EP1547938A1 - Two compartment container for photographic developers - Google Patents

Abstract

Package for storing photographic color development concentrates and for filling a tank of a processing apparatus with the concentrate, comprises at least two different chemicals spatially separated in chambers. The package is constructed such that the chemicals are brought into contact with one another within the package before the tank is filled with them and/or brought into contact with one another while the tank is filled with them. Independent claims are included for the following: (A) process for color photography materials involving the use for the package for replenishing the color development chemicals; and (B) production of the package involving producing the chambers of the package in one piece by a plastic extrusion blow molding process; filling the chambers with the color development chemicals; and subsequently closing the package.

Description

The invention relates to a container for storing photographic color development concentrates and for filling the color developing concentrates into one Tank of a processing device, wherein the container at least two different Contains chemicals spatially separated in chambers. The invention also relates a method for processing color photographic materials, in which such Used containers, a process for producing such containers and the Use of such containers.

Photographic color development chemicals are used in the context of the invention understood chemical substances or preparations of such substances, which are responsible for the Development of silver halide photographic recording materials can be used. The recording materials are described below also called photographic materials and include both film materials with transparent carrier, such. B. color negative or color reversal films as well Copying materials for the production of regulatory images, such. B. Color Negative Photo Paper.

For the processing of photographic materials, the used baths, such as e.g. Developer, bleach, fixer, bleach-fix or stabilizer first used as tank solutions. These are however during the processing by chemical reaction and by entrainment and carryover depending on Material throughput consumed. To compensate for this, come different ones Method of use. All the same is that the process additional processing chemicals must be supplied. Usually, both for the first tank approach as well as for dosing prefabricated preparations, often concentrated Solutions, used.

The prefabricated preparations for the post-dosing are commonly referred to as Concentrates supplied and referred to as regenerator or refill concentrates. she are usually not added directly to the processing tank, but in one Storage tank of the processing equipment, where they are with water to the desired concentration be diluted. These storage tanks will also be regenerator tanks and the solution contained therein replenisher solution or just regenerator called.

By metering the replenisher solutions into the corresponding processing tanks with either a fixed or manually variable replenishment rate (ml of solution per m ^{2 of} processed material), the processing solutions are always maintained at the typical activity and, in principle, can be used continuously without interruption.

From DE 199 64 300 a container is known, which in a carton, the chemical refill bottles for an automatic photographic processing apparatus. With such a container is a confusion fast docking to the Device ensures, but only with certain equipped processing equipment is possible. Such containers not only contain the replenishment chemicals for one, but for all regenerator tanks and the solutions are at the Removal via hoses led directly into the respective tanks and therefore meet only in the tank on each other.

In addition, photographic processing replenishers are known to be one-piece Solutions or concentrates or to reactions between the chemicals to avoid providing as multipart solutions or concentrates.

Thus, e.g. both one-piece for use as a color developer replenisher as well as multi-part concentrates commercially available. Color developers are at the Development of color photographic silver halide materials used. In the Color developer solutions are applied to the exposed areas of the emulsion layers of the Material reduces the silver halide to metallic silver. The at this The resulting oxidation products of the color developer react with the in The color couplers contained in the emulsion layers to yellow, purple and blue-green Image dyes. At the same time as the black-and-white images, this creates dye images, which remain when in the subsequent processing the metallic Silver is bleached and removed. Removing the metallic silver occurs when processing color negative paper predominantly in a bleach-fix, when processing color negative films predominantly in one Bleach bath and a subsequent fixer.

For the approach of multi-part color developer solutions are usually three used different concentrates, which are filled in separate containers, since Certain components of the developer bath with longer life not together are compatible. Thus, e.g. a concentrate the antioxidant, a Auxiliary solvent and a whitener, a second concentrate the color developing agent, e.g. 4- (N-ethyl-N-2-methylsulfonylaminoethyl) -2-methyl-phenylenediaminesesquisulfate (CD-3) or 4- (N-ethyl-N-2-hydroxyethyl) -2-methylphenylenediamine sulfate (CD-4), as well as usually also an antioxidant and a third Concentrate a buffer substance, alkali, a Kalkschutzmittel and optionally a Antifoggants.

In recent years, increasingly one-piece developer concentrates offered for color negative papers. These have the advantage that they are the Simplify approach of working solution and errors when preparing or supplementing a developer solution can be avoided. However, they have the disadvantage that after prolonged storage they contain undissolved constituents which are very are detrimental to the handling of the concentrates. In particular, when preparing the Regenerating solution can cause problems because the unresolved Solve ingredients only badly. To avoid these precipitations are often by technically complex measures certain compounds, such as e.g. Sulfates, separated. It is also disadvantageous to produce one-piece concentrates, the initially contain no undissolved constituents, but at low temperatures, e.g. during storage or transport to -7 ° C tend to precipitate during Do not heat or dissolve poorly.

From EP 980 024, EP 961 951 and US 5 914 221 are one-part color developer concentrates known. However, the concentrate according to EP 980 024 has the disadvantage that It contains a very high proportion of solvents (greater than 50%), which is often a negative Influence on the pictorial result leads and only for certain regeneration rates suitable is. The compositions according to EP 961 951 and US Pat. No. 5,914,221 have the disadvantage, already directly after the concentrate production unresolved To contain ingredients whose structure varies during storage and which are difficult to resolve.

When using the known multipart refill concentrates it comes despite their high storage stability always leads to problems with the reproducibility, which manifests itself in the fact that the effect of the processing baths produced therewith may vary from approach to approach, even if the refill solutions come from the same production batch. This unwanted effect by the the quality of processed photographic materials is compromised also depending on the processing equipment and the operating personnel different degrees pronounced and can even be completely useless Processing results, whereby in the case of originals the recording irretrievably lost.

The known containers for photographic color development chemicals are from the unsatisfactory reasons mentioned.

The invention is therefore based on the object, a container for photographic color development chemicals to provide the said disadvantages of the known Versions avoids and especially on conventional processing equipment works without additional installations, not the stability disadvantages one-piece Having preparations and that to a better reproducibility of processing leads.

It was surprisingly found that this succeeds with a multi-chamber container, containing photographic color developing chemicals, wherein the chemicals are present and / or during removal and before reaching the tank in contact with each other devices. Even with multi-chamber packages according to the invention, the more complex in Manufacture are as conventional containers, the higher effort is due to the Advantages more than outweighed.

The invention is therefore a container for storing photographic Color development concentrates and for filling the color development concentrates in a tank of a processing apparatus, wherein the container at least containing two different chemicals spatially separated in chambers, thereby characterized in that the container is designed so that the different chemicals before filling in the tank inside the container with each other in Be brought in contact and / or while filling in the tank (during the Removal) are brought into contact with each other.

Preferably, the different chemicals get in during the removal Contact each other to those described above for one-part preparations safely avoid known problems. The contact can be within and / or outside of the container. Preferably, the contact is made directly at the removal opening of the container.

A container according to the present invention will hereinafter also be multi-chamber containers and in a preferred embodiment also multi-chamber bottle and is to be understood as a solid entity during shipment and at the customer's usual use of the chambers as a unit preserved. It may additionally be packed with the known materials. The Mehrkammergebinde has at least one removal opening, which with a Closure is provided. For removal, the closure must be opened, wherein the closure in the open state continues with the multi-chamber container may be connected, as e.g. in the case of a snap closure, or of may be separate from the container, as e.g. with a screw cap the case is. The closure or a part thereof can also be pierced for opening, and the different types of closure can also be combined with each other. Since the contents of the multi-chamber package is usually taken as a whole, it does not have to be lockable after the first opening. A reclosability However, it may be useful to leak at disposal to prevent chemical residues.

The color photographic color development chemicals according to the invention are each Multi-chamber packages the replenishment chemicals necessary for a development step, where among replenishment chemicals are both the chemicals for the new batch the processing tank solution as well as the chemicals to the approach of the replenisher tank solution to be understood. This may be the pure chemical Compounds themselves or act to suitable preparations, but are common concentrated preparations of chemicals (concentrates). The present invention is for every color development step every color photographic processing process suitable for the at least two different refill solutions can be used.

