EP1548496A1 - Container for photographic processing chemistry - Google Patents

Abstract

Package for photographic processing chemicals and for filling a tank of a processing apparatus with the processing chemicals, comprises at least two different chemicals spatially separated in chambers. The chemicals belong to the same processing step. Package for photographic processing chemicals and for filling a tank of a processing apparatus with the processing chemicals, comprises at least two different chemicals spatially separated in chambers. The chemicals belong to the same processing step. The package is constructed such that the different 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 processing photographic 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 processing chemicals and for loading the processing chemicals into a tank a processing device, wherein the container at least two different Contains chemicals spatially separated in chambers, in particular such Container for two- or multi-part bleach-fix bath concentrates. The invention also relates to a process for processing photographic materials, in which such containers are used, a method for producing such containers, as well as the use of such containers.

Among photographic processing chemicals are within the meaning of the invention understood chemical substances or preparations of such substances, which are responsible for the Processing of recording materials, in particular silver halide-containing Recording materials can be used. The recording materials are also referred to below as photographic materials and include all materials exposed to actinic radiation, e.g. with light, UV, IR or X-rays can be exposed and after a chemical processing provide a visually or machine recognizable or readable record.

For the processing of photographic materials, the used baths, such as e.g. Developer, bleach, fixer, bleach-fix or stabilizer initially used as tank solutions. These are however during the processing by chemical reaction and by introduction and carryover depending on consumed by the material throughput. 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. for use as a bleach-fix replenisher both one-part as well as multi-part concentrates commercially available. Bleach-fix baths become predominant for processing photographic color negative silver halide paper, such as. Agfa Type 11, used to make the color developed during the color development To oxidise silver (to bleach).

From EP 1 209 520 and US Pat. No. 6,221,570, one-part bleach-fixing bath concentrates are known. However, these have the disadvantage that an oxidizing agent such as e.g. Iron (III) ethylenediaminetetraacetic acid (ferric-EDTA) and a reducing agent such as. Sulfite are contained in the same concentrate and therefore chemically react with each other. The sulfite is oxidized to sulfate and the iron (III) EDTA reduced to iron (II) EDTA. For long storage times or long Shipping times, this chemical reaction can occur almost completely, so that Most of the sulfite is converted to sulfate and the approach of the regenerator solution only a very small amount of sulfite is present. The durability of the Concentrate and the resulting regenerator is thereby significantly reduced. Another disadvantage arises from the fact that with longer storage times the iron (III) EDTA also by other processes to the iron (II) EDTA is reduced. This is after the preparation of the regenerator from the concentrate only a small amount of iron required for bleaching than Iron (III) EDTA before, whereby in a fresh batch of the tank solution or at high paper throughput bleaching problems occur. Another disadvantage of using One-part bleach-fix baths is the fact that through the reaction of Sulfite and ferric EDTA to sulfate and ferrous EDTA the solubility in the concentrate is significantly deteriorated. It can therefore strong Kristallausfällungen of Ammonium iron (II) EDTA occur, which are no longer brought into solution can cause the concentrate to become unusable and nothing more can be used. Because of the described disadvantages of one-part Bleachfixierbädern they have not been able to prevail on the market so far.

To avoid the problems with one-piece concentrates mentioned, therefore For refilling often two- or three-piece preparations of different Composition used, which are filled in separate containers. To exist e.g. commercially available bleach-fixer replenisher solutions of two to three concentrates, wherein one concentrate is the bleaching agent and a second concentrate is the fixing agent contains. A third concentrate can be an acid for pH adjustment However, the acid can also be in one of the concentrate parts for the bleach or the fixative, so in this case only two concentrate parts necessary.

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 processing chemicals are from the unsatisfactory reasons mentioned.

The invention is therefore based on the object, a container for photographic To provide processing chemicals, 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 processing 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 Processing chemicals and for filling the processing chemicals in a tank of a processing apparatus, wherein the container at least two different Contains chemicals spatially separated in chambers, characterized that the chemicals belong to the same processing step and that Container is designed so that the different chemicals before filling be brought into contact with each other in the tank inside the container and / or during filling in the tank (during removal) with each other be brought into contact.

