WO1981002934A1 - Photographic processing concentrates - Google Patents

Photographic processing concentrates Download PDF

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Publication number
WO1981002934A1
WO1981002934A1 PCT/US1981/000128 US8100128W WO8102934A1 WO 1981002934 A1 WO1981002934 A1 WO 1981002934A1 US 8100128 W US8100128 W US 8100128W WO 8102934 A1 WO8102934 A1 WO 8102934A1
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WIPO (PCT)
Prior art keywords
processing
photographic processing
concentrate
paste
agents
Prior art date
Application number
PCT/US1981/000128
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English (en)
French (fr)
Inventor
R Dillon
D Miroff
Original Assignee
Eastman Kodak Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Publication date
Application filed by Eastman Kodak Co filed Critical Eastman Kodak Co
Priority to BR8108307A priority Critical patent/BR8108307A/pt
Publication of WO1981002934A1 publication Critical patent/WO1981002934A1/en

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    • 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
    • G03C5/264—Supplying of photographic processing chemicals; Preparation or packaging thereof
    • G03C5/266—Supplying of photographic processing chemicals; Preparation or packaging thereof of solutions or concentrates

Definitions

  • This invention relates to new photographic processing concentrates.
  • photographic elements such as elements comprising one or more silver halide emulsion layers
  • aqueous processing solutions comprising one or more processing agents.
  • These solutions are conventionally relatively dilute, and thus, it is not generally feasible, from an economic standpoint, to package, transport and store processing solutions of working strength since this would involve the packaging, transporting and storage of large amounts of water.
  • One approach involves the preparation of dry powder mixes' hich must be dissolved in water and then diluted to the proper volume before use.
  • liquid concentrates that is, concentrated solutions which merely have to be diluted with water to obtain a working strength solution.
  • liquid concentrates that is, concentrated solutions which merely have to be diluted with water to obtain a working strength solution.
  • Examples of such packaged processing formulations are described in numerous patents and publications; for example, the dry powder developer mixes of U.S. patents 2,843,484 and 2,846,308, the black-and-white developer liquid concentrates of U.S. patents 3,467,521, 3,532,498, 3,854,948 and 4,046,571,. and the color developer liquid concentrates of U.S. patents 3,574,619,
  • black-and-white developers of the hydroquinone/pyrazolidone type are typically packaged as a two-part liquid concentrate system, as described in United States patents 3,532,498 and
  • paste-like processing concentrates have been prepared without the use of suspending, thickening, binding or gelling agents, but these co positions have exhibited similar disadvantageous characteris ics.
  • a photographic processing concentrate containing a photographic processing agent characterized in that the concentrate comprises a discontinuous solid phase distributed throughout a continuous liquid phase, the solid phase comprising finely divided solid particles associated in a stable three-dimensional network which imparts shear-thinning characteristics to the concentrate, at least one of the liquid phase and the solid phase containing a photographic processing agent, and the liquid phase being present in an amount sufficient to impart a paste-like consistency to the concentrate.
  • the photographic processing concentrates of the invention can be packaged, transported, and stored in the form of a stable paste that is adapted to be readily dissolved in water or other liquid medium to form a working processing solution.
  • the paste is comprised of a discontinuous solid phase comprising finely-divided solid particles associated in a stable three-dimensional network distributed throughout a continuous liquid phase.
  • the liquid phase is present in an amount which is much less than the amount that would be needed to form a solution of the solid phase and just sufficient to impart a paste-like consistency.
  • One or more photographic processing agents is present in either or both of the liquid and solid phases.
  • the three-dimensional network formed by the association of the finely-divided solid particles provides a high degree of stability to the concentrate, while still permitting it to be readily dissolved in a liquid medium.
  • the continuous liquid phase can consist of a single liquid or of two or more miscible liquids. It can be comprised of water, or of one or more organic liquids, or it can be a mixed aqueous- organic system.
  • the solid phase typically comprises one -or more of the ingredients of the processing composition which are normally solid materials. While liquid or solid ingredients which are not necessary components of the working processing solution can be incorporated in the paste when needed, it is frequently the case that the paste can be prepared solely from the necessary components ef the processing solution, without the need to delete any ingredients that would be used in the prior art - system of liquid concentrates nor to add any additional ingredients. Formulation of the stable paste is achieved by appropriate selection of the relative proportions of the ingredients, appropriate control of the particle sizes of the ingredients, and appropriate control of the procedures whereby they are combined.
  • the paste form of concentrate described herein In using the paste form of concentrate described herein, problems of chemical interaction between ingredients, which complicate the use of liquid concentrates, are frequently much less severe. Thus, in many instances, all of the necessary ingredients can be combined together to form a single paste, or the number of separate parts which is needed in a system can be reduced, for example, from three to two or from four to three.
  • the paste has excellent shelf- life properties, and is capable of being readily diluted with water or other liquid medium to form a working strength solution that performs in a manner indistinguishable from a working strength solution prepared from liquid concentrates.
  • the pastes of the invention are readily adaptable for use in automatic or semi-automatic procedures for delivery to the processing system, and thus are as convenient to use as liquid concentrates, and much more convenient to use than dry powder mixes.
  • the photographic processing concentrates of the invention are stable, non-separating, non-caking, non-crystallizing and readily dissolvable in a liquid medium to form processing solutions.
  • a processing concentrate can be formulated in paste form to obtain important advantages in regard to packaging, transport and storage resulting from its excellent stability and low bulk, and yet, the concentrate can be easily converted from the paste form to a processing solution that performs equally as well as solutions prepared from liquid concentrates. It is also unexpected to find that preparation of processing concentrates jin paste form can greatly simplify packaging by enabling all components to be incorporated together, or at least to reduce the number of component parts into which they must be separated.