It has been shown that a better reproducibility of the processing results can only be achieved if the different chemicals of a Mehrkammergebindes before removal and / or during removal and before Reaching the tank in contact with each other. This is especially pronounced when refilling the replenisher tank solutions using concentrates.

Without knowing the exact mechanism, it is believed that this contact a premix causes the inhomogeneities of the chemical distribution in the Processing device prevents. So z. B. the approach of a regenerator solution Use of the known multipartite concentrates in minilabs mostly directly in the Replenishing. For the approach, water is presented and then the required Concentrates added. The concentrates are as usual one by one added, there may be a stratification of the concentrates in the regenerator tank come, which can only be eliminated by intensive mixing. Indeed is in many minilabs for cost and space reasons for mixing only one Art paddle provided, whereby an intensive mixing takes a long time. in the Under the present invention, it has been found that even when long mixing times are often not observed by the operating personnel, to save time and it also happens that the regenerator solution after the Approach is not mixed. When using the insufficient Blended regenerator solution will become chemicals during processing different concentration and composition of the Added processing solution, which is the poor reproducibility of Processing and thus the fluctuating quality of the processed material. With the multi-chamber package this disadvantage can be surprisingly counteracted become. It turned out that this considerably reduces the necessary mixing times can be and when using particularly suitable inventive Containers can even be completely dispensed with the subsequent mixing.

In the context of the present invention, it has been found that when using the known multi-part concentrates also unsatisfactory and not reproducible Processing results are obtained that a concentrate part either completely forgotten or that e.g. Instead of Part A and Part B, two parts A are used become. In both cases, the processing solution becomes unusable and Photographic materials processed with them are often lost forever. moreover It may happen that concentrates from different production times when Approach mixed together, e.g. a new batch part A and one old batch part B are mixed. This can be in the ready-made solutions lead to stability losses as well as deviations in the pH and calls an undefined State, because no manufacturer of processing chemicals can all possible combinations of different aged concentrates on their effects and to test for side effects during processing. In addition, such a part a batch always remain unused and aging strongly. Especially high is the damage if the shelf life of the old batch has already expired, so this is no longer usable and the approach from this and a new batch becomes unusable. Especially in recent years, the workload of the frequent Only semi-skilled operating personnel increased more and more, which together with the Complexity of piecing explains that in non-automated regenerator approaches increasingly complaints occur and make clear how important is to increase the operation safety. As according to the present Invention, the individual concentrates are combined into a container, is their confusion is no longer possible and all concentrates of such Mehrkammergebindes have the same production time and have the same storage conditions run through. Moreover, it can not happen that a given Sequence and a specified timeout during preparation not met or that e.g. so much time passes between the addition of Part A and Part B, that in the meantime only with Part A is regenerated.

At the same time, the logistics for ordering and storage are simplified and the Handling is compared to the usual multi-part concentrates with several Bottles considerably more rational.

As contact within the meaning of the present invention, any contact with the chemicals or chemical preparations before they understand a tank of a Processing apparatus or e.g. reach a processing tray.

The contact before the removal is usually shortly before the use of the Canned manufactured and requires a handling or a machine operation. The timing of the contact must be so close to the removal in this variant be chosen that the disadvantages known for one-part preparations yet do not occur. This can be recognized by the fact that it is during the contact time does not come to precipitation and the activity and durability of the processing chemicals is not significantly reduced for photographic processing. at According to this embodiment of the present invention, the contents of the container become the contact and before removal preferably z. B. mixed by shaking.

The contact may e.g. during removal when pouring outside the container take place when the two streams of chemicals meet there; he can do it and / or during removal in a mixing device, hereinafter also Adapter called, take place, which is part of the container or attached to the container becomes; and it may be done before removal in the package by e.g. a Separator is removed or pierced between the chambers. As Examples of possible embodiments of the present invention may be given also be combined with each other when the container is constructed such that e.g. the chemicals from two chambers come into contact before removal and these Mixture with a chemical from a third chamber during removal in Contact device.

The multi-chamber package without the development chemicals will be described below Also called multi-chamber container, regardless of whether the closure included is or not.

A preferred embodiment of the multi-chamber container, which is a two-chamber bottle is shown in Figs. 1 and 2 . In Fig. 1 , the two-chamber bottle is shown in front view and has a bottleneck ( 1 ) with thread, which ends in a plane parallel to the bottle bottom surface ( 2 ). The bottle has the separate chambers ( 4 ) and ( 5 ). In the view from above according to FIG. 2 , in addition to the aforementioned features, a connecting web with an upper end surface ( 3 ) can be seen, which connects the chambers at its lower end and continuously separates them up to the edge ( 2 ). By a closure which seals the surfaces ( 2 ) and ( 3 ) in the closed state, it can be ensured that the contents of the chambers ( 4 ) and ( 5 ) do not come into contact with each other before removal.

When using a Zweikammergebindes from the aforementioned two-chamber bottle and the respective processing chemicals was completely surprisingly found that the reproducibility of the processing results may even depend on how the bottle is held during emptying. Although the advantages of the invention are achieved regardless of how the bottle is held, the reproducibility is on average better if the bottle is held so that the longer edge of the connecting web and thus also its upper end surface ( 3 ) is horizontal during pouring, whereby the chambers ( 4 ) and ( 5 ) are not arranged side by side, but one above the other.

The multi-chamber container is preferably designed so that a thorough mixing as directly as possible behind the removal opening (also referred to below as the pouring opening, Outlet opening, spout or spout called) is guaranteed and at the Withdrawal is preferably kept so that it is promoted.

The preferred handling can be influenced by the shape of the bottle, by e.g. Handles, handle indentations or handle bulges so on the container be attached that when using these grip aids the best possible and reproducible mixing takes place. The handle can be designed so that he holds the chambers together and / or stabilized. In a further embodiment of Mehrkammergebindes a handle attached to it, in particular latched become. Furthermore, a handle helps to the known advantages, in particular for safe handling during transport and emptying.

The bottle according to Figs. 1 and 2 is an example of a preferred embodiment of the multi-chamber container, in which at least two and in particular all chambers have a common closable removal opening, which allows immediate contact directly on the spout and flow in horizontal direction of the connecting web in the spout The concentrates apparently directly into each other, instead of flowing as in the vertical arrangement at least initially next to each other. Further advantageous embodiments of the multi-chamber container, which ensure a good mixing shortly before or during removal, are mentioned below, without the invention being limited thereto.

The container according to the present invention may be two, three, four or even more as four chambers; preferably it comprises two or three and especially it preferably contains two chambers.

In order to keep the production costs low, only so many chambers are used as necessary to achieve the benefits of the invention. Often The skilled person can orient themselves to the known multi-part concentrates to to find a suitable distribution of a concentrate for the multi-chamber container. However, the division may preferably also specifically for the container according to the be optimized present invention, z. By reducing the number of parts is to reduce the manufacturing cost of the multi-chamber package or by adjusting the volumes of the parts so that the before and / or during the removal takes place contact to a very intensive mixing leads.

Although the individual chambers of Mehrkammergebindes independently can take any volume, it has for mixing as Proved favorable if the contents of the individual chambers are not too different from each other differ.

In a preferred embodiment of the multi-chamber package, therefore, the ratio (Q _Vol ) between the volume of the largest chamber (V _max ) and the volume of the smallest chamber (V _min ) Q Vol = V Max V min at most equal to 4, in particular between 1 and 2.5. Most preferably, all chambers are about the same size, which means that Q _{vol is} between 1 and 1.2.

Under the volume of a chamber of Mehrkammergebindes the entire Interior of the chamber understood, so both with processing chemicals filled space as well as any remaining volume. For the safe Handling, it is further preferred if the container no more than 20 kg, in particular not more than 10 kg. Suitable multi-chamber packages are e.g. Two-chamber container with chamber volumes from 2 times 100 ml to 2 times 5 L, preferably with chamber volumes of 2 times 125 ml to 2 times 3 L and especially preferably with chamber volumes of 2 times 250 ml to 2 times 2.5 l.