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 However, reclosability may be useful in disposing of the Leakage of chemical residues to prevent.

The photographic processing chemicals in the context of the invention are each multi-chamber containers the replenishment chemicals necessary for a processing 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. These may be the pure chemical compounds themselves or to treat suitable preparations, however, are common concentrated preparations of chemicals (concentrates). The present Invention is for each processing step of each photographic processing process suitable for the at least two different replenishment chemicals in separate preparations 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 causes a premix that prevents inhomogeneities of chemical distribution in the processing equipment. So z. B. the approach of a regenerator when using the known multi-part concentrates in minilabs usually directly in the regenerator tank. For the approach, water is introduced and then added the required concentrates. If, as usual, the concentrates are added one at a time, stratification of the concentrates in the replenisher tank can occur, which can only be eliminated by thorough mixing. However, in many minilabs for cost and space reasons for mixing only one kind of paddle provided, so intensive mixing takes a long time. In the context of the present invention, it has been shown that even if long mixing times are specified, these are often not observed by the operating staff in order to save time and it also happens that the regenerator solution is not thoroughly mixed after the batch. When using the insufficiently mixed regenerator solution chemicals are added in the course of processing of different concentration and composition of the processing solution, which explains the poor reproducibility of the processing and thus the fluctuating quality of the processed material. With the multi-chamber container this disadvantage can be counteracted surprisingly. It turned out that in this way the necessary mixing times can be considerably reduced and, when using particularly suitable containers according to the invention, even the subsequent mixing can be completely dispensed with.
In the context of the present invention, it has been found that unsatisfactory and non-reproducible processing results are also obtained when using the known multipartite concentrates, that either a concentrate part is completely forgotten or that, for example, instead of part A and part B, two parts A are used. In both cases, the processing solution becomes unusable and photographic materials processed with it are often lost forever. In addition, it may happen that concentrates from different production times are mixed together in the batch, for example, a new batch Part A and an old batch Part B are mixed. This can lead to loss of stability and pH variations in the ready-to-use solutions and causes an undefined condition, because no manufacturer of processing chemicals can test all possible combinations of different aged concentrates for their effects and side effects during processing. In addition, such a part of a batch can always be left unused and age strongly. The damage is particularly high if the shelf life of the old batch has already expired, so that it is no longer usable and the approach from this and a new batch is useless. Especially in recent years, the workload of the often trained only operating personnel has increased more and more, which explains, together with the complexity of piecing that occur in non-automated regenerator approaches increasingly complaints and makes it clear how important it is to increase operating safety. Since according to the present invention, the individual concentrates are combined to form a container, their confusion is no longer possible and all concentrates of such a Mehrkammergebindes have the same production time and have undergone the same storage conditions. In addition, it can not happen that a predetermined sequence and a predetermined time is not adhered to when preparing or that eg between the addition of Part A and Part B so much time passes that will be regenerated in the meantime, only with Part A.

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 processing 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 present Be optimized invention, for. By reducing the number of parts, to reduce the manufacturing cost of the multi-chamber package or by the volumes of the parts are adjusted so that the before and / or during the Taking removal takes place as intensive as possible 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 thereby be sealed against each other. In particular, it may be at the Closure around a stopper, a seal, a hinged lid or a screw cap act, and particularly preferably is the closure to 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 to one 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.

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 processing chemicals can be used in the multi-chamber container as liquids, Containing solids or mixtures thereof, in particular as solutions, Pastes, powders, granules or dispersions such as slurries or emulsions. The chemicals are contained in the chambers either flowable, or can be 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 processing chemicals.

In a particularly preferred embodiment of the present invention the multi-chamber container the chemicals for a two- or multi-part bleach-fix concentrate. For this processing step, the known containers are special unsatisfactory and it turned out that the problems described above with regard to poorly reproducible processing results can be greatly reduced can, if for refilling the bleach-fixer-Regeneratorlösung a multi-chamber container is used. This advantage is particularly pronounced in the Processing of color photographic silver halide 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 Bleach-fix times of 10 to 130 seconds, especially 15 to 90 seconds and especially from 20 to 60 seconds.