  • processing concentrates With photographic processing compositions in which all processing agents are normally solid materials, it is ordinarily feasible to prepare the processing concentrate of the invention by combining these solid materials in finely-divided form in the correct proportion and appropriate order with the appropriate amount of water, or other liquid medium, and thoroughly blending them together, taking care to ensure that the finely-divided solid particles are associated in a stable three-dimensional network. Similarily, with processing concentrates in which some of the processing agents are normally solid materials and others are normally liquid materials, it is ordinarily feasible to prepare the processing concentrates of the invention by combining the solid materials, the liquid 'materials and water, all in the appropriate portions, and thoroughly blending them together. In instances where several of the processing agents are liquids, little or no water may be required.
  • the paste-like- processing concentrates of this invention are prepared without the use of any suspending, thickening binding or gelling agents, as these agents typically exhibit many characteristics which render their use undesirable in photographic
  • the term "photographic processing agent" is used herein to refer to a material used to develop or otherwise process a photographic element, for example, to develop, fix, bleach, harden, stabilize, etc.
  • the processing solutions prepared from the processing concentrates of the invention can be any of the solutions used in processing photographic materials such as, for example, black-and-white developing solutions, color developing solutions, fixing baths, bleaching baths, stabilizing baths, stop baths, nucleating baths, mono-baths, bleach-fixes, prehardeners, activators, conditioning baths, toners, neutralizers, and the like.
  • the invention is particularly useful for preparing processing concentrates containing photographic-processing agents useful for processing silver halide photographic elements.
  • organic developing agents include hydroquinones, catechols, aminophenols, pyrazolidones, phenylenediamines, tetrahydro- quinolines, bis(pyridone) amines, cycloalkenones, pyrimidines, reductones and coumarins.
  • useful inorganic developing agents include compounds of a metal, having at least two distinct valence states, which are capable of reducing ionic silver to metallic silver. Such metals include iron, titanium, vanadium, and chromium. The metal compounds employed are typically complexes with organic compounds such as polycarboxylic acids or aminopolycarboxylic acids.
  • a particularly important class of black- and-white developing agents useful in the invention are the dihydroxybenzenes such as, for example, hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, toluhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-dimethylhydroquinone, 2,3-dibromohydroquinone, l,4-dihydroxy-2-acetophenone-2,5-di- methyIhydroquinone, 2,5-diethyIhydroquinone, 2,5-di-p-phenethyIhydroquinone, 2, 5-dibenzoylaminohydroquinone, and
  • a further particularly important class of black-and-white developing agents useful in the invention are the 3-pyrazolidones.
  • Useful compounds of this class include those substituted in the
  • pyrazolidone nucleus can be substituted in the 4-position, particularly by lower alkyl and substituted lower alkyl groups such as methyl and hydroxymethyl.
  • Representative compounds of this class are l-phenyl-4-methyl-3-pyrazolidone, l-phenyl-4-hydroxymethyl-3-pyrazolidone, l-phenyl-4, 4-dimethyl-3-pyrazolidone, and l-phenyl-4,4-di
  • Color developers useful in the invention typically contain primary aromatic amino color developing agents. These color developing agents are well known and widely used in a variety of color photographic processes. They include aminophenols and p-phenylenediamines.
  • aminophenol developing agents examples include o-aminophenol, p-aminophenol, 5-amino-2- hydroxytoluene, 2-amino-3-hydroxy-toluene, 2-hydroxy- 3-amino-l,4-dimethylbenzene, and the like.
  • aromatic primary amino color developing agents are the p-phenylenediamines and especially the N-N-dialkyl-p-phenylenediamines in which the alkyl groups or the aromatic nucleus can be substituted or unsubstituted.
  • Examples of useful p-phenylenediamine color developing agents include: N-N-diethyl-p-phenylenediamine monohydro- chloride, 4-N,N-diethyl-2-methylphenylenediamine monohydrochloride, 4-(N-ethyl-N-2-methanesulfonylaminoet.hyl)- ' 2-methylphenylenediamine sesquisulfate monohydrate, 4-(N-ethyl-N-2-hydrox ethyl)-2-m th lpheny- lenediamine sulfate, and 4,N,N-die hyl-2,2'-methanesulfonylamino- ethylphenylenediamine hydrochloride.
  • An especially preferred class of p-phenylenediamine developing agents are those containing at least one alkylsulfo ⁇ amidoalkyl substituent attached to the aromatic nucleus or to an amino nitrogen.
  • Other especially preferred classes of .p-phenylenediamines are the 3-alkyl-N- alkyl-N-alkoxyalkyl-p-phenylenediamines ⁇ and the 3-alkox -N-aIky1-N-aIkoxyalkyl-p-phenylenediamines.
  • n is an integer having a value of from 2 to 4
  • R is an alkyl group of from 1 to 4 carbon atoms
  • R is an alkyl group of from 1 to 4 carbon atoms or ah alkoxy group of from 1 to 4 carbon atoms.
  • these developing agents include the following compounds: N-ethy1-N-methox butyl-3-me hyl-p-pheny ⁇ lenediamine, N-etbyl- -etboxyethyl-3-metb l-p-pheny- lenediamine, N-ethyl-N-methoxyethyl-3-n-propyl-p-pheny- lenediamine,
  • color developer compositions typically contain a variety of other agents such as alkalines to control pH, bromides, iodides, benzyl alcohol, anti-oxidants, solubilizing agents, sequestering agents, brightening agents, etc. which can be used in the processing concentrates of the invention. «
  • bleaching agents are known for use in photographic processing, for example, ferricyanide bleaching agents, persulfate bleaching agents, dichromate bleaching agents, permanganate bleaching agents, ferric chloride and water-soluble quinones. Such processing agents can be used in the processing concentrates of the invention.
  • a particularly important group of photographic bleaching agents are the aminopoly- carboxylic acid bleaching agents. They are typically utilized in the form of water-soluble salts, such as ammonium or alkali metal salts, of a ferric aminopolycarboxylic acid complex.