Optimizing the parts of a processing refill concentrate in the manner that they fit from the volume to the multi-chamber packages, the skilled person in the field of photographic processing chemicals and is the invention not limited to a particular type of division.

In order to save manufacturing costs, contain the chambers of a multi-chamber package prefers all different preparations and are all at least 50% by volume, especially at least 70% by volume and more preferably too at least 80 vol .-% filled with the preparation. The rest, not from the preparation filled volume of the chambers is usually with air or a Equilibrium mixture of air and the escaping from the preparations Filled with gases. Instead of air, however, at least partially can also contain a protective gas or the air pressure can be reduced in the chambers. As a protective gas For the purposes of the invention, any gas or gas mixture is to be understood that among the usual storage conditions not with the concentrate in the same chamber responding. Particularly preferably, the protective gas is free of oxygen and it acts e.g. around nitrogen, carbon dioxide or argon.

However, the multi-chamber container may also contain chambers in which no Preparation is or two or more chambers, which have the same preparation. Not used for receiving preparations, unused Partial volumes and multiple chambers with the same preparation will be if possible avoided, but z. B. for reasons of stability or manufacturing technology Be necessary.

In a preferred embodiment of the multi-chamber package possess at least two chambers, preferably all chambers, a common closable Removal opening and the chambers are in the closed state of each other separated.

In a further preferred embodiment of the multi-chamber package according to of the present invention have at least two chambers, preferably all Chambers, separate openings with an adapter to a removal opening are connected. In this embodiment, it is crucial that the different Chemicals are not already in the adapter during transport and storage Contact advised. The adapter can z. B. consist of channels, by the individual Going out chambers and led separately to a closure on the spout where they are also sealed against each other.

If the different chemicals in the adapter during removal in Should be advised, the individual chambers during transport and Storage should be closed and only shortly before removal and before placing the Adapters are opened. This can z. B. happen that the adapter during Put on the container while the chambers opens by z. Legs Breakage point or a seal breaks through and docks at this point. Such a Adapters can also contain elements that cause mixing of chemicals promote. Also possible are adapters with valves and in particular those with check valves.

Preferably, the multi-chamber container has only one closure, all chambers closes, for which any known type of closure is suitable, as long as the Chambers are thereby sealed against each other. In particular, it may be the closure around a stopper, a seal, a hinged lid or a Actuate screw, and particularly preferably is in the Closure around a screw cap.

A screw cap, the z. As used for the two-chamber container according to FIGS. 1 and 2 , by molding and selection of materials alone may be sufficient to seal the container according to the invention, but preferably it contains an insert, for example in the form of a sealing washer made of softer or more flexible and chemical-resistant material that allows a secure sealing.

A hinged lid is preferably part of a closure device, via the or the spout of the chambers is pushed and there form-fitting, e.g. by Snap is attached. By attaching the closure device are at the same time the chambers are stabilized and held together.

In a particularly advantageous embodiment of the present invention, the chambers of the container are also gas-tightly separated from each other. This avoids that volatile components of the different chemicals come into contact during transport and storage. This can be achieved with known types of closure, but particularly advantageous it is achieved with a mounted on the bottleneck seal, which simultaneously seals all the chambers and which is withdrawn or pierced before removal. In the bottle according to FIGS. 1 and 2 , the seal z. B. attached so that it seals the surfaces ( 2 ) and ( 3 ) and thus also the chambers ( 4 ) and ( 5 ). The seal can z. B. glued, welded or formed from the bottle material itself and welded. Particularly preferably, the seal consists of a suitable film, in particular of aluminum-laminated polyethylene and is in particular connected by high-frequency welding firmly with the multi-chamber container opening.

The multi-chamber container according to the present invention can be known from all known Materials that are resistant to the solutions used are. In order to allow a low weight, however, it is preferred if the Container consists predominantly of plastic and especially if it is complete made of plastic. Plastic containers are also very resistant to breakage and can be used in the Compared to other materials in the production easier to be formed. When Plastics are all moldable plastics, which are commonly used e.g. for the Production of plastic bottles are used. For the multi-chamber packages Particularly suitable plastics are polyethylene (PE), polypropylene (PP), polyethylene terephthalate (PET) or polyvinyl chloride (PVC); Mixtures thereof; or copolymers from the monomers underlying said polymers. To one Disposal, the containers are preferably made from single-grade plastics, especially made of PE, PP or PET. Advantageous can also be recycled plastic be used.

In principle, multi-chamber containers made of glass can also be used because of their fragility and the high weight but less well suited as such Plastic.

The advantages of the invention can already be achieved by separate containers which are mechanically connected to a container, e.g. by being in a packaging, in particular a carton, or e.g. through suitable integrated interlocking profiles or clamping devices are held together, or by e.g. with a shrink film and / or an adhesive film and / or an elastic and / or resilient material are firmly connected. Especially Advantageously, they are held together with an adhesive label, which also for the warning and use instructions are needed.

Regardless of whether separate containers or firmly connected chambers are used, it is preferred if the bottle necks of the individual containers or chambers are asymmetrically arranged or designed such that the individual bottle necks come as close as possible. As a result, for example, simply a closure screwed or plugged. For two-chamber container, an embodiment according to FIGS. 1 and 2 is particularly preferred, in which the necks of the two chambers open into a round screw thread. This design can be z. B. realize with separate containers or bottles, each having a semicircular bottle neck on the outer edge of the bottle and are accurately connected with each other. The exact connection can be z. B. be achieved in that the contact surfaces of the bottles include features such as groove and rib or generally recess on a surface and increase on the adjacent surface, which fit accurately into one another.

In an advantageous embodiment of the invention, however, the chambers are firmly connected to each other physicochemically and / or chemically. By a physicochemical compound is meant, for example, adhesion-based bonding, and chemical bonding, for example, bonding based on a chemical reaction, fusion of the container parts or manufacture of the container parts as a coherent unit. It is particularly preferred to produce the container parts as a coherent unit in which the multi-chamber container is produced, for example by extrusion blow molding (extrusion blown) in one step with a mold or in combination with a separate second step by injection molding. Initially, only a large chamber can be produced as a blank, from which then the required number of chambers is obtained in the shaping subsequent step. Figs. 1 and 2 show such a two-chamber container produced in the extrusion blown process. The containers can be additionally stabilized in that the chambers which are firmly connected in this case are also connected to a shrink or adhesive film. It is particularly advantageous to connect the chambers with an adhesive label. This gives a large label area for the required instructions and at the same time a higher stability of the multi-chamber container.

Particularly preferred are multi-chamber containers, in particular two-chambered bottles, consisting of at least two container parts with spout, which in one piece are molded from plastic and their container parts via a connecting web connected to each other, which is approximately parallel to the axial extent of the container parts runs and at the same time the partition between the container chambers forms. Each container part can on both sides of the axial connecting web over at least one substantially radially extending, web-like stiffening of the or be attached to the adjacent container part (s).

The radial stiffening webs of the container parts give the multi-chamber container a greater rigidity. In particular, this is a tilting or pivoting prevents the container parts around the axial connecting web. Due to the design-related Increasing the container stiffness can increase the wall thickness of the container parts be reduced, which is advantageous to the production of the multi-chamber container effect.

A particularly tilt-resistant construction of the multi-chamber container, even at reduced wall thickness of the container parts, results when the radial stiffening webs are connected to the axial connecting web.

The particularly preferred multi-chamber container with at least two similar, via an axial connecting web interconnected container parts with Spout, which together form a container neck, is advantageous with the Extrusion blow molding produced. The extrusion blow molding process is Tried and allowed the mass-technical, cost-effective production of one-piece Multi-chamber plastic containers in large quantities. This is a Preform in a for the production and connection of the container parts accordingly equipped with separate mold chambers blow mold and a in the Blow mold introduced Blasdom by means of a gas injected under pressure inflated. The preform, usually made of melted plastic granules can be prepared in various forms. For example, he can be formed as a hose or have an elongated cylindrical shape. Of the Preform is immediately after its production or even later Time introduced into the cavity of a blow mold and according to the Mold cavity inflated and thereby formed into its final shape.

