the competing developing agents of this invention provides such merit that the formation of cyan fog of blue-sensitive layer and green-sensitive layer is effectively prevented, while the decrease in density of cyan dye image of the red-sensitive layer can be prevented.
• the color developer containing the competing developing agent of this invention shows better stability or gives less degradation of its properties and provides images having good photographic characteristics when the developer is stored or repeatedly used for a long period of time, as compared with the same solution containing a conventional competing developing agent.
• Compound I a u'-di(p-hydroxyunilino[-p-xylene Compound 2 a. a'-di(p-hydroxyunllinnHit-xylene Compound 3 a. a-di(3-methyl-4-hydroxyunilinn)- p-xylene Compound 4 a. u'-di(3-methyl-4-hydroxyunilinu)- m-xylenc
• concentration of the competing developing agents of this invention will vary, depending upon the type and concentration of the color developing agent and coupler used in the color developer, and will also vary with the pH of the color developer. However, in general, a concentration of 0.0l-5.0 g./liter of developer is preferably employed. Further, it has been found that the most effective concentration utilized is about 0. l-l .0 g./liter.
• the competing developing agents of this invention are commonly used in the form of a salt, such as the hydrochloride, which is more stable than the free amine.
• the competing developing agents of this invention can be effectively used in any cyan color developer, magenta color developer or yellow color developer, but it is most effectively used in a cyan color developer.
• the color developing agent used in the color developer composition of this invention is a general p-phenylene diamine derivative, such as: N, N-diethyl-p-phenylenediamine sulfite; N, N-diethyl-3-methyl-p-phenylenediamine hydrochloride; 4- amino-3-methyl-N-ethyl-N-methanesulfonamido ethylaniline sulfate; 4-amino-3-methyl-N-ethyl-N-hydroxyethylaniline sulfate; N-ethyl-N-hydroxyethyl-p-phenylenediamine sulfate, etc.
• the p-aminophenols and their substituted materials may also be used.
• color formers used in this invention there are: 2,4-dichloro-l-naphthol; 2,4-dichloro-5- tolysulfonamido- 1 -naphthol; l-oxy-2-benzylnaphtham ide; 2,6-dibromol ,S-dihydroxynaphthalene; benzoylacetanilide; w-benzoyl-4-(p-toluenesulfonamido)acetanilide; l-phenyl-3- (m-nitrobenzoylamino)-5-pyrazolone; and cyanoacetyl coumaron.
• other color formers which are conven tionally utilized may be employed in this invention.
• acetic acid and a solid formed was separated, and recrystallized from n-butanol to yield l3 g. of a, a-di(p-hydroxyanilino)-p-xylene having a melting point of 1835-"? C.
• the hydrochloride of this compound is in the form of colorless needles having a melting point ofabove 300 C. (decomposed).
• EXAMPLE 1 A multilayer color photographic film was formed of the following layers (in the order given) on a photographic film support: a red-sensitive gelatino silver iodo-bromide emulsion layer, a green-sensitive gelatino silver iodo-bromide emulsion layer, a blue-absorbing yellow filter layer comprising colloidal silver, and a blue-sensitive gelatino silver iodo-bromide emulsion layer. This film was exposed by means of a sensitometer and subjected to the following processings:
• compositions of the processing baths used in the above processings are as follows:
• Cyan Color Developer Sodium sulfite 5.0 g. 2-Arnino-5N.N-diethylamino toluene hydrochloride 0.6 g. Sodium carbonate (mono-hydrate) 15.0 g. Potassium bromide 0.5 g. Potassium iodide (0.1% aq. solution.) 5 ml. 1.5-dihydroxy-2.fi-dibromonaphthalene 1.2 g. Sodium hydroxide 2.0 g. Water to make 1000 ml.
• Magenta Color Developer Sodium sulfite 5.0 g. Z-Amino-5-N,N-dietl ylaminotoluene hydrochloride 2.0 g. Potassium bromide 0.8 g.
• the competing developing agents shown in the following table were (individually) added to the cyan color developer, and the effect of the competing developing agents on the photographic properties of the film was measured.
• the photographic properties of the film processed are shown in the following table, with each of the three competing developing agents in which: (1 the reversal sensitivity is shown by the inverse logarithm of the amount of exposure at which the coupling density obtained corresponds to 1.0; 2) the purity of the red color reproduction is shown by the ratio of the red filter density to the green filter density (D /D of a portion of the film exposed to red light (called red patch): and (3) the ratio of the red filter density to the blue filter density (D /D of said portion is also shown.
• the ratio D /D or D,/D, is a value which illustrates the color purity of a reproduced color when a red object is reproduced in a color photograph, and the smaller than this value is, the better the reproduction.
• EXAMPLE 2 Using the same basic procedures as in example 1, a cyan color development was carried out. After being washed with water for eight minutes after the cyan development, the cyandeveloped color film was subjected to bleaching, washing and fixing, as in example i, to provide cyan-colored images. in this case, the photographic properties of the color photographs which were improved by the competing developing agent of this invention were measured, the results of which are shown in the following table.
• the reversal sensitivity (A) relates to the red-sensitive emulsion layer
• the cyan contamination density (B) is shown by the sum of the cyan coupling density in the portion of the green-sensitive emulsion layer exposed to red light and the cyan coupling density in the portion of the blue-sensitive emulsion layer exposed to red light.
• These two light sensitive emulsion layers are ones which will not be developed to any extent in a cyan color development, and hence, cyan coupling these portions causes undesirable developing fogs in the green-sensitive emulsion layer to be magenta coupled and undesirable fogs in the blue-sensitive emulsion layer to be yellow coupled. in other words, the cyan coupling causes color turbidity, which results in degrading of the quality of the color photographic image.