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

In particular, compared to the known one-part bleach-fix bath 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 container consists of 2 chambers, the one containing a concentrate with a bleaching agent consisting of a Fe (III) complex salt, e.g. Iron (III) EDTA or iron (III) EDDS and a Buffer substance, e.g. Acetic acid, imidazole, phosphoric acid or dicarboxylic acids or their salts. The other chamber contains a concentrate with one Fixing agent, preferably thiosulfate, in particular ammonium thiosulfate and advantageous additionally a stabilizing agent for the fixing agent, e.g. a sulfite salt. The Both concentrates may additionally contain nitrate or bromide.

Fe (III) complex salts suitable for photographic bleach and bleach-fix baths, are known from a variety of documents (e.g., EP 329,088, 584,665, 507,126, 556,782, 532,003, 750,226, 657,777, 599,620, 588,289, 723,194, 851,287, 840 168, 871065, 567 126, 726 203 and US 5,670,305).

Preferred complexing agents for Fe (III) are: ethylenediaminetetraacetic acid (EDTA), Propylenediaminetetraacetic acid (PDTA), β-alaninediacetic acid (ADA), diethylenetriaminepentaacetic acid (DTPA), methyliminodiacetic acid (MIDA), ethylenediamine monosuccinate (EDMS), methylglycinediacetic acid (MGDA), ethylenediamine disuccinate (EDDS), especially (S, S) -EDDS, iminosuccinic acid, iminosuccinic acid propionic acid and 2-hydroxypropyliminodiacetic acid and a preferred bleaching agent contains at least one iron complex with one of said complexing agents.

Mixtures of complexing agents can also be used and Fe (III) complexing agents are used in the concentrate between 0.15 to 1.5 and preferably between 0.2 and 1.2 and particularly preferably 0.3 to 0.9 mol / L ,
In addition, bleach accelerators such as 3-mercapto-1,2,4-triazole or thioglycerol can be used.

Other concentrate ingredients may e.g. Aminopolycarboxylic acids, rehalogenating agents, Acids and alkalis for pH adjustment, bleach accelerators, White couplers and buffering agents (see Research Disclosure 37 038, February 1995, pages 107 to 109).

Preferred buffers besides acetic acid are dicarboxylic acids, e.g. malonic, Succinic acid or adipic acid and their salts. A buffer substance can Both in the chamber with the bleach and in the chamber with the Be contained fixative.

The pH in the concentrate containing the bleaching agent is 1 to 9, preferably 2 to 8 and more preferably 2.5 to 7.5.

As phosphates, the alkali metal salts and / or ammonium salts can be used, e.g. Ammonium dihydrogen phosphate, di-ammonium hydrogen phosphate, tri-ammonium phosphate, Potassium dihydrogen phosphate, di-potassium hydrogen phosphate, tri-potassium phosphate, Sodium dihydrogen phosphate, di-sodium hydrogen phosphate, trisodium phosphate.

As nitrates and bromides alkali and / or ammonium nitrates and bromides be used.

The phosphates, nitrates and bromides are preferably added to the concentrate in one Amount of 0.1 to 2.0 mol / l, in particular 0.2 to 1 mol / l added.

Particularly suitable fixing agents are sodium, potassium and in particular ammonium thiosulfate. In addition, sodium, potassium and ammonium thiocyanate can also be used as a fixative. In addition, fixer accelerators such as e.g. Imidazole be used.

Suitable sulfite salts are e.g. Ammonium sulfite, ammonium hydrogen sulfite, sodium sulfite, Sodium bisulfite, sodium bisulfite, potassium sulfite, potassium bisulfite, Potassium hydrogen sulfite. Suitable sulfinic acids are e.g. hydroxymethanesulfinic Formamidinesulfinic acid, benzenesulfinic acid, p-toluenesulfinic acid, methanesulfinic acid, o-amidosulfinic acid and its salts.