As an alternative to the one-hose method described above can also from 2 or more simultaneously generated and closely adjacent preforms become. Each preform represents a preliminary stage for a chamber and during the blowing process These blanks are transformed into the final multi-chamber container. This more complex manufacturing process has the advantage that the common Partition wall between 2 chambers is double-layered, resulting in an increased mechanical Stability and leakage safety results.

Multi-chamber container with three, four or more separate chambers can be constructed and prepared analogously, as described for the two-chamber container. The individual bottles can be z. B. arranged in a row or concentrically, but they are preferably Tortenstück-like arranged (3 circle segments each 120 ° in a three-chamber bottle) and the necks of the individual bottles or chambers complement each other to a preferably round neck of Mehrkammergebindes. In the neck, the boundary surfaces of the chambers continue in a ridge, as previously described for the two-chamber bottle according to FIGS. 1 and 2 .

For a three-chamber container, the bar divides the neck into 3 culverts, for a four-chambered bottle in four, etc ..

Further advantages can be achieved with a multi-chamber container similar to that shown in FIGS. 1 and 2 , if, instead of the straight connecting web according to FIG. 2, a connecting web which is not straight is provided, eg curved or in stepped, S or Z shape. Such a non-straight connecting web, of which a particularly advantageous embodiment with step-shaped connecting web ( 6 ) is reproduced in FIG. 3 , acts as a forced mixer with particularly high reproducibility and independence from the position of the bottle during emptying. The multi-chamber containers with non-straight connecting web have similar mixing properties as containers with a suitable adapter, but can be more expensive to produce, as those with adapter. Nevertheless, the multi-chamber container with non-straight connecting web can be advantageous if an adapter application is not possible or undesirable for technical reasons, on customer request or because of the space required.

Also to ensure confusion with chemicals for other processing baths To exclude, the multi-chamber packages may be provided with features that easily and clearly indicate for which processing step the container is provided. This can e.g. by a color coding on the container, which is found at the corresponding inlet of the processing tank. Yet safer is an embodiment of the removal opening of the container and to match the inlet of the processing tank such that only the designated container can be emptied into the appropriate processing tank. This is e.g. by the shape of the outer outline of the removal opening possible to the inner Outline of the inlet fits and may e.g. through different geometric Shapes such as circle, rectangle, grooves, etc. be achieved.

Although the multi-chamber container can also be withdrawn subsets, it is preferred, however, to completely empty a multi-chamber container at a removal. This allows for greater passage of the neck of the bottle from the passage, which would allow for accurate dosing. It has been found that a larger passage cross-section is favorable for the mixing. Preferably, the passage cross section at the bottleneck for at least one chamber is at least 50 mm ² , in particular at least 150 mm ² and particularly preferably at least 250 mm ² . Further advantages are achieved if all the chambers of the multi-chamber container have such a cross-section. Larger passage cross sections also facilitate the filling of the multi-chamber container.

The color development chemicals may be used in the multi-chamber package as liquids, Containing solids or mixtures thereof, in particular as solutions, Pastes, powders, granules or dispersions such as slurries or emulsions. The chemicals contained in the chambers are either flowable or can transferred by handling before removal in a flowable state become. Suitable manipulations may e.g. Be shaking or that before the Removal of at least 2 chambers are interconnected and mixed. The multi-chamber package preferably contains concentrated solutions of the color development chemicals.

For the color development step, it was found that the problems described above with regard to poorly reproducible processing results can be greatly reduced can, if for refilling the color developer replenisher solution a multi-chamber container is used. This advantage is particularly pronounced in processing of silver halide color photographic materials, in particular of Copying materials with a silver chloride content of at least 95 mol% based on the entire silver halide in the material and occurs most in short Development times of 15 to 110 seconds, especially from 20 to 90 seconds and especially from 25 to 60 seconds.

Particularly pronounced advantages of the invention also occur in the processing of Recording materials, the predominantly bromide-rich Silberbromidiodidemulsionen contain, in particular if the recording materials in at least a layer of tabular silver halide crystals having an aspect ratio of at least 2, in particular from 4 to 16, wherein the proportion of the tabular Crystals at least 50 mol% of the silver in the layer makes up and the tabular crystals at least 85 mol% of silver bromide and at least 1 mol% Silver iodide, in particular at least 90 mol% of silver bromide and between 2 and 10 contain mol% of silver iodide. The development time is in such recording materials from 45 to 300 seconds, especially from 60 to 270 seconds and more preferably from 90 to 240 seconds.

Particularly good results can be achieved with a multi-chamber container, in which the developer substance and the alkali are in separate chambers and in particular each contained as a concentrate.

In particular, compared with the known one-part color developer concentrates thereby an increased self-oxidation of the concentrate can be avoided, whereby the durability of both the concentrate itself and the resulting Regenerator tank solution (regenerator) is significantly improved.

In addition, it is possible to produce a more concentrated preparation and thereby Save transport and storage costs without causing precipitation.

In a preferred embodiment, the multi-chamber package consists of 2 Chambers, one containing a concentrate with a color developing agent, e.g. 4- (N-ethyl-N-2-methylsulfonylaminoethyl) -2-methyl-phenylenediaminesesquisulfate (CD-3) or 4- (N-ethyl-N-2-hydroxyethyl) -2-methylphenylenediamine sulfate (CD-4) contains and has a pH less than 7. The other chamber contains a concentrate, which has a pH greater than 7 and u.a. contains a buffer and alkali.

The color developing agent may be in the concentrate as sulfate, as in CD-3 or CD-4 is common, but also as phosphate, p-toluenesulfonate, chloride or as free base, to be added. But it can also CD-3 (sesquisulfate) or CD-4 (Sulfate) used and the sulfate ions by precipitation with metal ions and filtration be separated.

The color developer substances are in the concentrate between 0.04 to 2.3 mol / l, preferably between 0.05 to 2.1 mol / l and more preferably between 0.06 to 1.9 mol / l used.

The concentrates for a color developer (developer concentrate) according to the invention contain besides the color developing agent still the usual, for the development a color photographic material required chemicals, in particular Anti-oxidants, solvents, wetting agents, anti-scale agents, whiteners, Complexing agent for heavy metal ions, a buffer system, antifoggant and Acids or alkalis for pH adjustment.

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n

0 oder 1

bedeuten, vorzugsweise solche, bei denen wenigstens einer der Reste R₁ und R₂ wenigstens eine -OH-, -COOH- oder -SO₃H-Gruppe enthält;

worin

R₃

eine Alkyl- oder Acylgruppe bedeutet;

worin

R₄

eine gegebenenfalls durch O-Atome unterbrochene Alkylengruppe und

m

eine Zahl von wenigstens 2 bedeutet.

Suitable antioxidants are alkali sulfites or alkali disulfites, hydroxylamine (HA), diethylhydroxylamine (DEHA), N, N-bis (2-sulfoethyl) hydroxylamine (HADS) and compounds of the formulas (I), (II) and (III) :

wherein

R ₁

optionally substituted alkyl,

R ₂

optionally substituted alkyl or optionally substituted aryl and

n

0 or 1

preferably, those in which at least one of the radicals R ₁ and R _{2 contains} at least one -OH, -COOH or -SO ₃ H group;

wherein

R ₃

an alkyl or acyl group;

wherein

R ₄

an optionally interrupted by O atoms alkylene group and

m

a number of at least 2 means.

The alkyl groups R ₁ , R ₂ , R ₃ , the alkylene group R ₄ and the aryl group R ₂ may have further substituents beyond the specified substitution.

(0-3)   CH₃CH(CH₃)NHOH

Examples of suitable antioxidants are

(0-3) _CH3 CH _(CH3) NHOH

When using 4- (N-ethyl-N-2-methylsulfonylaminoethyl) -2-methyl-phenylenediamine sesquisulfate (CD-3) or 4- (N-ethyl-N-2-hydroxyethyl) -2-methylphenylenediamine sulfate (CD-4) as color developing agent are sulfites, hydroxalymin, Diethylhydroxylamine and antioxidant (0-2) are preferred. Especially preferred Oxidation inhibitors are hydroxylammonium sulfate, sodium sulfite, potassium sulfite, (0-2) and diethylhydroxylamine. They are also combinations of antioxidants or the use of multiple antioxidants possible.