  • a typical example is the ammonium salt of ferric ethylene- diaminetetraacetic acid (NH,FeEDTA) , which is also known as ammonium ethylenedinitrilotetraacetato ferrate (III).
  • aminopolycarboxylic acids is addition to ethylenediamine tetraacetic acid are also useful such as, for example: nitrilotriacetic acid, diethylenetriamine pentaacetic acid, ortho-diamine cyclohexane tetraacetic acid ethylene glycol bis(aminoethyl) ether) tetraacetic acid, diaminopropanol tetraacetic acid, N-(2-hydroxyethyl)ethylenediamine triacetic acid, and ethyliminodipropionic acid.
  • the aminopolyacetic acids are preferred, as they are readily available and provide particularly good bleaching action.
  • Fixing agents used in photographic processing and which can be used in the processing concentrates of the invention include thioureas, thiocyanates, thiosulfates, mercapto-containing compounds such as mercapto acetic acid, quaternary ammonium salts, polyamines such as tetraethylene pentamine, and the like.
  • thiosulfates as fixing agents, typically ammonium thiosulfate or alkali metal thiosulfates such as sodium thiosulfate and potassium thiosulfate.
  • Bleach and bleach-fix processing agents used in the invention can contain a wide variety of addenda known to the art to be useful in such form ⁇ ulations, including amines, sulfites, mercapto- triazoles, alkali metal bromides, alkali metal iodides, and the like.
  • Agents for hardening of gelatin or other hydrophilic colloids employed in photographic elements are often used in processing. Such agents can also be used in the invention. For example, they can be incorporated in fixing baths, or in developing baths or utilized in the form of prehardener solutions. In hardening fix baths, it is common to utilize an aluminum or zirconium salt as the hardening agent. In developers and pre- hardeners, any of a very wide variety of hardening agents can be employed. Such hardening agents include aldehydes such as formaldehyde, * dialdehydes such as succinaldehyde and glutaraldehyde, ⁇ -diketones, sulfonate esters, active halogen compounds, etc.
  • nucleating agents In color reversal processing of photo ⁇ graphic elements, it is common to utilize nucleating agents to take the place of reversal re-exposure. Nucleating agents can be incorporated in a color developing solution or in a separate bath which is used between first development and- color develop ⁇ ment. Useful classes of nucleating agents useful in the invention include alkali metal borohydrides, ionic boron hydrides containing two or more boron atoms per molecule, amine boranes, polyamine boranes, phosphine boranes, arsine boranes, stibine boranes, borazines, chelated stannous salts, and the like.
  • a final step in many color photographic processes involves treatment of the element with a stabilizing bath, which serves to stabilize the dye images.
  • a stabilizing bath which serves to stabilize the dye images.
  • Such baths frequently include a wetting agent, for example, a polyoxyalkylene compound, and an aliphatic aldehyde, for example, formaldehyde, paraformaldehyde, acetaldehyde, aldol, crotonaldehyde and the like.
  • a wetting agent for example, a polyoxyalkylene compound
  • an aliphatic aldehyde for example, formaldehyde, paraformaldehyde, acetaldehyde, aldol, crotonaldehyde and the like.
  • the agents comprising such baths can be used in the processing concentrates of the invention.
  • WH O _ process employing the steps of color developing and bleach-fixing, or more complicated processes such as a process employing a prehardener, a neutralizer, a first developer, a color developer, a bleach, a fix and a stabilizer.
  • the concentrates of the invention can be advantageously utilized with simple processes or with those employing a complicated series of steps. It is useful in black-and-white processing (including X-ray processing and processing of lith- ographic films), in the processing of photographic elements designed for reversal color processing, in the processing of negative color elements, and in the processing of color print materials.
  • the present processing concentrates can be employed with photographic elements which are processed in color developers containing couplers or with photographic elements which contain the coupler in the silver halide emulsion layers or in layers contiguous thereto.
  • the photosensitive layers present in the photographic elements processed with processing concentrates of this invention can contain any of the conventional silver halides as the photo ⁇ sensitive material, for example, silver chloride, silver bromide, silver bromoiodide, silver chlorobromide, silver chloroiodide, silver chloro- bromoiodide, and mixtures thereof.
  • These layers can contain conventional addenda and be coated on any ofc the photographic supports, such as, for example, cellulose nitrate film, cellulose acetate film, poly- vinyl acetal film, polycarbonate film, polystyrene film, polyethylene terephthalate film, paper, polymer-coated paper, and the like.
  • the solid material used in preparing the paste-like photographic processing concentrates of this invention is typically comprised of one or more normally solid processing agents, e.g., such solid processing agents as the salts of p-phenylene ⁇ diamines which are commonly used as color developing agents.
  • normally solid processing agents e.g., such solid processing agents as the salts of p-phenylene ⁇ diamines which are commonly used as color developing agents.
  • inert particulate components which do not perform a processing function, but are added solely to facilitate formation of the paste, can be utilized.
  • Useful materials for this purpose include a wide variety of finely-divided photographically inert solid materials such as silicon dioxide, sodium sulfate, and diatomaceous earth.
  • the paste-like photographic processing concentrates of this invention requires the use of solid particles in very f nely-divided form. Because the solid particles are very finely- divided, they provide a very large .surface area per unit of weight. The amount of surface area is an important factor in determining the physical characteristics of the paste-like concentrate, especially its rheological properties.
  • the desired small particle size and high surface area can be achieved by grinding which takes place during blending of the materials in forming the concentrate, or by grinding individual ingredients prior to blending.
