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
  • G03C5/29—Development processes or agents therefor
  • G03C5/305—Additives other than developers
• • 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
  • G03C5/29—Development processes or agents therefor
  • G03C5/30—Developers

Definitions

• This invention is related to photography, including developer compositions for use in rapid processing of color photographic materials and rapid processes for color photographic materials.
• Multilayer, multicolor photographic materials are well known in the art. Some of these materials contain incorporated color-forming couplers in the appropriately sensitized silver halide emulsion layers. Usually a cyan-forming (e.g., phenolic or naphtholic) coupler is incorporated in the red-sensitized silver halide emulsion layer, a magenta-forming (e.g., 5-pyrazolone coupler is incorporated in the green-sensitized silver halide emulsion layer and a yellow-forming open chain (e.g., acylacetanilide, an acylacetamide, a pivalylacetanilide, a pivalylacetamide, etc.) coupler is incorporated in the blue-sensitive silver halide emulsion layer.
• a cyan-forming (e.g., phenolic or naphtholic) coupler is incorporated in the red-sensitized silver halide emulsion layer
• these layers are coated on a support in the same order mentioned, however, they are sometimes coated on the support in other orders.
• the other color materials do not contain incorporated couplers, so the appropriate coupler is usually incorporated in separate color developer solutions used to color develop the differently sensitized silver halide emulsion layers.
• a cyan-forming coupler is incorporated in the developer used to form a cyan dye image in the red-sensitized layer
• a magenta-forming coupler is used in the developer solution that forms the magenta image in the green-sensitive layer
• a yellow-forming coupler is used in the developer solution that forms the yellow image in the blue-sensitive layer.
• Photographic developer compositions are desired which make it possible to combine the prehardening and development functions in a single step so that the number of steps required in the processing of color material can be reduced.
• Rapid color development processes are desired which require fewer process steps and shorter processing times than prior art processes.
• Another object is to provide a novel hardener-developer composition which is used to advantage in rapid color processing using fewer process steps.
• my hardener-developer composition comprises a chelate compound inorganic developing agent for silver halide and a hardening agent for photographic hydrophilic colloid layers.
• My rapid process is made possible by a substitution of inorganic developers for the conventional organic developers which makes it possible to develop rapidly at low pHs and in the presence of hardening agents. In this way, the prehardening and development are accomplished in a single step which is not possible in conventional color processes because of the reaction of aldehyde hardeners with emulsion incorporated color-forming couplers at the high pHs required by organic developing agents.
• the chelate compound, inorganic developing agents for silver halide used according to my invention include chelate compounds of a metal ion, such as, Ti+++, V+++, Fe chelated by a polybasic compound having one of wherein L and L each represent radicals, such as H I?
• Q (Q3 M and M each represent the same or different members, such as, hydrogen, an alkali metal, e.g., sodium, potassium, lithium, etc., and an ammonium group, e.g., ammonium, triethanol ammonium, triethyl ammonium, etc.;
• Q, Q Q and Q each represent the same or diiferent member, such as, hydrogen, an alkali metal, e.g., sodium, potassium, lithium, etc., an ammonium group, e.g., dium, potassium, lithium, etc., an ammonium group, e.g., ammonium, triethanol ammonium, triethyl ammonium, etc., an alkyl group, e.g., methyl, ethyl, propyl, butyl, cyclopentyl, cyclohexyl, etc., including an aralkyl group, e.g., benzyl, fl-phenethyl,
• radical, a NR radical, etc,;
• R and R each represent the same or different members, such as, hydrogen, a lower alkyl group, e.g., methyl, chloromethyl, hydroxyethyl, ethoxyethyl, bromoethyl, propyl, butyl, cyclopentyl, cyclohexyl, etc., including an aralkyl group, e.g., benzyl, 8- phenethyl, o-acetamidobenzyl, etc., and including a heterocyclylalkyl group, e.g., pyrrolidylmethyl, pyrrolidylbutyl, benzothiazolylmethyl, tetrahydroquinolylmethyl, etc., an alkoxy group, e.g., methoxy, ethoXy, butoxy, etc., a phenyl group, e.g., phenyl, carboxy
• M represents a member selected from the class consisting of hydrogen, an alkali metal, e.g., sodium, potassium, lithium, etc., and an ammonium group, e.g., ammonium, triethanol ammonium, triethyl ammonium, etc.;
• Q and Q each represent the same or different member, such as, hydrogen, an alkali metal, e.g., sodium, potassium, lithium, etc., an ammonium group, e.g., ammonium, triethanol ammonium, triethyl ammonium, etc., an alkyl group, e.g., methyl, ethyl, propyl, butyl, cyclopentyl, cyclohexyl, etc., including an aralkyl group, e.g., benzyl, B-phenethyl, oacetamidobenzyl, etc., and including a heterocyclylalkyl group, e.g., pyrrol
• L represents a radical having the formula (Q M30 0- 0r (Q7O)I O
• M represents a member, such as, hydrogen, an alkali metal, e.g., sodium, potassium, lithium, etc., and an ammonium group, e.g., ammonium, triethanol ammonium, triethyl ammonium, etc.