In addition, the concentrates may contain other complexing agents individually or in the Mixture be added. For this preferred complexing agents are polycarboxylic acids such as. Oxalic acid, malonic acid, glutaric acid, adipic acid, suberic acid, fumaric acid, Maleic acid, itaconic acid or phthalic acid. Also preferred are polyhydroxy polycarboxylic acids such as. Citric acid, glycolic acid, lactic acid, malic acid, Tartaric acid or galactaric acid.

After opening and emptying the container, the two concentrates of the Get in touch with each other directly behind the spout and afterwards usually with water in the ratio 1: 1 to 1:20, preferably in the ratio 1: 2 to 1: 15 and more preferably 1: 3 to 1:12 diluted. The concentrates can be used undiluted after opening and emptying the container.

The multi-chamber package for a bleach-fix replenisher may also have a third Concentrate comprising e.g. an acid such as e.g. Acetic acid, succinic acid, phosphoric acid, Nitric acid or sulfuric acid, with which the pH value in the regenerator tank the bleach-fix solution can be adjusted. The acid, however, is preferably in the bleach chamber and / or fixative chamber so that in this case only two concentrate parts are necessary.

In a preferred embodiment of the present invention, not only the chemicals for a processing step with a multi-chamber container refilled, but also for at least one further processing step required chemicals refilled with a multi-chamber container. Will as above described a multi-chamber container for refilling the bleach-fix chemicals used, it is e.g. advantageous, also for refilling the color developer chemicals to use a multi-chamber container.

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.

Color developers are used in the development of color photographic silver halide materials used. In the color developer solutions becomes at the exposed places the emulsion layers of the material, the silver halide to metallic silver reduced. The resulting in this process oxidation products of the color developer react with the color couplers contained in the emulsion layers yellow, purple and blue-green picture dyes. Simultaneously with the black and white pictures So arise dye images that remain when in the following Processing the metallic silver is bleached and removed. The removal of metallic silver occurs predominantly in the processing of colomegative paper in a bleach-fix bath, when processing color negative films predominantly in a bleach bath and a subsequent fixer.

For the approach of color developer solutions are usually three different Concentrates used because certain components of the developer bath at longer Life are incompatible with each other. Thus, e.g. a concentrate the antioxidant, a co-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), and usually also an antioxidant and a third concentrate, a buffering agent, alkali, a limescale preventing agent and optionally an antifoggant.

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-phenylendiarninsesquisulfat (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.

worin

R₁

gegebenenfalls substituiertes Alkyl,

R₂

gegebenenfalls substituiertes Alkyl oder gegebenenfalls substituiertes Aryl und

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 (RADS) and compounds of 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-methylsulphonylaminoethyl) -2-methyl-phenylenediamine sesquisulphate (CD-3) or 4- (N-ethyl-N-2-hydroxyethyl) -2-methylphenylenediamine sulphate (CD-4) As the color developing agent, sulfites, hydroxalymine, diethylhydroxylamine and antioxidants (0-2) are preferable. Particularly preferred antioxidants are hydroxylammonium sulfate, sodium sulfite, potassium sulfite, (0-2) and diethylhydroxylamine.
It is also possible combinations of antioxidants or the use of multiple antioxidants.

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, Aminotrismethylenephosphonic acid, ethylenediamine-tetramethylenephosphonic 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.

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 have a comparatively high proportion of 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 processing photographic Materials, characterized in that for refilling the processing 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 Chemicals are filled in the chambers and then the Container is closed.

The invention is also the use of the multi-chamber package for Refilling a processing tank or a replenisher tank of a photographic Processing unit.

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

Examples Execution of processing trials

In the following Examples 3 to 5, 7 and 8, commercial color paper Agfa Type 11 was processed, which is a photographic color negative paper for rapid processing, which has a total silver content of about 0.6 g of silver per m ² and its Consist of silver halide emulsions to over 95 mol% of 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 (CD, BX, SB) of the initially completely emptied (processing and replenisher tanks) Minilabs were made with an approach from the commercial Agfa MSC 101 tank kit (process AP 94) and the regenerator container for the developer and stabilizer from the commercial MSC 101 Paper CD-R and MSC 101 Paper SB-R. The regenerator tank for the Bleach-fix bath was filled as described in the examples.