The antioxidants are in the concentrate in amounts of 0.1 mmol to 10.0 mol / l, preferably in amounts of 0.5 mmol to 8.0 mol / l, more preferably in Amounts of 1.0 mmol to 6.0 mol / l used.

The concentrates for processing color negative papers may, in a preferred Embodiment one or more water-soluble organic solvents contain.

In a preferred embodiment for concentrates for processing color negative papers The organic solvent contains a mixture of polyethylene glycols different molecular weight of monoethylene glycol to the Polyethylene glycol having an average molecular weight of 20,000, for example a Mixture of diethylene glycol, polyethylene glycol with the average molecular weight of 400 and polyethylene glycol having the average molecular weight of 15,000 Molweights are weight average.

The polyethylene glycol mixture makes in particular at least 90% by volume of the organic Solvent.

Ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propanediol, triethylene glycol monophenyl ether and diethylene glycol monoethyl ether can also be used as preferred glycols.
In addition to glycols, it is also possible with preference to use triethanolamine, triisopropanolamine, caprolactam, propylene glycol or propylene glycol mixtures or p-toluenesulfonic acid or salts thereof.

As water-soluble organic solvents are those from the series of glycols, Polyglycols, alkanolamines, aliphatic and heterocyclic carbonamides, aliphatic and cyclic monoalcohols, where 50 to 95 wt .-%, preferably 60 to 90% by weight of the sum of water and water-soluble Solvent is water.

Examples of suitable water-soluble solvents are carboxylic acid amide and urea derivatives such as dimethylformamide, methylacetamide, dimethylacetamide, N, N'-dimethylurea, tetramethylurea, methanesulfonic acid amide, dimethylethyleneurea, N-acetylglycine, N-valeramide, isovaleramide, N-butyramide, N, N-dimethylbutyramide, N - (2-hydroxyphenyl) acetamide, N- (2-methoxyphenyl) acetamide, 2-pyrrolidinone, ε-caprolactam, acetanilide, benzamide, toluenesulfonic acid amide, phthalimide;
aliphatic and cyclic alcohols, for example isopropanol, tert-butyl alcohol, cyclohexanol, cyclohexanemethanol, 1,4-cyclohexanedimethanol;
aliphatic and cyclic polyalcohols, for example glycols, polyglycols, polywaxes, trimethyl-1,6-hexanediol, glycerol, 1,1,1-trimethylolpropane, pentaerythritol, sorbitol;
aliphatic and cyclic ketones, for example acetone, ethyl-methyl-ketone, diethyl ketone, tert-butyl-methyl-ketone, diisobutyl ketone, acetylacetone, acetonylacetone, cyclopentanone, acetophenone;
aliphatic and cyclic carboxylic acid esters, for example triethoxymethane, methyl acetate, allyl acetate, methyl glycol acetate, ethylene glycol diacetate, glycerol 1-acetate, glycerol diacetate, methylcyclohexyl acetate, methyl salicylate, phenyl salicylate;
aliphatic and cyclic phosphonic acid esters, for example dimethyl methylphosphonate, diethyl allylphosphonate;
aliphatic and cyclic oxy-alcohols, for example 4-hydroxy-4-methyl-2-pentanone, salicylaldehyde;
aliphatic and cyclic aldehydes, eg, acetaldehyde, propanal, trimethylacetaldehyde, crotonaldehyde, glutaraldehyde, 1,2,5,6-tetrahydrobenzaldehyde, benzaldehyde, benzenepropane, terephthalaldehyde;
aliphatic and cyclic oximes, eg butanone oxime, cyclohexanone oxime;
aliphatic and cyclic amines (primary, secondary or tertiary), for example ethylamine, diethylamine, triethylamine, dipropylamine, pyrrolidine, morpholine, 2-aminopyrimidine;
aliphatic and cyclic polyamines (primary, secondary or tertiary), for example ethylenediamine, 1-amino-2-diethylaminoethane, methyl-bis- (2-methylamino-ethyl) amine, permethyldiethylenetriamine, 1,4-cyclohexanediamine, 1,4- benzenediamine;
aliphatic and cyclic hydroxyamines, for example ethanolamine, 2-methylaminoethanol, 2- (dimethylamino) ethanol, 2- (2-dimethylamino-ethoxy) -ethanol, diethanolamine, N-methyldiethanolamine, triethanolamine, 2- (2-aminoethylamino) ethanol, triisopropanolamine , 2-amino-2-hydroxymethyl-1,3-propanediol, 1-piperidineethanol, 2-aminophenol, barbituric acid, 2- (4-aminophenoxy) ethanol, 5-amino-1-naphthol.

The concentrates for processing color negative films preferably contain no or only small amounts of one or more water-soluble organic Solvent.

Suitable anticaking agents are, for example, aminopolycarboxylic acids, e.g. Ethylenediaminetetraacetic acid (EDTA), propylenediaminetetraacetic acid (PDTA), β-alaninediacetic acid (ADA), diethylenetriaminepentaacetic acid (DTPA), methyliminodiacetic acid (MIDA), ethylenediamine monosuccinate (EDMS), methylglycine diacetic acid (MGDA), ethylenediamine disuccinate (EDDS), especially (S, S) -EDDS, iminosuccinic acid, Iminosuccinic acid propionic acid, 2-hydroxypropyliminodiacetic acid.

Further suitable complexing agents for calcium and also for heavy metals are e.g. Polyphosphates, phosphonic acids, polyaminopolyphosphonic acids, hydroxyalkylidenediphosphonic acids, Aminopolyphosphonic acids and hydrolyzed polymaleic anhydride, e.g. Sodium hexametaphosphate, 1-hydroxyethane-1,1-diphosphonic acid, Aminotrismethylene phosphonic acid, ethylenediamine tetramethylene phosphonic acid, 4,5-dihydroxy-1,3-benzenedisulfonic acid, 5,6-dihydroxy-1,2,4-benzenetrisulfonic acid, 3,4,5-trihydroxybenzoic acid, morpholinomethanediphosphonic acid and diethylenetriaminepentamethylenephosphonic acid.

The concentrates preferably contain no undissolved constituents and are in particular precipitation-free during storage, particularly preferably during storage below 0 ° C, especially between 0 ° C and -7 ° C.

The concentrates used can be a comparatively high proportion water-miscible, hydroxyl-bearing, in particular straight-chain organic Solvents having a molecular weight of about 50 to 200 and a contained therein soluble buffer substance. Preferably, the weight ratio of Water to the organic solvent between 15:85 and 50:50.

The wetting agents used in the concentrate may be anionic, cationic or nonionic be. Preference is given to nonionic wetting agents with polyalkylene oxide structural units.

The buffer substance preferably has a pKa value between 9 and 13. Suitable Buffer substances are z. Carbonates, borates, tetraborates, salts of glycine, Triethanolamine, diethanolamine, phosphates and hydroxybenzoates, of which alkali metal carbonates, Alkaline phosphates and triethanolamine are preferred and alkali metal carbonates such as For example, sodium carbonate and potassium carbonate are particularly preferred.

In the preparation of low-sulphate color developer-containing concentrates is an aqueous solution containing the sulfate of the color developer and optionally contains further additives, mixed with an alkali metal base and then For example, by adding the organic solvent, alkali metal sulfate precipitation be completed. The alkali metal sulfate is replaced by any suitable separation technique, eg. B. by filtration, separated.

For this purpose, particularly suitable organic solvents are, for. As polyols and thereof especially glycols such as ethylene glycol, diethylene glycol and triethylene glycol, Polyhydroxyamines and especially polyalkanolamines and alcohols, in particular Ethanol and benzyl alcohols. The best for the production of single-phase one-part concentrates suitable organic solvent is diethylene glycol.