• Q and Q each represent the same or different member, such as, hydrogen, an alkali metal, e.g., sodium, potassium, lithium, etc., an ammonium group, e.g., ammonium, triethanol ammonium, triethyl ammonium, etc., an alkyl group, e.g., methyl, ethyl, propyl, butyl, cyclopentyl, cyclohexyl, etc., including an 4 a
• (CH2)h-L group a phenylene group, e.g., o-phenylene, p-phenylene, etc., and a cyclohexylene group
• R, R R R R R R and R are as described previously; it is as described previously
• k represents an integer of from 2 to 4
• L rep resents a radical, such as those of the formulas H (Q M4OO and (Q5)
• OP O M represents a member, such as, hydrogen, an alkali metal, e.g., sodium, potassium, lithium, etc., and an ammonium group, e.g., ammonium, triethanol ammonium, triethyl ammonium, etc.
• Q and Q each represent a member, such as, hydrogen, an alkali metal, e.g., sodium, potassium, lithium, etc., an ammonium group, e.g., ammonium, triethanol ammonium, triethyl ammonium, etc.,
• illustrative chelating agents used to advantage according to my invention are the following which illustrate polycarboxylic acids and polyphosphonic acids (and their salts) of Formula I:
• the chelating compound inorganic developing agents of my invention are advantageously prepared by contacting the metal ion, preferably Ti+++, V+++ or Fe with an aqueous solution of my chelating compounds including those of Formulas I and II.
• the metal ions are advantageously supplied by dissolving any suitable watersoluble salt of the metal desired including, for example, a halide, e.g., chloride, bromide, fluoride, iodide, a sulfate, etc.
• a halide e.g., chloride, bromide, fluoride, iodide, a sulfate, etc.
• salts used to advantage include:
• Titanium trichloride (2,) Titanium tribromide, (3') Titanium triiodide
• Vanadium trichloride (7) Vanadium tribromide, 8) Vanadium triiodide, (9) Vanadium trifluoride, Ferrous sulfate,
• My chelate compound inorganic developing agents are prepared and isolated in the dry form, such as, titanous oxalate, for example, and supplied as a single component to be added to the hardening agent or alternatively the appropriate chelating agent and an appropriate source of the desired metal ion are supplied as separate components that are added to the hardening agent to prepare my hardener developer compositions.
• My compositions are advantageously prepared and stored in the dry form for ease of storage and shipping or can be prepared directly from the raw materials in a concentrated solution form or as a working developer solution.
• My chelate compound inorganic developing agents or the components used to make them are readily water-soluble and my dry compositions are easily and quickly made up into the concentrated solution form for subsequent dilution for the working developer solution.
• Organic aldehyde hardening agents used in photographic processing to harden hydrophilic colloids such as, gelatin and gelatin substitutes are used to ad vantage in my hardener developer compositions.
• Organic aldehyde hardening agents used to advantage include those represented by the formulas:
• R represents a divalent member, e.g'., an alkylene group (e.g., ethylene, l-methylethylene, l-butylethylene, 1,1-dimethylethylene, 1,2-dimethylethylene, 1- methoxyethylene, 1-methyl-2-methoxyethylene, l-butoxyethylene, propylene, l-methylpropylene, l-butylpropylene, l-methyl2-methylpropylene, 1-methyl-2-ethoxypropylene, 1 butoxypropylene, butylene, 1 methylbutylene, 1- methoxybutylene, l-hydroxybutylene, 2-hydroxybutylene, l-hydroxyethylene, l-hydroxypropylene, 1,2 cyclopentylene, 1,3 cyclopentylene, 1,2 cyclobutylene, 1,3 cyclobutylene, etc.), a vinylene group (e.g., vinylene, l-methylvinylene, 1 butylvinylene, 1,2 dimethylvin
• aldedhydes are known in the chemical art. It is to be understood that the bisulfite addition complexes of the above and and other aldehydes are used advantageously as the hardening agent in my hardener-developing compositions.