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

The replenishment rates were in all tests, 90 ml / m ² for the color developer, 100 ml / m ² for the bleach-fix bath, and 200 ml / m ² for the stabilizer.

In order to bring the process into a state of equilibrium, in each case so much of processed with pictorial motifs exposed color paper, up to 1 L bleach-fix regenerator was consumed. Then black leaves were, so the whole area and processed in all colors to maximum density exposed sheets to the To assess bleaching effect. Black leaves are a suitable test material for a Bleach-fix, because with the so-exposed leaves must after development total amount of silver contained in the paper will be bleached. The bleaching effect can easily visually under IR light with the fully processed leaves IR sight, because the material is IR transparent, with no residual silver, Silver, on the other hand, is IR-impermeable. The observations of the test results are indicated as "residual silver" in the examples when residual silver was observed or as "no residual silver" if the bleaching effect was ok.

For the experiments according to the invention, a two-chamber bottle according to FIGS. 1 and 2 was used and during pouring the bottle was held so that the spout dividing connecting web and the upper end surface (3) was aligned horizontally.

example 1

With this experiment, the mixing in the regenerator tank of the Minilabs Agfa MSC 101 checked. It only has to be prepared as a preparation the regenerator container for the bleach-fix solution is emptied. A processing was not accomplished.

1 liter of concentrate contains part A.
700 ml of ammonium thiosulfate solution, 58% by weight
100 g sodium disulfite
pH 5.5
The pH is adjusted with NH ₃ or H ₂ SO ₄ .

1 liter of concentrate contains part B.
700 ml of NH ₄ Fe (III) EDTA solution, 48% by weight
pH 7.0
The pH is adjusted with NH ₃ or H ₂ SO ₄ .

To make 1 liter of ready-to-use bleach-fix replenisher solution 200 ml Part A and 100 ml Part B needed.

im ersten Versuch a)

nacheinander (erst Teil A, dann Teil B) aus einer 1000 ml Flasche und einer 500 ml Flasche zugegeben und

im zweiten Versuch b)

gleichzeitig aus einer Zweikammerflasche mit einer Entnahmeöffnung zugegeben,

wobei im Versuch b) die Konzentrate direkt hinter der Entnahmeöffnung in Kontakt geraten und die Kammern ein Volumen von ca. 1000 ml und ca. 500 ml aufweisen.With the above concentrates, two 5 liter batches were made in the previously completely deflated bleach-fixer tank of an Agfa MSC 101 minilab. For each 3.5 liters of water were submitted and the concentrates Part A and Part B

in the first attempt a)

successively (first part A, then part B) from a 1000 ml bottle and a 500 ml bottle and added

in the second attempt b)

simultaneously added from a two-chamber bottle with a removal opening,

wherein in experiment b) the concentrates come into contact directly behind the removal opening and the chambers have a volume of about 1000 ml and about 500 ml.

In order to simulate a handling error of the operators, the batches in the bleach-fixer tank were not stirred. From the two batches samples were taken at different heights of the regenerator tank and analyzed for the content of thiosulfate and iron. The results are shown in Table 1.

From the results it can be clearly seen that by the simultaneous inflow the two concentrates of a two-chamber bottle surprisingly a substantial better mixing of the approach than with the use of two individual bottles.

Example 2 Concentrate Part A according to Example 1

1 liter of concentrate contains part B.
350 ml of NH ₄ Fe (III) EDTA solution, 48% by weight
40 g of succinic acid
pH 3.0
The pH is adjusted with HNO ₃ .

To make 1 liter of ready-to-use bleach-fix replenisher solution 200 ml Part A and 200 ml Part B needed.

im ersten Versuch a)

nacheinander aus zwei 1000 ml Flaschen und

im zweiten Versuch b)

gleichzeitig aus einer Zweikammerflasche zugegeben werden,

wobei die Kammern der Zweikammerflasche jeweils ein Volumen von ca. 1000 ml aufweisen. Die Ergebnisse sind in Tabelle 2 aufgeführt.