  • the actual particle size employed can vary widely, depending on the particular processing formulation involved. How ⁇ ever, the photographic processing concentrates of this invention are typically characterized by the presence of particles of very small size. Generally speaking, it is desirable that the finely-divided solid particles have a size less than 100 microns, preferably less than 25 microns, and most preferably
  • the liquid phase of the paste-like photographic processing concentrates of this invention can take a variety of forms. In appropriate situations, e.g., those where the processing formulation does not employ any processing agents which are liquids, water can be used as the sole liquid ingredient forming the liquid phase. In other instances, one or more liquid processing agents, or a combination of water plus one or more liquid processing agents can be utilized. Inert water-miscible organic liquids, i.e., those which do not have a processing function, can be added in order to promote formation of the paste, if desired.
  • the paste-like photographic processing concentrates of the invention are made up of a discontinuous solid phase that is distributed throughout a continuous liquid phase.
  • the two phases are in intimate association with one another and interact to provide the properties exhibited by the paste.
  • the liquid phase must not be present in either too great or too small an amount in relation to the solid phase or the resulting product will not have the desired paste-like consistency.
  • the actual ratio of liquid to solid in the concentrate can vary widely, depending on the particular processing formulation involved, and such factors as particle size. Generally speaking, it is desirable that the liquid phase be present in an amount of from 0.05 to 0.8 parts per part of solid phase by weight, and more preferably in an amount of from 0.1 to 0.6 parts per part of solid phase by weight.
  • the photographic processing concentrates of the invention are characterized by a very low ratio of liquid to solid in comparison to prior art photographic processing concentrates.
  • This developer concentrate contains 2 grams of sodium sulfite and 6.4 grams of 4-amino-N-e hyl-N-( ⁇ -methanesuIfonamidoethyl)-m- toluidine sesquisulfate monohydrate dissolved in 11 grams of water. This is a weight ratio of liquid to solid of 1.3 to 1.
  • the same formula ⁇ tion prepared in the form of a paste-like concentrate in accordance with this invention would typically have a ratio of liquid to solid of about 0.6 to 1.
  • a typical example of a black-and-white developer liquid concentrate of the prior art is that described in Example 1 of U.S.
  • This developer paste is prepared by adding 24.0 grams of sodium sulfite, 45.0 grams of sodium carbonate, 1.6 grams of onomethyl p-aminophenol sulfate, 4.8 grams of hydroquinone, 1.0 grams of potassium bromide and 2.0 grams of sodium tetraphosphate to 90 milliliters of a 2% solution of the sodium derivative of algin.
  • This is a weight ratio of liquid to solid of approximately 1.1 to 1.
  • a comparable developer prepared in the form of a paste-like concentrate in accordance with the invention would omit the algin derivative and would typically have a ratio of liquid to solid of 0.25 to 1.
  • Photographic processing agents present in the paste-like concentrates of the invention can be present in either or both phases.
  • a processing agent which is a solid material will be distributed between the solid and liquid phases, with the amount present in each being determined, in part, by its solubility characteristics.
  • the p-phenylenediamines that are used in color developers will typically be distributed between both phases with a major portion, e.g. , 90% being in the liquid phase, and a minor proportion, e.g., 10%, being in the solid phase.
  • the photographic processing concentrates of the invention are prepared in the form of a stiff paste, but the degree of fluidity of these compositions can be varied to a very considerable extent, as desired, so that pastes with either a pourable or non-pourable consistency are within the contemplated scope of this invention.
  • Thickening or suspending agents are not usually needed in the processing concentrates of this invention, but their use is optional, and they can be employed, if desired.
  • the paste-like concentrates are readily dissolved in water, even with the use of only very simple stirring equipment such as a hand-held paddle. Improved results, however, are usually obtained when they are dissolved with the aid of mechanical stirring devices that provide much higher mixing speeds that can be achieved by hand.
  • concentrates disclosed herein can be characterized as being stable, nonseparating, non-caking, non-crystallizing and readily dissolvable in a liquid medium to form a working processing solution, such terms are, of course, relative terms, and it is intended by use of these terms only to indicate that the concentrate possesses these characteristics to a degree sufficient to be useful for its intended purpose.
  • processing concentrates prepared in the paste form described herein are not intended to be used, as such, in processing photographic materials, but only after being dissolved in the appropriate amount of water or other liquid medium to f'orm a working strength solution.
  • the objectives and purposes of this invention are clearly different than in the case of prior art inventions where photographic processing compositions have been converted to forms other than true solutions with the intention that they be used in such form in the processing of photographic elements, for example, the processing compositions in the form of a foam as described in U.S. patent 2,860,977, the solid fusible, processing compositions of U.S. patents 3,347,675 and 3,438,776, and the viscous processing compositions of U.S. patent 3,392,019.
  • the processing concentrates of this invention are designed to facilitate packaging, transport and storage, and this involves distinctly different considerations and problems that were involved in the above prior art that were seeking to simplify processing operations per se.
  • the paste ⁇ like concentrates of the invention are characterized by a very low ratio of liquid to solid. It is this feature that provides the desired low bulk character ⁇ istics that provide substantial cost savings in pack- aging, transport and storage.
  • the photographic concentrates of this invention are clearly distinct from photographic processing con ⁇ centrates of the prior art, which have utilized relatively large portions of water, but have had high viscosity in spite of the high water content because of the presence of large amounts of colloidal thickening, binding, gelling, or suspending agents.
  • the paste-like photographic processing concentrates of the invention are characterized by the presence of f nely-divided solid particles associated in a stable three-dimensional network.
  • the finely-divided solid particles are present in the form of aggregates or clusters of particles, and such systems can, therefore, be described as flocculated.
  • particles associate, through electrical forces, to other particles, and it is this attraction into a network which imparts stability.
  • network formation is dependent upon morphological association. For example, particles of needle-like structure are generated in blending and grinding of the ingredients, and such particles associate in a stable three-dimensional network as a consequence of their shape.
  • certain of the components are present in the form of intermolecular association products which create a stable three-dimensional network through physical and chemical interaction, but readily dissociate when the paste is diluted with water.