• One aldehyde, a mixture of an aldehyde and its bisulfite addition complex, mixtures of two or more aldehydes or mixtures of aldehydes and bisulfite addition complexes of aldehydes are used to advantage as the hardening agent in my compositions.
• Aldehyde precursors which hydrolyze in acid solution to release an aldehyde are also used to advantage. For example, dimethoxytetrahydrofuran is used to advantage to form succinaldehyde in my compositions.
• My developer compositions advantageously have pHs in the range from about 0.5 to about 6.9. The preferred range being from about 4 to about 5.5.
• the concentration of the components of my hardenerdeveloper composition are advantageously used over a wide range.
• the optimum concentration can be readily determined by methods well known in the art and need not be discussed further here.
• suificient chelating compound inorganic developing agent is included in my composition to produce a concentration in the range from about 1 to about 400 grams per liter when dissolved and sufiicient aldehyde hardening agent(s) to produce a concentration in the range of from about 0.1 to about 60 grams per liter when dissolved in water.
• a sufficient amount of the chelating agent is provided to produce a concentration in the range of from about 0.1 to about 200 grams per liter and a sufficient amount of the water-soluble metal salt is provided to produce a concentration in the range of from about 1 to about 400 grams per liter when disolved in water.
• Hardener-developer compositions are prepared containing mixtures of titanium trichloride, ethylenediaminetetraacetic acid, tetrasodium salt, and formaldehyde alone and in combination with succinaldehyde as indicated in Table I below.
• composition Titanium trichloride g 1through400 Ethylenediaminetetraaectic acid, tetrasodium salt g through 200 Formaldehyde (37%) ml lthrough 150 succinaldehyde g Othroug'n 34 pH of a water solution of this composition 0.5 through 6.9
• Multilayer color film containing incorporating cyanforrning coupler in the red-sensitive layer, magentaforming coupler in the green-sensitive layer and a yellowforming coupler in the blue-sensitive layer is exposed to a color image.
• One piece of the exposed color film is given the ECO2 Process steps listed in Table II below.
• the processing solutions used are those described in the Manual for Processing of Ektachrome Commercial Film (Process ECO-2) published by and available from Motion Picture and Education Markets Division, Eastman Kodak Company, Rochester, N.Y. 14650. Ektachrome is a registered trademark of Eastman Kodak Company.
• Other pieces of the exposed color film are given my process steps listed in Table III below using one liter hardener-developer solutions prepared from compositions of Table I.
• the other solutions e.g., neutralizer, reversal bath, color developer, acid stop, bleach, fix, and stabilizer are the same as used in the ECO-2 Process for the respective steps.
• Example 2 Similar results are obtained when Example 1 is repeated using my hardener-developer composition in the lO-step process listed below in Table IV place of the 13-step process listed in Table III of Example I.
• Hardener-developer compositions are prepared containing mixtures of titanous oxalate and succinaldehyde indicated in Table V.
• Example I is repeated using one liter solutions of the compositions of Table V in place of the compositions of Table I.
• the results obtained in this example are similar to those obtained in Example I.
• Example 1 is repeated using one liter solutions of the compositions of Table VI in place of the compositions of Table I.
• the results obtained in this example are similar to those obtained in Example 1.
• the preferred composition of Example 4 is found to have sufiicient titanium trichloride to produce a concentration of 26 grams per liter, suflicient diethylenetriamine pentaacetic acid, pentasodium salt to produce a concentration of 160 milliliters per liter, sufiicient formaldehyde to produce a concentration of 5.2 grams per liter and suflicient succinaldehyde to produce a concentration of 8 grams per liter when dissolved in the solution.
• Example 1 is repeated using a hardener-developer having the composition shown in Table VII in place of that shown in Table I.
• Example 2 The results obtained in this example are similar to those obtained in Example 1. Temperatures of about 212 F. are preferred for purposes of rapid access to the processed film, however, temperatures down to 65 F. are advantageously used in conventional processing machines. At
• Example 1 is repeated using a hardener-developer having the composition shown in Table VIII.
• any of the other chelate compound inorganic developing agents for silver halide formed by chelating Ti+++, V+++, or Fe++ with any of the chelating agents of Formulas I and II are used with any of the hardening agents of my invention as the hardener-developer composition in my rapid color process.
• the following example will illustrate the use of my hardener-developer composition as a replacement for the prehardener, wash and first developer steps in a color process for a color film that does not contain incorporated colorforming couplers.