The experiments and analyzes are carried out analogously to Example 1, with the difference that submitted for each test in each case 3 liters of water and the concentrates Part A and Part B

in the first attempt a)

in succession from two 1000 ml bottles and

in the second attempt b)

be added simultaneously from a two-chamber bottle,

wherein the chambers of the two-chamber bottle each have a volume of about 1000 ml. The results are shown in Table 2.

From the results it can be clearly seen that by the simultaneous inflow of the two concentrates even in the case of a two-chamber bottle with gleichvolumigen Chambers surprisingly a much better mixing of the approach takes place than when using two equal-volume individual bottles.

Example 3

To study the effect of mixing on the processed material, the experiments a) and b) of Example 1 were repeated, but this time as under "Processing experiments" described.

The results are shown in Tab. 3.

From Table 3 it can be clearly seen that in the course of paper processing residual silver occurs when the regenerator from the commonly used 2 bottles is set, while this problem in the use of the invention Two-chamber bottle surprisingly does not occur.

Example 4

a) zwei einzelne Flaschen und

b) in eine Zweikammerflasche abgefüllt
   und 4 Wochen lang bei 40°C gelagert.

The concentrates Part A and Part B prepared in Example 1 were used in

a) two individual bottles and

b) filled into a two-chamber bottle
and stored at 40 ° C for 4 weeks.

a) 2 L Teil A und 1 L Teil B aus den einzelnen Flaschen bzw.

b) 2 L Teil A und 1 L Teil B aus der Zweikammerflasche

auf 10 Liter aufgefüllt, mit Ammoniak auf einen pH-Wert von 6,0 eingestellt und in ein MSC 101-Gerät eingefüllt wurden. Die übrigen Bäder wurden wie unter "Durchführung der Verarbeitungsversuche" beschrieben angesetzt. Anschließend wurde Type 11-Papier verarbeitet und sensitometrisch ausgemessen.
Dabei wurde festgestellt, dass bei Verarbeitung von Type 11-Papier unterschiedliche Gelbschleier (Gb-D_min) erzeugt wurden. Die Tanklösung aus den BX-Konzentraten der Zweikammerflasche zeigte einen geringeren Gelbschleier auf dem entwickelten Papier als bei Verwendung der Tanklösung aus den zwei einzelnen Flaschen. Die Meßergebnisse sind in Tabelle 4 wiedergegeben.

Subsequently, tank solutions were prepared from the concentrates by

a) 2 L part A and 1 L part B from the individual bottles or

b) 2 L part A and 1 L part B from the two-chamber bottle

made up to 10 liters, adjusted to pH 6.0 with ammonia and filled into an MSC 101 instrument. The remaining baths were prepared as described under "Processing experiments". Subsequently, Type 11 paper was processed and measured sensitometrically.
It was found that during processing of Type 11 paper different yellow haze (Gb-D _min ) were generated. The tank solution from the BX concentrates of the two-chamber bottle showed less yellow haze on the developed paper than when using the tank solution from the two individual bottles. The measurement results are shown in Table 4.

From Table 4 can be clearly seen that when using the tank solution from the two individual bottles after processing a high yellow haze occurs while this problem when using the two-chamber bottle, surprisingly does not occur.

Example 5

After processing, the paper materials processed in Example 4 were stored for 32 days at 35 ° C., 90% relative humidity, and then the yellow haze was measured again. The results are shown in Table 5.

From Table 5 can be clearly seen that when using the tank solution from the two single bottles after processing and climatic storage the yellow veil compared to the fresh development significantly increased, while this problem in the Use of the two-chamber bottle surprisingly much less occurs.