The processing conditions, suitable color developing agents, suitable buffering agents, suitable anti-scale agents, suitable whiteners, auxiliary developers, Development accelerators and antifoggants are described in Research Disclosure 37 038 (February 1995) on pages 102 to 107 and 111 to 112.

Farbentwickeln, Bleichfixieren, Wässern/Stabilisieren

Farbentwickeln, Bleichen, Fixieren, Wässern/Stabilisieren

Farbentwickeln, Bleichen, Bleichfixieren, Wässern/Stabilisieren

Farbentwickeln, Stoppen, Wässern, Bleichen, Wässern, Fixieren, Wässern/Stabilisieren

Farbentwickeln, Bleichfixieren, Fixieren, Wässern/Stabilisieren

Farbentwickeln, Bleichen, Bleichfixieren, Fixieren, Wässern/Stabilisieren

The following processing sequences are particularly suitable:

Color development, bleach fixing, watering / stabilizing

Color development, bleaching, fixing, watering / stabilizing

Color development, bleaching, bleach-fixing, watering / stabilizing

Color development, stopping, watering, bleaching, watering, fixing, watering / stabilizing

Color development, bleach-fix, fix, rinse / stabilize

Color development, bleaching, bleach-fixing, fixing, watering / stabilizing

The multi-chamber package for a color developer replenisher may also include third concentrate, e.g. Antioxidant, whitener with solvents or stabilizers.

The invention also provides a process for the development of color photographic Materials, characterized in that for refilling the color developing chemicals a multi-chamber container is used.

The invention also provides a process for producing a multi-chamber package, characterized in that the chambers of the container in one piece be prepared by a plastic extrusion blown, then the different Color development chemicals are filled into the chambers and then the container is closed.

The invention is also the use of the multi-chamber package for Refill a color development tank or a color developer replenisher tank a photographic processing device.

Further preferred embodiments of the present invention are the subclaims refer to.

Examples Execution of processing trials a) Processing experiments with color negative films

In the following Examples 2 to 4, commercial Agfa Vista films 100, 200 and 400 were processed which have a total silver content of about 3.5 to 8 g silver per m ² and their silver halide emulsions are predominantly tabular silver bromoiodide emulsions having a bromide content of over 90 mol% and an iodide content between 1 and 10 mol% exist. The processing was carried out in an Agfa MSC 101 film minilab, preparing the minilab for each individual experiment as follows.

Für je 1 Liter Tanklösung:

750 ml des angesetzten Regenerators

Zugabe von 40 ml 71/72 CD-Starter

Mit 210 ml Wasser auf 1 Liter auffüllen

The processing tanks (CD, BL, FX, SB) of the initially completely emptied (processing and replenishment tank) minilab were set up using a commercial Agfa MSC 101 film tank kit (Process AP 72) and the bleach, fixer replenisher tanks and Stabilizer from the commercially available MSC 101 film BL-R, MSC 101 film FX-R and MSC 101 film SB-R. The regenerator container for the developer was filled as described in the examples. If necessary, the regenerator was prepared from the respective concentrates to determine the sensitometry, in order to then prepare the developer tank solution as follows:

For every 1 liter of tank solution:

750 ml of the attached regenerator

Add 40 ml of 71/72 CD starter

Make up to 1 liter with 210 ml of water

To simulate a handling error of the operators, the Batches in the developer recovery tank are not stirred. All tank solutions and the rest of the regenerator solutions were made according to the type.

The replenishment rates were 22.5 ml per 135-24 film in all experiments Color developer, 5 ml per 135-24 film for the bleach, 33 ml per 135-24 film for the fixer and 40 ml per 135-24 film for the stabilizer.

To bring the process in a state of equilibrium, was one each certain amount of those exposed to standard motifs given in the examples Color negative films processed. After that, grayscale wedges were replaced by a blue, green or red filter were exposed to the sensitometry to judge. This procedure was repeated several times as needed.

In experiments where regeneration was not performed, sensitometry was used the grayscale wedges directly in the MSC 101 film minilab with those in the trials determined tank solutions determined.

For the experiments according to the invention, a two-chamber bottle according to FIGS. 1 and 2 or an analogously constructed three-chamber bottle was used, which also had a common spout for the three chambers, wherein the passage openings on the spout circular segments at an angle of 120 ° made. When pouring the two-chamber bottle was held so that the spout separating the connecting web and its upper end surface (3) was aligned horizontally. In the three-chamber bottle, the orientation during pouring had no observable influence on the test results.

b) Processing trials with color negative paper

In the following Example 6, commercial Agfa type 11 color paper was processed, which is a photographic color negative paper for rapid processing, which has a total silver content of about 0.6 g silver per m ² and whose silver halide emulsions exceed 95 mol. % consist of cubic silver chloride. The processing was carried out in an Agfa Minilab of type MSC 101, the minilab being prepared for each individual experiment as follows.

The processing tanks of the initially completely emptied (processing and replenishment tank) minilab were prepared using a commercial Agfa MSC 101 paper tank kit (Process AP 94) and the regenerator tanks for the bleach-fix bath and stabilizer from the commercial MSC 101 Paper BX-R and MSC 101 Paper SB-R. The regenerator container for the developer was filled as described in the examples.
The sensitometry was determined directly from the MSC 101 paper minilab using the tank solutions described in the experiments with the aid of grayscale wedges illuminated by a blue, green or red filter.

To simulate a handling error of the operators, the Batches in the developer recovery tank are not stirred. All tank solutions and the rest of the regenerator solutions were made according to the type.

Also for the paper processing were the above for the film processing used two- or three-chamber bottles.

example 1

With this experiment, the mixing in the regenerator was a Agfa MSC 101 (movie part) checked. It only has to be prepared as a preparation the regenerator container for the color developer solution is emptied. A processing was not accomplished.

1 liter of concentrate contains part A. 700 ml Potash solution, 50% by weight 10 g potassium 50 g DTPA 70 ml Potassium hydroxide, 45% by weight

1 liter of concentrate contains part B. 50 g hydroxylammonium

1 liter of concentrate contains part C. 100 g CD 4 60 g sodium metabisulfite PH value 4.0 The pH is adjusted with potassium hydroxide solution.

For the production of 1 liter of ready-to-use color developer replenisher solution 60 ml of Part A, 60 ml of Part B and 60 ml of Part C are required.

a) nacheinander in der genannten Reihenfolge aus jeweils einer 750 ml Flasche mit jeweils 600 ml Flüssigkeitsvolumen zugegeben und
im zweiten Versuch

b) gleichzeitig aus einer Dreikammerflasche mit 3 x 600 ml Flüssigkeitsvolumen zugegeben,

wobei im Versuch b) die Konzentrate direkt hinter der Entnahmeöffnung in Kontakt geraten und die Kammern ein Volumen von jeweils ca. 700 ml aufweisen.With the above concentrates, two 10 liter batches were made in the previously completely deflated color developer replenisher container of an Agfa MSC 101 minilab. For each 8.2 liters of water were submitted and the concentrates Part A, Part B and Part C.
in the first attempt

a) successively added in the order mentioned from each of a 750 ml bottle, each with 600 ml of liquid volume and
in the second attempt

b) added simultaneously from a three-chamber bottle with 3 x 600 ml liquid volume,

wherein in experiment b) the concentrates come into contact directly behind the removal opening and the chambers have a volume of approximately 700 ml each.

In order to simulate a handling error of the operators, the batches in the color developer regenerator container were not stirred. From the two batches samples were taken at different heights of the regenerator tank and analyzed for potash, hydroxylammonium sulfate (HAS) and CD4 content. The results are shown in Table 1. comparison invention analyzed ingredient sampling point a)
3 individual bottles b)
Three-compartment bottle potash above 14.7 g / l 28.9 g / l center 87.0 g / l 36.5 g / l below 43.6 g / l 34.2 g / l HAS above 1.4 g / l 2.6 g / l center 2.1 g / l 2.9 g / l below 5.7 g / l 3.3 g / l CD 4 above 1.8 g / l 4.9 g / l center 3.7 g / l 5.2 g / l below 12.4 g / l 5.6 g / l

From the results it can be clearly seen that by the simultaneous inflow the three concentrates from a three-chamber bottle surprisingly a substantial better mixing of the approach than when using three individual bottles.