  • stable is used herein with reference to the three-dimensional network in the sense of being descriptive of its capability of functioning to maintain the desired even distribu- tion of materials throughout the paste-like concentrate during a shelf life of adequate duration to meet the requirements of the photographic art.
  • the presence in a photographic processing concentrate of the stable three-dimensional network described herein is evidenced by a yield point and by rheological behaviour that can be characterized as shear-thinning or pseudoplastic.
  • the network results from the association of finely-divided particulates through mechanisms such as those outlined above.
  • the dimensions of the network are perhaps best characterized by the distances over which a disruption of one point has an effect at another point. These dimensions are dependent on the materials and methods of formulation and can range from a few tens of microns up to many centimeters.
  • a processing concentrate of the invention in the form of a flocculated colloidal suspension is illustrated by a p-phenylenediamine color developer formulation containing both benzyl alcohol and triethanolamine. Color developers containing these two ingredients are described in U.S. patent 4,170,478.
  • benzyl alcohol and water are made miscible by the addition of a third solvent, triethanolamine, which is completely miscible with both of the other solvents.
  • benzyl alcohol and water are immiscible in any quantity of benzyl alcohol greater than one gram in twenty-five milliliters of water, and of more than one milliliter of water in ten grams of benzyl alcohol.
  • the photographic processing concentrates are the photographic processing concentrates.
  • association of the finely-divided particles in a stable three-dimensional network maintains larger particles in suspension, and avoids settling or stratification.
  • additives which are not processing agents, such as dispersing agents or thickeners.
  • Characteristic features of paste-like photographic processing concentrates of the invention comprising finely divided solid particles associated in a stable three-dimensionaj network include their shear-thinning properties and high sedimentation volumes.
  • a shear-thinning material is one which has a high viscosity under low shear conditions, and a low viscosity under high shear conditions).
  • the shear-thinning properties possessed by these concentrates are especially significant in that they greatly facilitate dispensing of the concentrates from the containers in which they are packaged.
  • the particular viscosity and degree of shear-thinning exhibited varies greatly among the very wide range of different processing compositions coming within the scope of the present invention.
  • typical concentrates have an apparent viscosity in the range of from 250 to 1300 centipoises at a shear rate of 800 reciprocal seconds (sec. ) .
  • a shear rate of 4500 reciprocal seconds an apparent viscosity in the range of from about 100 to about 500 centipoises is typical.
  • These values refer to viscosity measurements made in a HERCULES HI-SKEAR VISCOMETER (rational concentric cylinder type) at ambient temperature.
  • the rotor or inner cylinder (radius 1.95 cm., height 5.0 cm.) is rotated at a constant angular acceleration of approximately 5.49
  • the sedimentation volume is large, whereas the sediment from a stable suspension tends to pack closely, i.e., to approximate closest packing behavior, so as to exhibit a considerably smaller sedimentation volume for particles of the same dimensions. Brownian motion can be observed in a stable suspension, but not in a flocculated system.
  • the flocculated suspensions have been found to exhibit pronounced thixotropic behavior.
  • the paste-like photographic processing concentrates of the invention are especially advantageous in the packaging of color developing compositions comprising primary aromatic amino color developing agents.
  • color developers are packaged and sold in liquid concentrate form, with the chemical formulation for a given process being divided into the least possible number of concentrated parts that will provide good shelf life.
  • the color developer formulation will contain numerous ingredients, sometimes as many as fifteen or more, and it will be necessary to separate it into three or four parts in order to package it in the form of liquid concentrates.
  • Formation of stable paste-like concentrates in accordance with the teachings herein, will often permit packaging of complex color developers containing as many as fifteen or more ingredients in the form of a single paste or, perhaps, two different pastes. It was particularly surprising to find that problems of chemical interaction between components of complex color developer formulations which complicate the use of liquid concentrates, and necessitate packaging of as many as four separate liquid concentrates, are frequently much less severe with the paste-like concentrates of this invention.
  • the aromatic primary amino color developing agents are solid materials which will distribute themselves between the liquid and solid phases of the concentrate.
  • the liquid phase will typically be comprised of water and at least one organic liquid, since organic liquids, e.g. , benzyl alcohol, are necessary components of many currently used photographic color developing compositions.
  • the starting ingredients for forming the paste-like concentrates can be liquids, powders, or slurries. Typically, the slurries are saturated solutions with excess solutes present as undissolved solids. The ingredients are blended in a high shear
  • mixing vessel can be conveyed to this vessel by any of several methods. Liquids and slurries are usually pumped, while powders are handled with a screw conveyor or other powder transport system. Agitated storage tanks can be used with the slurries in order to keep the solids in suspension. For uniformity and proper consistency, it is necessary to thoroughly disperse the solids and homogenize the product. This is best accomplished with hydraulic and mechanical shear provided by high speed agitators.
  • the next step is to convey it to the package-filling apparatus.
  • the concentrate can be conveyed by gravity through a vibrated chute.
  • the concentrate can be conveyed by pumping, typically by pumps of the positive-displacement type.
  • Package filling can be carried out with the use of an auger system or a piston system.
  • Packages of a wide variety of types can be utilized and inexpensive packaging materials, for example, thermoplastics such as polyethylene, can be employed.
  • Dispensing of the paste and combining it with water or other liquid medium to form a working processing solution can be carried out by any suitable method. There are two basic approaches which are feasible.
  • the first of these is to dispense and dissolve the entire contents at one time, i.e., a batch-dispensing approach. In this instance, it is not necessary that the paste be entirely homogeneous, since' all of the contents of the package are utilized to form a single batch of processing solution.
  • the second approach is to dispense a portion of the contents of the package intermittently as needed. In this case, the paste must be completely homogeneous, since each portion dispensed must be like every other to give a consistent working solution.
  • Photographic processing chemicals must be dissolved in water or other liquid medium in very precise amounts in order to prepare working processing solutions.