Example 6

a) ein einteiliges Bleichfixierbad sowie

b) ein Zweikammer-Bleichfixierbad hergestellt,

die zum Ansatz von je 10 L Regenerator verwendet werden sollten. Für das Konzentrat des Zweikammer-Bleichfixierbades wurde eine 2 mal 1L Flasche und für das einteilige Bleichfixierbadkonzentrat eine 2 L Flasche verwendet. Zum Ansatz der Regeneratoren wurden je 2 mal 100 ml des Zweikammer-Bleichfixierbades bzw. 200 ml des einteiligen Bleichfixierbades verwendet, so dass der Regenerator nach Ansatz aus beiden Konzentraten die gleiche Konzentration der eingesetzten Wirkstoffe enthielt.There were concentrates for

a) a one-part bleach-fix bath as well

b) a two-chamber bleach-fix bath is prepared,

which should be used to approach each 10 L regenerator. For the concentrate of the two-chamber bleach-fix bath, a 2-by-1 liter bottle was used and for the one-part bleach-fix bath concentrate, a 2-liter bottle was used. For the preparation of the regenerators, 2 × 100 ml of the two-chamber bleach-fix bath or 200 ml of the one-part bleach-fix bath were used, so that the regenerator contained the same concentration of the active ingredients used after mixing from both concentrates.

a ) Formulation for a one-part bleach-fix bath:

Contains 1 liter of concentrate
350 ml of ammonium thiosulfate solution, 58% by weight
50 g of sodium disulfite NH ₄ Fe (III) EDTA solution, 48% by weight, according to Table 6
10 g of succinic acid
pH 5.7
The pH is adjusted with NH ₃ or H ₂ SO ₄ .

b ) Recipe for a two-chamber bleach-fix bath :

1 liter of concentrate contains part A.
700 ml of ammonium thiosulfate solution, 58% by weight
100 g sodium disulfite
pH 5.3
The pH is adjusted with NH ₃ or H ₂ SO ₄ .

1 liter of concentrate contains part B.
NH ₄ Fe (III) EDTA solution, 48% by weight, according to Table 6
20 g of succinic acid
pH 6.5
The pH is adjusted with NH ₃ or H ₂ SO ₄ .

The concentrates prepared under a) and b) were stored for the simulation of a cold and warm storage during transport to the customer and the customer first at 60 ° C for one week and then at -5 ° C for one week. Subsequently, the samples were visually inspected for precipitates in the concentrate. The results are shown in Table 6.

As can be clearly seen from Table 6, occur after storage of the concentrates in all concentrates of the one-part bleach-fixer despite reduced concentration of NH ₄ Fe (III) EDTA precipitations, while in the two-chamber bottle in spite of each twice as high concentration of NH ₄ Fe (III) EDTA is surprisingly not the case.

Example 7

a) 2 L des einteiligen Konzentrates, bzw.

b) 1 L Teil A und 1 L Teil B des Zweikammerkonzentrates aus einer Zweikammerflasche,

jeweils auf 10 Liter aufgefüllt, mit Ammoniak auf einen pH-Wert von 6,0 eingestellt und gut durchmischt wurden. Die Versuche wurden jeweils durchgeführt, wie unter "Durchführung der Verarbeitungsversuche" beschrieben. The concentrates prepared in Example 6 under a) and b) were stored at 60 ° C for 1 week. Subsequently, tank solutions were prepared from the concentrates by

a) 2 L of the one-part concentrate, or

b) 1 L part A and 1 L part B of the two-chamber concentrate from a two-chamber bottle,

each made up to 10 liters, adjusted with ammonia to a pH of 6.0 and mixed well. The experiments were each carried out as described under "Processing experiments".

It was found that when processing with the one-piece BX concentrate regenerant tank solution produced significantly residual silver in the paper, while surprisingly when using the two-chamber concentrate tank solution produced no residual silver was observed and that the differences even when the BX regeneration solution mixes well becomes.

Example 8

The experiments a) and b) from Example 7 were repeated, but with the difference that the pH values of the regenerators were set to 5.0.

Subsequently, the minilab Agfa MSC 101 was prepared as described under "Execution processing trials "described.

However, no black leaves were processed, but in each case 350 m ² color paper Agfa Type 11 exposed with conventional motifs.