Example 2

To the influence of mixing on the processed material and the sensitometric To investigate effects, experiments a) and b) were carried out Example 1 repeated, but this time as under "carrying out the processing experiments" described. As the imagewise result the sensitometric parameters Purple Sensitivity and Yellow Veil Dmin exert the greatest influence These parameters were determined depending on the number of processed movies in the MSC 101 movie minilab.

The results are shown in Tables 2 and 3. comparison invention Film throughput
(Movies 135-24) a) from 3 bottles
a 750 ml b) from three-chamber bottle 0
(Fresh batch) Relative pp sensitivity 100 100 200 127 108 400 144 111 600 119 105 800 92 103 1200 86 101

It can be clearly seen from Table 2 that during the course of the film processing a significant change in the pp sensitivity occurs when the regenerator is made up of the 3 bottles usually used, while surprisingly this problem does not occur when using the three-chamber bottle according to the invention.

From Table 3 it can be seen clearly that in the course of the film processing a significant increase in yellow haze occurs when the regenerator from the usual used 3 bottles, while this problem in the Surprisingly, not using the three-chamber bottle according to the invention occurs.

Example 3

a) zusammen in eine Flasche gefüllt sowie

b) in eine Dreikammerflasche gefüllt,

die zum Ansatz von je 10 L Regenerator verwendet werden sollten. Dafür wurden jeweils 600 ml Teil A, B und C benötigt. Für die Konzentrate der Dreikammerflasche wurde eine 3 mal 700 ml Flasche und für das einteilige Farbentwicklerkonzentrat eine 2 L Flasche verwendet.
Die Flaschen wurden

1. im Warmen bei 60 °C im Heizschrank und

2. im Kühlen bei - 5 °C im Kühlschrank gelagert.

Of the concentrates of Example 1, in each case 600 ml of Parts A, B and C.

a) filled together in a bottle as well

b) filled in a three-chamber bottle,

which should be used to approach each 10 L regenerator. For each 600 ml part A, B and C were needed. For the concentrates of the three-chamber bottle, a 3 times 700 ml bottle and for the one-piece color developer concentrate, a 2 L bottle was used.
The bottles were

1. in warm at 60 ° C in the heating cabinet and

2. refrigerated at - 5 ° C in the refrigerator.

The storage at 60 ° C was carried out so that the 2 L bottle and the 3 times 700 ml bottle were stored at 60 ° C for 2 weeks. Afterwards, the appearance, the analysis values of HAS and sulfite as well as the sensitometry against fresh samples were compared. The sensitometric determination was carried out after processing with an MSC 101. The results are shown in Table 4. comparison invention rating Result 2 L bottle 3 times 700 ml bottle fresh stored fresh stored Appearance Part A yellowish dark purple colorless unchanged part B colorless unchanged Part C yellowish unchanged analysis HAS 16.3 g / l 0g / l 49.8 g / l 49.4 g / l sulfite 16.5 g / l 0g / l 50.2 g / l 49.7 g / l sensitometry Dmin
yellow 0.92 1.27 0.91 0.93

From Table 4 can be clearly seen that the developer in the 2 L bottle at Hot storage is completely unstable while the developer in the three-chamber bottle no change shows.

The storage at -5 ° C was carried out so that the 2 L bottle and the 3 times 700 ml three-chamber bottle were stored at -5 ° C for 2 weeks. The result after storage is shown in Table 5. comparison invention rating Result 2 L bottle 3 times 700 ml bottle stored stored Appearance Part A precipitations without precipitates part B without precipitates Part C without precipitates

From Table 5 it can be clearly seen that the developer in the 2 L bottle at Cold storage shows precipitations while the developer is in the 3 by 700 ml three-chamber bottle no change shows.

Example 4

1 Liter Konzentrat Teil A enthält 700 ml Pottaschelösung, 50 Gew.-%ig 10 g Kaliumbromid 10 g HADS 50 g DTPA 70 ml Kalilauge, 45 Gew.-%ig

1 Liter Konzentrat Teil B enthält 100 g CD 4 90 g Natriumdisulfit pH-Wert 4,0 Die pH-Einstellung erfolgt mit Kalilauge.

A two-part color developer concentrate without HAS and with more sulfite was thus produced with HADS:

1 liter of concentrate contains part A. 700 ml Potash solution, 50% by weight 10 g potassium 10 g HADS 50 g DTPA 70 ml Potassium hydroxide, 45% by weight

1 liter of concentrate contains part B. 100 g CD 4 90 g sodium metabisulfite PH value 4.0 The pH is adjusted with potassium hydroxide solution.

a) zusammen in eine Flasche gefüllt sowie

b) in eine Zweikammerflasche gefüllt,

die zum Ansatz von je 10 L Regenerator verwendet werden sollten. Dafür werden jeweils 600 ml Teil A und 600 ml Teil B benötigt. Für die Konzentrate der Zweikammerflasche wurde eine 2 mal 700 ml Flasche und für das einteilige Farbentwicklerkonzentrat eine 1,25 L Flasche verwendet.
Die Flaschen wurden

1. im Warmen bei 60 °C im Heizschrank und

2. im Kühlen bei - 5 °C im Kühlschrank gelagert.

There were each 600 ml of parts A and B

a) filled together in a bottle as well

b) filled in a two-chamber bottle,

which should be used to approach each 10 L regenerator. For each 600 ml of Part A and 600 ml Part B are needed. For the concentrates of the two-chamber bottle, a 2 x 700 ml bottle and for the one-part color developer concentrate, a 1.25 L bottle was used.
The bottles were

1. in warm at 60 ° C in the heating cabinet and

2. refrigerated at - 5 ° C in the refrigerator.

The storage at 60 ° C was carried out so that the 1.25 L bottle and the 2 x 700 ml bottle were stored at 60 ° C for 2 weeks. Afterwards the appearance, the analysis values of sulfite as well as the sensitometry against fresh samples were compared. The sensitometric determination was carried out after processing with an MSC 101. The results are shown in Table 6. comparison invention rating Result 1.25 L bottle 2 times 700 ml bottle fresh stored fresh stored Appearance color Part A yellowish dark purple colorless unchanged part B yellowish unchanged analysis sulfite 25.1 g / l 14.8 g / l 75.6 g / l 73.2 g / l sensitometry Dmin yellow 0.91 1.23 0.92 0.95

From Table 6 it can be clearly seen that the developer in the 1.25 L bottle at Hot storage is unstable, while the developer in the two-chamber bottle no Change shows.

Storage at -5 ° C was carried out so that the 1.25 L bottle and the 2 x 700 mL bottles were stored at -5 ° C for 2 weeks. The result after storage is shown in Table 7. comparison invention rating Result 1.25 L bottle 2 times 700 ml bottle stored stored Appearance Part A precipitations without precipitates part B without precipitates

The developer in the 1.25 L bottle shows precipitations during cold storage, while the developer in the two-chamber bottle shows no change.

Example 5

A two-part color developer concentrate for paper development was prepared.