  • a photographic concentrate must not only possess features facilitating packaging, transport and storage, but must be capable of being dispensed . in such a way as to ensure the necessary precision in the preparation of working processing solutions. It is particularly advantageous for the photographic processing concentrate to be "volumetrically dis ⁇ pensable.”
  • volumetrically dispensable is meant a 'composition which has flow properties such that it can be dis ⁇ claimedd from a package in a metered amount on a volumetric basis, and which has a high degree of uniformity such that each unit volume dispensed contains essentially the same amount of active agents on a weight basis.
  • a predetermined volume of concentrate with a predetermined volume of liquid, e.g., 100 cubic centimeters of concentrate combined with one liter of water, and consistently obtain the same weight of active agents in the resulting working solution.
  • the dilution ratio employed with the processing concentrate that is, the amount of water or other liquid used to convert the pas «te to a working processing solution, will vary greatly depending on the nature of the photographic element being processed, the processing procedure, and the particular processing formulation involved. In general, the dilution ratio will be in the range of 1 part of paste to 8 parts by weight of liquid to 1 part of paste to 100 parts by weight of liquid.
  • a photographic processing concentrate is used herein to refer to a composition comprising one or more processing agents, such as developing agents, bleaching agents, fixing agents, etc.
  • the processing concentrate can be (but not necessarily) complete in the sense that it merely needs to be combined with water, or other liquid medium, to form a working strength processing solution.
  • a processing concentrate of the invention can be combined with another photographic processing concentrate, as well as water or other liquid medium, to form a working strength processing solution, this other process ⁇ ing concentrate suitably being a paste, a powder, or a liquid.
  • a photographic developing solution might comprise five active agents, namely, a developing agent, an alkali, an antifoggant, an anti-oxidant and a sequestering agent.
  • a first paste containing the developing agent and anti-oxidant and a second paste containing the alkali, the antifoggant and the sequestering agent, and then to combine the first and second pastes together, along with an appropriate quantity of water, to form a working strength developing solution.
  • a photographic processing composition might require several different solid processing agents and one liquid processing agent, and the paste-like concentrate could include only water and the several solid processing agents, while the working strength solution would be prepared by combining the liquid processing agent and the paste, along with an appropriate quantity of water.
  • photographic processing concentrates of the invention have been referred to throughout the specification as “pastes,” and this term is aptly descriptive of their character ⁇ istics, they could also be referred to by a variety of other terms, such as, for example, the terms “semi solid,” or “semi fluid” or “plastic.”
  • a photographic processing solution is intended to include working solutions, replenisher solutions, starter solutions, and so forth.
  • the paste-like photographic processing concentrates of the invention can be evaluated by the preparation of rheograms, that is, plots of shear rate versus shear stress.
  • the viscosity is inversely proportional to the slope of the curve.
  • the values of shear stress obtained during an ascending series of shear rates correspond to those obtained in a descending series of shear rates.
  • the curve for a descending series retraces the curve for an ascending series.
  • the occurrence of thixotropic loops in a rheogram provides Theological evidence that the composition is a structured fluid, that is, one comprising a three-dimensional network.
  • the rheogram exhibits what can be termed a thixotropic loop or hysteresis loop in that the descending series does not retrace the curve for the ascending • series.
  • a thixotropic fluid is one which exhibits a time-sensitive viscosity. In other words, the viscosity decreases with increasing shear duration.
  • a thixotropic fluid When a thixotropic fluid is sheared at a constant shear rate, the viscosity decreases with time until some equilibrium value is reached. This is inter ⁇ preted by rheologists as the breakdown of a structure present in the fluid.
  • an ascending series of shear rates is imposed on a thixotropic pseudoplastic fluid, and immediately followed by a descending series, the curve is not retraced.
  • a hysteresis loop is produced, with the curve of the descending series displaced toward the shear rate axis. This loop is also known as a thixotropic loop and is due to the breakdown of structure with time.
  • the photographic processing concentrates of the invention comprise finely-divided solid particles associated in a stable three-dimensional network which imparts shear-thinning characteristics to the concentrate. Thus, they can be character ⁇ ized as thixotropic pseudoplastic fluids.
  • the present invention is pre ⁇ dicated on the discovery that thickening, gelling, binding or suspending agents are not necessary in processing concentrates of paste-like consistency, and that the desired shelf stability can be achieved by careful control of the parameters of the manufacturing process, including, in particular, such important parameters as the particle size, the order in which the ingredients are combined, the degree of mixing and the ratio of liquid to solid components.
  • Example 1 The invention is further illustrated by the following examples of its practice.
  • Example 1
  • a photographic processing concentrate intended to be diluted with water to form a color developing solution for developing negative-positive color film was prepared in the following manner: 780 illiliters of a 47% by weight aqueous solution of potassium carbonate and 240 grams of powdered potassium sulfite were added to a 3.8 liter stainless steel Waring Blender, equipped with a cooling jacket, and blended for two minutes at low speed. 516 grams of 4-(N-ethyl-N-2-methanesulfonyl- aminoethyl)-2-methylphenylenediamine sesquisulfate monohydrate color developing agent in the form of a finely-divided powder was then added slowly while stirring with a spatula. 502 grams of powdered potassium carbonate was then added, and the mixture was blended for three minutes at high speed.
  • the product obtained was a pourable paste having a weight ratio of liquid to solid of 0.16 to 1 which exhibited shear-thinning characteristics. It was diluted with water in a ratio of 50 grams of water to one gram of paste and dissolved readily to produce a working color developing solution.
  • Example 2 A photographic processing concentrate intended to be diluted with water to form a hardening developer for processing X-ray film was prepared as a two-part paste formulation in the following manner:
  • the product obtained was a pourable paste which had a weight ratio of liquid to solid of 0.22 to 1 and exhibited shear-thinning characteristics.