In order to simulate the practical conditions in paper processing, a high throughput of at least 50 m ^{2 of} color paper per day was also driven. At the end of each day, the appearance of residual silver was visually inspected by processing a black sheet with the IR glasses. The result is shown in Table 7.

As Table 7 clearly shows, occurs after about 4 days at high throughput of paper to the replenisher produced from the one-part bleach-fixer while surprisingly with the regenerator made from the two-chamber bottle no residual silver is formed over the entire duration of the experiment.

Example 9

a) ein einteiliges Bleichfixierbad sowie

b) ein Zweikammer-Bleichfixierbad hergestellt

There were concentrates for

a) a one-part bleach-fix bath as well

b) a two-chamber bleach-fix bath

a ) Formulation for a one-part bleach-fix bath:

Contains 1 liter of concentrate Ammonium thiosulfate solution, 58% by weight 350 ml potassium 100 g NH ₄ Fe (III) EDTA solution, 48% by weight 140 g Succinic acid 10 g PH value 5.7 The pH is adjusted with NH ₃ or H ₂ SO ₄ .

b ) Recipe for a two-chamber bleach-fix bath :

1 liter of concentrate contains part A. Ammonium thiosulfate solution, 58% by weight 700 ml potassium 200 g PH value 5.5 The pH is adjusted with NH ₃ or H ₂ SO ₄ .

1 liter of concentrate contains part B. NH ₄ Fe (III) EDTA solution, 48% by weight 280 g Succinic acid 20 g PH value 6.0 The pH is adjusted with NH ₃ or H ₂ SO ₄ .

The concentrates prepared under a) and b) were stored at 40 ° C. for 6 weeks. The sulfite content was determined fresh and after storage analytically. The result is shown in Table 8.

After storage of the concentrates, the concentrates became regenerators in each case 2 × 1 L parts A and B of the two-chamber concentrate or 2 L of the one-part concentrate were made up to 10 liters. The regenerators were then stored at room temperature for 5 weeks. During the Storage was determined at regular intervals of sulfite content and the regenerator checked visually for sulfur precipitates.

The result is shown in Table 9.

As Table 9 shows, after about 4 weeks of service life at room temperature the regenerator produced from the one-part bleach-fix bath precipitates, while in the regenerated from the two-chamber bottle regenerator on the no precipitation is observed throughout the experimental period. The appearance of precipitates in the regenerator made from the one-part bleach-fix bath can cause blockage of the regenerator pumps and silver sulfide precipitates in the tank solution, causing a production outage for the minilab operator and a complete cleaning of the Minilab wet part is required becomes.

Claims (18)

Containers for storing photographic processing chemicals and for charging the processing chemicals into a tank of a processing apparatus, the container containing at least two different chemicals spatially separated in chambers, characterized in that the chemicals belong to the same processing step and the container is designed so that the different Chemicals are brought into contact with each other before filling into the tank inside the container and / or brought into contact with each other during filling into 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 multi-part bleach-fix bath concentrate. Container according to claim 11, characterized in that it contains the bleaching agent and the fixing agent in separate chambers. Container according to one of claims 11 or 12, characterized in that it contains as bleaching agent at least one iron complex with one of the complexing agents 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), iminosuccinic acid, iminosuccinic acid propionic acid or 2-hydroxypropyliminodiacetic acid. Container according to one of claims 11 to 13, characterized in that it contains as fixing ammonium thiosulfate. Container according to one of claims 11 to 14, characterized in that it contains in the chamber with the bleaching agent and / or in the chamber with the fixing agent a buffer substance. Process for the processing of photographic materials, characterized in that a container according to one of claims 1 to 15 is used to replenish the processing chemicals. Process for the production of the container according to one of claims 1 to 15, characterized in that the chambers of the container are produced in one piece by a plastic extrusion blow molding method, then the different chemicals are filled into the chambers and then the container is closed. Use of the container according to one of claims 1 to 15 for refilling a processing tank or a replenisher tank of a photographic Processing unit.

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