• EXAMPLE 3 The cyan color developer used in example 2 was forcibly degraded by developing 2800 sq. cm. ofa color film with 1000 ml. of the cyan developer in a light room. Thereafter, the same basic procedure used in example 2 was repeated using the thus degraded cyan developer, the results of which are shown in the following table. (in this experiment, the amount of competing developing agent used was the same as that in example l Reversal sensitivity. 2 Cyan contamination color density.
• the cyan developer containing the competing developing agent of this invention again gave excellent results in comparison to the cynn developer containing the known competing developing agent.
• Cyan Color Developer The photographic properties obtained by adding the competing developing agent of this invention to the cyan developer were compared with those obtained by adding thereto a conventional competing developing agent, N -benzylp-aminophenol hydrochloride.
• the amount and type of competing developing agent used are shown below:
• the competing developing agent of this invention illustrated an excellent effect during this experi ment, when compared with the known competing developing agent.
• a color developer composition comprising a primary aromatic amino developing agent, a color-forming coupler, an alkali, and a water-soluble competing developing agent having the formula:
• X and X each represents a p-hydroxyanilino group of which the benzene ring may further be substituted by a member selected from the class consisting of an alkyl group having from one to four carbon atoms, a hydroxyalkyl group having from one to four carbon atoms, an alkoxy group having from one to four carbon atoms and a halogen atom, and the X'-CH group may be located at the o-, mor p-position to the position of the X-Cll group.
• a color developer composition as in claim 1 containing a member selected from the class consisting of an alkali metal bromide, an alkali metal sulfite and an alkali metal iodide.
• a color developer composition of claim 1 containing a color-forming coupler selected from the class consisting of the phenolic couplers, the naphtholic couplers, the pyrazolone couplers, the coumarone couplers and the open-chain ketomethylene couplers.
• a color developer composition of claim 1 containing a primary aromatic amino developing agent selected from the class consisting of a 4-aminophenol and a p-phenylenediamine.
• a color developer composition as claimed in claim 1 comprising a primary aromatic amino developing agent, a color-forming coupler, an alkali, anda, a-di(p-hydroxyanilino)-p-xylene hydrochloride, wherein said competing developing agent is present in the amount of 0.01 to 5.0 g./liter of developer.
• a color developer composition as claimed in claim 1 comprising a primary aromatic amino developing agent, a color-forming coupler, an alkali, and a, a-di(p-hydroxyanilino)-m-xylene hydrochloride, wherein said competing developing agent is present in the amount of 0.01 to 5.0 g./1iter of developer.
• a color developer composition as claimed in claim 1 comprising a primary aromatic amino developing agent, a color-forming coupler, an alkali, and a, a'-di(3-methyl-4- hydroxyanilino)-p-xylene hydrochloride, wherein said competing developing agent is present in the amount of0.0l to 5.0 g./liter ofdeveloper.
• a color developer composition as claimed in claim 1 comprising a primary aromatic amino developing agent, a color-forming coupler, an alkali, and a, a'-di(3-methyl-4- hydroxyanilino)-m-xylene hydrochloride, wherein said competing developing agent is present in the amount of 0.01 to 5.0 g./liter of developer.
• X and X each represents a p-hydroxyanilino group of which the benzene ring may further be substituted by a member selected from the class consisting of an alkyl group having from one to four carbon atoms, a hydroxyalkyl group having from one to four carbon atoms, an alkoxy group having from one to four carbon atoms, and a halogen atom, and the XCl-l group may be located at the o-, mor p-position to the position of the XCH,-group.
• X and X each represents a p-hydroxyanilino group of which the benzene ring may further be substituted by a member selected from the class consisting of an alkyl group having from one to four carbon atoms, a hydroxyalkyl group having from one to four carbon atoms, an alkoxy group having from one to four carbon atoms and a halogen atom, and the X'-Cl-l -group may be located at the o-, m-, or p-position to the position of the X-Cl-l group.
• the improvement in the said process comprising the use of a, a'-di(phydroxyanilino)-p-xylene as a competing developing agent in the cyan developer solution, wherein the competing develop ing is present in the amount of 0.01 to 5.0 g./liter of the developer.
• the improvement in the said process comprising the use of a, a'-di(phydroxyanilino)-p-xylcne as a competing developing agent in the magenta developer solution, wherein the competing developing is present in the amount of 0.01 to 5.0 g./liter of the developer.
• composition for preparing a color developer solution comprising a primary aromatic amino developing agent and a water-soluble competing developing agent having the formula:
• X and X each represents a p-hydroxyanilino group of which the benzene ring may further be substituted by a member selected from the class consisting of an alkyl group competing developing agent is a, a-di(p-hydroxyanilino)-mxylene hydrochloride.
• composition as claimed in claim 14 wherein the competing developing agent is a, a'-di(3-methyl-4-hydroxyanilino)-p-xy1ene hydrochloride.
• composition as claimed in claim 14 wherein the competing developing agent is a, a-di(3-methyl-4-hydroxyanilino)-m-xylene hydrochloride.

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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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Citations (1)

• 1969
  • 1969-06-19 NL NL6909431A patent/NL6909431A/xx unknown
  • 1969-06-19 DE DE1931122A patent/DE1931122C3/de not_active Expired
  • 1969-06-20 GB GB31418/69A patent/GB1242656A/en not_active Expired
  • 1969-06-20 US US835216A patent/US3619156A/en not_active Expired - Lifetime

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