1 Liter Konzentrat Teil A enthält 50 ml Polyglykol P 400 80 g HADS 80 ml Diethylhydroxylamin, 85 Gew.-%ig 20 g Tinopal SFP (Weißtöner der Firma CIBA) 100 g CD 3-Base pH-Wert 4 Die pH-Einstellung erfolgt mit Salzsäure

1 Liter Konzentrat Teil B enthält 120 ml Kalilauge, 45 Gew.-%ig 50 g EDTA 750 ml Pottaschelösung, 50 Gew.-%ig

The following concentrates were used:

1 liter of concentrate contains part A. 50 ml Polyglycol P 400 80 g HADS 80 ml Diethylhydroxylamine, 85% by weight 20 g Tinopal SFP (whitener from CIBA) 100 g CD 3-Base PH value 4 The pH is adjusted with hydrochloric acid

1 liter of concentrate contains part B. 120 ml Potassium hydroxide, 45% by weight 50 g EDTA 750 ml Potash solution, 50% by weight

a) zusammen in eine Flasche gefüllt sowie

b) in eine Zweikammerflasche gefüllt,

die zum Ansatz von je 10 L Regenerator verwendet werden sollten. Dafür werden jeweils 500 ml Teil A und 500 ml Teil B benötigt. Für die Konzentrate der Zweikammerflasche wurde eine 2 mal 500 ml Flasche und für das einteilige Farbentwicklerkonzentrat eine 1 L Flasche verwendet.Of the concentrates, 500 ml portions A and B were each used

a) filled together in a bottle as well

b) filled in a two-chamber bottle,

which should be used to approach each 10 L regenerator. For each 500 ml of Part A and 500 ml Part B are needed. For the concentrates of the two-chamber bottle, a 2 x 500 ml bottle and for the one-piece color developer concentrate, a 1 L bottle was used.

The bottles were refrigerated at -5 ° C for 2 weeks in the refrigerator, the result after storage is shown in Table 8. rating Result comparison invention 1 L bottle 2 times 500 ml bottle Appearance Part A precipitations without precipitates part B without precipitates

The developer in the 1 L bottle shows precipitations during cold storage, while the Developer in the 2 x 500 ml bottle shows no change.

If the CD 3-sesquisulfate is used in the concentrate part A instead of the CD 3-base is, occur when pouring the two partial concentrates in the 1 liter bottle without storage already on precipitations, while in the 2 times 500 ml bottle too in cold storage no precipitation occurs.

Example 6

1. Einteiliger Farbentwickler 1 Liter Konzentrat enthält 500 ml Diethylenglykol 44 ml Diethylhydroxylamin (DEHA), 87 Gew.-%ig 35 g CD 3-Base 5 g Blankophor REU 6 g EDTA 230 ml Pottaschelösung, 50 Gew.-%ig pH-Wert 13 pH-Einstellung erfolgt mit Kalilauge.

2. Zweiteiliger Farbentwickler 1 Liter Konzentrat Teil A enthält 150 g Caprolactam 114 ml Diethylhydroxylamin, 87 Gew.-%ig 20 g Blankophor REU (Weißtöner der Firma BAYER) 150 g CD 3 pH-Wert 3,5 Die Einstellung erfolgt mit Schwefelsäure 1 Liter Konzentrat Teil B enthält 250 ml Kalilauge, 45 Gew.-%ig 70 g EDTA 650 ml Pottaschelösung, 50 Gew.-%ig

3. Dreiteiliger Farbentwickler 1 Liter Konzentrat Teil A enthält 250 ml Triethanolamin 143 ml Diethylhydroxylamin, 87 Gew.-%ig 20 g Blankophor REU (Weißtöner der Firma BAYER) pH-Wert 3,5 Die Einstellung erfolgt mit Schwefelsäure 1 Liter Konzentrat Teil B enthält 190 g CD 3 4 g Natriumdisulfit 1 Liter Konzentrat Teil C enthält 260 ml Kalilauge, 45 Gew.-%ig 90 g EDTA 700 ml Pottaschelösung, 50 Gew.-%ig

For a comparison between one-, two- and three-part CD concentrates, the following concentrates were used:

1. One-part color developer contains 1 liter of concentrate 500 ml diethylene glycol 44 ml Diethylhydroxylamine (DEHA), 87% by weight 35 g CD 3-Base 5 g Blankophor REU 6 g EDTA 230 ml of potash solution, 50% by weight PH value 13 pH adjustment is carried out with potassium hydroxide solution.

2. Two-part color developer contains 1 liter of concentrate part A. 150 g caprolactam 114 ml Diethylhydroxylamine, 87% by weight 20 g Blankophor REU (whitener from BAYER) 150 g CD 3 PH value 3.5 The adjustment is carried out with sulfuric acid 1 liter of concentrate contains part B. 250 ml Potassium hydroxide, 45% by weight 70 g EDTA 650 ml Potash solution, 50% by weight

3. Three-part color developer contains 1 liter of concentrate part A. 250 ml triethanolamine 143 ml Diethylhydroxylamine, 87% by weight 20 g Blankophor REU (whitener from BAYER) PH value 3.5 The adjustment is carried out with sulfuric acid 1 liter of concentrate contains part B. 190 g CD 3 4 g sodium metabisulfite 1 liter of concentrate contains part C. 260 ml Potassium hydroxide, 45% by weight 90 g EDTA 700 ml Potash solution, 50% by weight

For the production of 1 liter of ready-to-use color developer replenisher solution for the one-piece 130 ml, for the two-piece 50 ml Part A and 50 ml Part B 40 ml Part A, 40 ml Part B and 40 ml Part C are required for the 3-part.

The concentrates were prepared so that each set 10 L regenerator become. The one-piece was bottled in a 1300 ml bottle, the two-piece in a 2 times 700 ml two-chamber bottle and the three-part in a 3 times 500 ml Three-compartment bottle. After preparation from the concentrates contain the ready to use Regenerators comparable amounts of active ingredient.

The bottles were stored at 60 ° C for 2 weeks. The appearance, analytical values of DEHA and sensitometry were compared to fresh samples. The sensitometric determination was carried out after administration with an MSC 101. The results are shown in Table 9. comparison invention invention rating Result 1300 ml bottle 2 times 700 ml bottle 3 times 500 ml bottle fresh stored fresh stored fresh stored Appearance Part A light yellow dark yellow yellowish unchanged yellowish unchanged part B colorless unchanged yellowish unchanged Part C - - colorless unchanged analysis DEHA 34.5 g / l 28.1 g / l 89.6 g / l 89.2 g / l 112.3 g / l 112.1 g / l sensitometry Dmin yellow 0,101 0,117 0,102 0.103 0,099 0,100

From Table 9 it can be seen that the one-part developer in the 1300 ml bottle when warmed up darkens in color and shows an increased yellow haze. The however, both developers in the multi-chamber bottles show no change.

Claims (15)

Containers for storing photographic color developing concentrates and for filling the color developing concentrates in a tank of a processing apparatus, wherein the container at least two different chemicals spatially separated in chambers, characterized in that the container is designed so that the different chemicals before filling into the tank be brought into contact with each other within the container and / or be brought into contact with each other during the filling in the tank. Container according to claim 1, characterized in that the different chemicals are brought into contact with each other during the filling in the tank within the container. Container according to claim 1, characterized in that the different chemicals are brought into contact directly with the removal opening during the filling into the tank. Container according to one of claims 1 to 3, characterized in that at least two chambers have a common closable removal opening. Container according to claim 4, characterized in that all chambers have a common closable removal opening. Container according to one of claims 1 to 4, characterized in that at least two chambers have separate openings which are connected to an adapter to a removal opening. Container according to one of claims 1 to 6, characterized in that the container has only one closure which closes all chambers. Container according to claim 7, characterized in that it is the closure is a screw cap. Container according to one of claims 1 to 8, characterized in that at least one removal opening is sealed with a film or sealed with a sealing washer. Container according to one of claims 1 to 9, characterized in that it consists of plastic. Container according to one of claims 1 to 10, characterized in that it contains the chemicals for a two- or three-part color developer concentrate. Container according to one of claims 1 to 11, characterized in that it contains as color developing agent 4- (N-ethyl-N-2-methylsulfonylaminoethyl) -2-methyl-phenylenediaminesesquisulfate (CD-3) or 4- (N-ethyl-N- 2-hydroxyethyl) -2-methylphenylenediamine sulfate (CD-4). Process for processing color photographic materials, characterized in that a container according to one of claims 1 to 12 is used for replenishing the color development chemicals. A process for producing the container according to one of claims 1 to 12, characterized in that the chambers of the container are produced in one piece by a plastic extrusion blown, then the different color development chemicals are filled into the chambers and then the container is closed. Use of the container according to one of claims 1 to 12 for refilling a color development tank or a color developer replenisher tank a photographic processing device.

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