• EXAMPLE 7 Exposed multilayer color film not containing colorforming couplers is advantageously processed in a K-lZA process using my hardener-developer solutions, such as those described in Examples 1 through 6, in place of the K-12A process, prehardener, wash, and first developer solution.
• the Ti+++, V+++, or Fe++ ions in the chelate (developing agent) are oxidized to the Ti++++, V++++, or Fe+++ ions, respectively.
• the oxidized developing agents in my hardener-developer solutions are advantageously reduced (to the lower valence state) by electrolysis, using conventional equipment.
• Aldehyde hardening agent can be added to the electrolytically rejuvenated solution as is necessary and the hardener-developer solution reused to harden-develop additional photographic material. This is an important advantage provided by use of my hardenerdeveloper compositions that is not provided by conven- 1 1 tional developer solutions with organic developers used in prior art color processing.
• My hardener-developer compositions are valuable for use in my rapid color processes. These hardener-developer compositions are characterized by having pHs in the range of from 0.5 to 6.9 which makes them particularly valuable for combining the hardening and development steps in a color process for processing color materials containing incorporated couplers because at their pHs the aldehyde hardening agents do not react with the color-forming coupler. This is a very valuable technical advance since prior art developer solutions used in color processing require higher pHs where any aldehyde present would react very detrimentally or disastrously with color-forming couplers present in the photographic element, thus making it impossible to combine the prehardening and developing functions in a single step.
• a hardener-developer composition comprising:
• a hardener-developer composition comprising:
• L and L represent radicals selected from the class consisting of those having the formulas M and M represent members selected from the class consisting of hydrogen, an alkali metal and an ammonium group; Q, Q Q and Q repersent members selected from the class consisting of hydrogen, an alkali metal, an ammonium group, an alkyl group, an aryl group, and a heterocyclic group; R, R R R R R R and R each represent a member selected from the class consisting of hydrogen, hydroxyl, an amino group, nitro, halogen, a lower alkyl group, and a lower alkoxy group, such that no single carbon atom in the chain contains more than one hydoxyl group, more than one amino group and more than one nitro group; d, e, f and g represent intergers of from 1 to 4; p represents an interger of from 1 to 2; X represents a member selected from the class consiting of oxygen, sulfur, a
• radical, and a NR radical
• R and R each represent members selected from the class consisting of hydrogen, a lower alkyl group and a group; It represents an integer of from 1 to 4
• L represents a radical selected from the class consisting of those having the formulas
• M represents a member selected from the class consisting of hydrogen, an alkali metal and an amonium group
• Q and Q each represent members selected from the class consisting of hydrogen, an alkali metal, an ammonium group, an alkyl group, an aryl group and a heterocyclic group
• a hardener-developer composition comprising:
• a water-soluble salt which upon solution in water forms ions selected from the class consisting of Ti+++, V+++, Pe++ and ions selected from the class consisting of chloride, bromide, iodide, fluoride, and sulfate;
• L and L represent radicals selected from the class consisting of those having the formulas M and M represents members selected from the class consisting of hydrogen, an alkali metal and an ammonium 13 group; Q, Q Q and Q represent members selected from the class consisting of hydrogen, an alkali metal, an ammonium group, an alkyl group, an ary group, and a heterocyclic group; R, R R R R R R and R each represent a member selected from the class consisting of hydrogen, hydroxyl, an amino group, nitro, halogen, a low alkyl group, and a lower alkoxy group, such that no single carbon atom in the chain contains more than one hydroxyl group, more than one amino group and more than one nitro group; d, e, f and g each represent integers of from 1 to 2; X represents a member selected from the class consisting of oxygen, sulfur,
• R and R each represent members selected from the class consisting of hydrogen, a lower alkyl group and a group; h represents an integer of 1 to 4; and L represents a radical selected from the class consisting of those having the formulas (Q M oo and (Q O)P M represents a member selected from the class consisting of hydrogen, an alkali metal and an ammonium group; Q and Q each represent members selected from the class consisting of hydrogen, an alkali metal, an ammonium group, an alkyl group, an aryl group, and a heterocyclic group; and
• L represents a radical selected from the class consisting of those having the formulas M3OC and (Q7O)P 0
• M represents a member selected from the class consisting of hydrogen, an alkali metal, an ammonium group, an alkyl group, an aryl group and a heterocyclic group
• Q and Q each represent members selected from the class consisting of hydrogen, an alkali metal, an ammonium group, an alkyl group, an aryl group, and a heterocyclic group
• i, j, m and n each represent integers of from 2 to 4
• Z represents a group selected from the class consisting of a group, a phenylene group and a cyclohexylene group, anda N '1 1 a 1'15 f u 2)hL group
• an aldehyde selected from the class consisting of formaldehyde, a succinaldehyde, a glutaraldehyde, a maleic dialdehyde, a cyclopentane dicarboxaldehyde, and a bisulfite addition complex or said aldehydes.