  • Example 3 A photographic processing concentrate intended to be diluted with water to form a color developing solution for developing color prints was prepared from the following ingredients:
  • the product obtained was a pourable paste having a weight ratio of liquid to solid of 0.3 to 1 which exhibited shear-thinning characteristics. It was diluted with water in a ratio of 18 grams of water to one gram of paste and dissolved readily to produce a working color developing solution.
  • Example 4 A photographic processing concentrate tended to be diluted with water to form a color developing solution for developing color prints was prepared from the following ingredients:
  • Components 1 to 5 were added to a 6-liter VME-6 mixer manufactured by Fryma-96 AG, and blended while cooling to a temperature of 17°C. The mixer was then started and components 6 to 13 were added through the addition port, allowing about 2 to 5 minutes between additions for thorough mixing. After addition of the first five components, the dissolver (a rotating disk with a saw tooth type configuration) was started, and allowed to run throughout the mixing procedure. The colloid mill (two rotating conical disks) was started after all components had been added, and allowed to run for one hour.
  • the product obtained was a pourable paste having a weight ratio of liquid to solid of 0.61 to 1 which exhibited shear-thinning characteristics. It was diluted with water in a ratio of 11.75 grams of water to one gram of paste, and dissolved readily to produce a working color developing solution.
  • the paste described above was analyzed by a technique involving high speed centrifugation to separate the continuous liquid paste and the dis- continuous solid paste, followed by analysis of the separated phases.
  • the continuous liquid phase was analyzed by ultraviolet spectroscopy, gas chromato- graphy, Karl Fischer titration and total alkalinity titrimetry.
  • the discontinuous solid phase was analyzed by ultraviolet spectroscopy, gas chromato- graphy, Karl Fischer titration, total alkalinity titrimetry, and gravimetric sulfate analysis.
  • a photographic processing concentrate intended to be diluted with water to form a black- and-white developing solution was prepared with the use of a mortar and pestle from the following ingredients: Component Weight(grams)
  • Component 1 was ground ' for four minutes and set aside.
  • Components 6 and 7 were each ground for three minutes and were also set aside.
  • Components 1 to 7 were then combined in the mortar and ground for two minutes.
  • Component 8 was added slowly with mixing.
  • Component 9 was then added slowly with mixing. The composition was mixed for three minutes after the final addition. Within five hours, the material had set to a stiff paste. No separation, caking, or crystal ⁇ lization was evident even after two days. Rheograms of both freshly-prepared and two-hour old composition had distinct thixotropic loops.
  • a photographic processing concentrate intended to be diluted with water to foxm a color developing solution was prepared with the use of a mortar and pestle from the following ingredients Component We igh t (grams )
  • Lithium sulfate 19.6 Lithium sulfate 19.6 10. Hydroxylamine sulfate 44.1 11. 4-(N-ethyl-N-2-methanesulfonyl- aminoethyl)-2-methylphenylene- diamine sesquisulfate monohydrate (color developing agent) 47.6
  • Potassium carbonate 175.0 Components 3, 10, 11, and 12 were ground separately and set aside. Components 1 to 5 were added to the mortar in numerical order with mixing. Components 6 to 9 were combined together and then added slowly with mixing. Then components 10, 11, and 12 were slowly added in order with mixing. When all additions were complete, the composition was mixed for five minutes. The total time of mixing was about thirty-three minutes.
  • Example 7 A photographic processing concentrate intended to be diluted with water to form a fixing solution was prepared with the use of a mortar and pestle from the following ingredients:
  • Components 2 and 5 were ground separately and set aside. All components were added together, slowly, in order, and with mixing. When all addi ⁇ tions were complete, the composition was mixed for two more minutes.
  • the composition had set to a smooth, stiff paste. No signs of separation, caking, or crystallization were apparent even after four days.
  • Rheograms of fresh and two-hour old samples had thixotropic loops. The rheogram of the two-hour old sample had a very distinct loop.
  • a paste-like photographic processing concentrate was made according to the formula and procedure of British patent No. 4689.
  • the concentrate was prepared in a mortar and pestle from the following ingredients:
  • the material had separated into a fluid upper layer and a dense sediment and was not useful for preparation of a working photographic processing solution.
  • a paste-like photographic processing concentrate was made according to the formula and procedure of Example 5 of the U.S. patent 2,735,774. • The concentrate was prepared in a mortar and pestle from the following ingredients:
  • Components 1 to 5 were ground together in the mortar for five minutes. Component 6 was added slowly with mixing. Component 7 was ground separately before adding it to the mixture. When all additions were complete, the composition was mixed for five minutes.
  • the paste-like concentrates of this invention provide many important advantages in the photographic art. For example, they result in a major reduction in the cost for transport and storage of packaged chemicals, as compared to liquid concentrates. This is because of the much lower content of water that is required as compared to liquid concentrates, which results in much less bulk and weight, and thus much lower costs. Many processing chemicals are not sufficiently soluble in water to form highly concentrated solutions, so liquid concentrates often require a substantial water content. With the paste-like concentrates of this invention, a given quantity of processing solution can often be made from a package which has half or less than half of the weight and volume of a corresponding package of liquid concentrate.
  • a further advantage of paste concentrates is that they tend to be more, chemically stable and to require less separation of ingredients and, accordingly, fewer separate parts in the total package. Keeping properties are generally significantly better with pastes because of such features as reduced suscept ⁇ ibility to oxidation, reduced susceptibility to deterioration caused by temperature changes, and reduced tendency for crystallization to occur.
  • the paste concentrates are amenable to use with processing compositions in which some of the necessary ingredients are normally liquid, and some are normally solid, whereas dry powder formulations are useful only with compositions in which all necessary ingredients are normally solid. Paste formulations also effectively avoid the problems of caking and dusting that plague the use of dry powder formulations.