• a hardener-developer composition of claim 3 containing a sufiicient amount of the said water-soluble salt to produce a concentration in the range of from about 1 to about 400 grams per liter, a suflicient amount of the said chelating agent to produce a concentration in the range of from about 0.1 to about 200 grams per liter, and a sufficient amount of the said aldehyde hardening agent to produce a concentration in the range from about 0.1 to about 60 grams per liter when dissolved in water.
• An aqueous hardener-developer solution in accordance with claim 21 comprising titanium trichloride in the concentration range from about 1 to about 400 grams per liter, diethylene triamine pentaacetic 'acid, pentasodium salt in the concentration range of from about 0.1 to about 200 grams per liter, formaldehyde in the concentration range from about 0.3 to about 6 ml. per liter and succinaldehyde in the concentration range from 0 up to about 34 grams per liter.
• An aqueous hardener-developer solution of claim 11 containing 26 grams per liter of titanium trichloride, 160 ml. per liter of diethylene triamine pentaacetic acid, pentasodium salt, 5.2 grams per liter of formaldehyde and 8 grams per liter of succinaldehyde.
• An aqueous hardener-developer solution in accordance with claim 21 comprising:
• said solution having a pH of about 4.8
• a rapid process for Simultaneously hardening and developing a silver image in an exposed color photographic element comprising contacting said element with an aqueous hardener-developer having a pH of about 4 to 6.9 and a temperature of 65 to 212 F. comprising:
• a rapid process for simultaneously hardening and developing a silver image in an exposed color photographic element comprising contacting the said element with an aqueous hardener-developer solution having a pH in the range of from about 4 to about 6.9 and temperature 652)12 F. and containing:
• radical, and a NH radical
• R and R each represent members selected from the c ass consisting of hydrogen, a loyver alkyl group and a group
• h represents an integer of from 1 to 4
• L represents a radical selected from the class consisting of those having the formulas
• M represents a member selected from the class consisting of hydrogen, an alkali metal and an ammonium group
• Q and Q each represent members selected from the class consisting of hydrogen, an alkali :metal, an" ammonium group, an alkyl group, an aryl group, and a heterocyclic group
• V wherein L, L and L are as defined previouslyfL represents a radical selected from the class consisting of those having the formulas I 4;
• Z represents a group selected from the class consisting group, a phenylene group, a cyclohexylene group and a 5 R R2 R4 e i (CHz)h--L group; R, R R R R R R R R and R are
• a rapid process for simultaneously hardening and developing a silver image in an exposed colorlphotographic element comprising contacting said element with an aqueous hardener-developer having temperature of 6 5212 F, comprising:
• said solution having a pH of about 4.8
• a rapid process for processmg an exposed color photographic element comprising the steps at contacting the said element with:
• an aqueous hardening developer having a pH of about 4 to 6.9 and a temperature of about 65 to 212 F. comprising:
• compositionfor hardening gelatin and-develop ing exposed photographic silver halide comprising:
• a hardener-developer composition for hardening photographic hydrophilic colloid layers and developing exposed photographic silver halide comprising:
• At least one hardening agent for photographic hydrophilic colloid layers selected from the class consisting of formaldehyde, acrolein, dimethylglyoxyl, a succinaldehyde, a glutaraldehyde, a maleic dialdehyde, a cyclopentane dicarboxaldehyde, a cyclobutane dicarboxaldehyde, and a bisulfite addition complex of said aldehydes.
• An aqueous hardener-developer solution comprising:
• At least one aldehyde and a chelate compound produced by reacting a water soluble polyaminopolyacetic acid or a Water soluble salt thereof With titanium trichloride, said solution having a pH of about 4 to about 6.9.

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

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Cited By (7)

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• 1968
  • 1968-01-04 US US695564A patent/US3567441A/en not_active Expired - Lifetime
  • 1968-12-31 FR FR1602242D patent/FR1602242A/fr not_active Expired
• 1969
  • 1969-01-03 DE DE19691900332 patent/DE1900332A1/de active Pending
  • 1969-01-03 GB GB1228702D patent/GB1228702A/en not_active Expired

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