  • the paste-like photographic processing concentrates of the invention combine many of the advantages of liquid concentrates with many of the advantages of dry powder formulations to solve longstanding problems in the art of packaging photographic processing agents. They dissolve easily and speedily to form working processing solutions, for example replenisher solutions, and can be adapted for use in systems in which replenisher solution is held in a storage tank or for direct use in continuous replenishment of processing machines.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
PCT/US1981/000128 1980-04-11 1981-01-30 Photographic processing concentrates WO1981002934A1 (en)

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BR8108307A BR8108307A (pt) 1980-04-11 1981-01-30 Concentrados para processamento fotografico

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US13951880A 1980-04-11 1980-04-11
US139518 1980-04-11

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BE (1) BE888398A (es)
BR (1) BR8108307A (es)
CA (1) CA1156868A (es)
FR (1) FR2480451A1 (es)
IT (1) IT8120856A0 (es)
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4987060A (en) * 1989-04-03 1991-01-22 Minnesota Mining And Manufacturing Company Concentrated photographic developer composition and method of making it
US5210010A (en) * 1991-05-15 1993-05-11 Ilford Limited Silver halide developing solutions
EP0580372A2 (en) * 1992-07-16 1994-01-26 Konica Corporation Black-and-white photographic processing compound
US5891608A (en) * 1996-04-02 1999-04-06 Fuji Photo Film Co., Ltd. Photographic processing composition in slurry-form
US5914221A (en) * 1998-03-11 1999-06-22 Fuji Hunt Photographic Chemicals, Inc. Single part color photographic processing composition in slurry form

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DE3515440A1 (de) * 1985-04-29 1986-10-30 Tetenal Photowerk GmbH & Co, 2000 Norderstedt Lagerstabiles farbentwickler-konzentrat
US4814260A (en) * 1986-06-20 1989-03-21 Konishiroku Photo Industry Co., Ltd. Method of storing photographic processing solution in a package having specific oxygen permeability
JP2934997B2 (ja) * 1993-01-21 1999-08-16 コニカ株式会社 黒白ハロゲン化銀写真感光材料の処理方法
US6020113A (en) * 1997-03-31 2000-02-01 Fuji Photo Film Co., Ltd. Process for producing photographic suspended processing agent composition
US5998111A (en) * 1997-03-31 1999-12-07 Fuji Photo Film Co., Ltd. Process for producing photographic suspended processing agent composition
US7879922B2 (en) 2007-11-20 2011-02-01 PolyuMAC Inc. Rigid, closed-cell, graft-polymer foam; rigid flexible cellular foam; rigid flexible cellular foam mixtures; and method for manufacturing a rigid, closed-cell, graft-polymer foam
RU2681263C1 (ru) * 2017-09-27 2019-03-05 Даниил Васильевич Волков Насадка для шприца

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US935156A (en) * 1906-02-09 1909-09-28 William Fraser Claughton Kelly Photographic developer.
GB191227589A (en) * 1908-12-30 1913-10-23 Evan Allan Glen Improvements in or relating to the Lubrication of Internal Combustion Engines.
US1277048A (en) * 1917-04-20 1918-08-27 Alfred De Brayer Substance for use in photography and method of making the same.
US2735774A (en) * 1954-07-26 1956-02-21 Concentrated photographic fixing
US2784086A (en) * 1953-07-28 1957-03-05 Eastman Kodak Co Concentrated developers
DE1077059B (de) * 1956-08-28 1960-03-03 Leonar Werke Ag Verfahren zur Schnellentwicklung photographischer Schichten
US3667368A (en) * 1968-09-03 1972-06-06 Itek Corp Gel roller for use in photographic processing

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US935156A (en) * 1906-02-09 1909-09-28 William Fraser Claughton Kelly Photographic developer.
GB191227589A (en) * 1908-12-30 1913-10-23 Evan Allan Glen Improvements in or relating to the Lubrication of Internal Combustion Engines.
US1277048A (en) * 1917-04-20 1918-08-27 Alfred De Brayer Substance for use in photography and method of making the same.
US2784086A (en) * 1953-07-28 1957-03-05 Eastman Kodak Co Concentrated developers
US2735774A (en) * 1954-07-26 1956-02-21 Concentrated photographic fixing
DE1077059B (de) * 1956-08-28 1960-03-03 Leonar Werke Ag Verfahren zur Schnellentwicklung photographischer Schichten
US3667368A (en) * 1968-09-03 1972-06-06 Itek Corp Gel roller for use in photographic processing

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4987060A (en) * 1989-04-03 1991-01-22 Minnesota Mining And Manufacturing Company Concentrated photographic developer composition and method of making it
US5210010A (en) * 1991-05-15 1993-05-11 Ilford Limited Silver halide developing solutions
EP0580372A2 (en) * 1992-07-16 1994-01-26 Konica Corporation Black-and-white photographic processing compound
EP0580372A3 (en) * 1992-07-16 1995-08-23 Konishiroku Photo Ind Black-and-white photographic processing compound
US5891608A (en) * 1996-04-02 1999-04-06 Fuji Photo Film Co., Ltd. Photographic processing composition in slurry-form
US5914221A (en) * 1998-03-11 1999-06-22 Fuji Hunt Photographic Chemicals, Inc. Single part color photographic processing composition in slurry form
US6197484B1 (en) 1998-03-11 2001-03-06 Fuji Hunt Photographic Chemicals, Inc. Method of making a single part color photographic processing composition in slurry form

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BE888398A (fr) 1981-10-13
EP0049245A1 (en) 1982-04-14
BR8108307A (pt) 1982-03-09
FR2480451B1 (es) 1983-11-18
FR2480451A1 (fr) 1981-10-16
CA1156868A (en) 1983-11-15
EP0049245A4 (en) 1982-05-28
IT8120856A0 (it) 1981-03-31
JPS57500485A (es) 1982-03-18

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