EP1513009A1 - Container for photochemicals - Google Patents

Abstract

A system for simultaneous replenishing of chemicals in automated color silver halide photographic processing has >=1 vessel for replenishing solution for the developer and >=2 vessels for replenishing solution for the bleach- fixing bath, the developer-replenishing vessel containing >=60 g developer per liter vessel volume. An independent claim is also included for automated color processing using the above system by passing the silver halide material through a developer solution, a bleach-fixing solution and a stabilizing solution, the developer and bleach-fixing solutions being in regenerating containers and being regenerated by dosing and the containers being replenished via a chemical system.

Description

The invention relates to a container for the simultaneous refilling of chemicals for Processing color photographic silver halide materials (photographic materials) in a automatic processing apparatus, wherein the container at least one bottle with the refill solution for a color developer and at least two bottles with Refill solutions for a bleach-fix contains.

Usually, to approach color developer solutions, three different Concentrates used because certain components of the developer bath at longer Life are incompatible with each other. Thus, e.g. a concentrate that Antioxidant, an 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) and a third one Concentrate a buffer substance, alkali and a limescale.

In recent years, one-piece or larger ones are increasingly being used multiphase developer concentrates are offered. These have the advantage of being simplify the approach of the working solution and errors when preparing or supplementing a developer solution can be avoided.

In modern minilabs where image data can be processed digitally increasingly also containers, mostly cardboard boxes, for several chemical concentrates used as refill systems. The ones used in it Concentrated bottles are made of plastic and contain the chemicals as Solids in the form of tablets or granules or as highly concentrated liquid Solutions. In most instrument versions, the concentrate bottles are stored in a common cardboard stored in the machine upside down, wherein the spout openings are seen from the bottom of the box at the same height. If necessary, the seal with which the inverted bottles are closed, pierced on the machine side with a dome and the concentrates flow over Plastic hoses each in a suitable regenerator reservoir (Regenerator tank) in the machine. There are always all the bottles of a container open at the same time, so that the individual chemical solutions are so dimensioned need that they are consumed at the same time. After the expiry of the Concentrates are the boxes with the emptied bottles out of the unit removed and then disposed of.

Conventional photo-processing equipment has replenisher tanks from which the processing solutions in the processing tanks are regenerated by metering in the replenisher solutions, depending on the amount of material processed. In order to be able to handle customer orders as quickly as possible, small processing devices for photo materials, so-called minilabs, are often set up directly in the stores today. Since the replenishment containers of Minilab devices have a certain specified volume (replenisher volume) due to the design in the device, only a certain amount of photo material can be processed at a given replenishment rate. For example, a commercially available Minilabgerät has a predetermined regenerator volume for the color developer of 4.5 liters, which is obtained by the closure (seal) of a bottle with the color developer concentrate from the container is pierced, the concentrate flows into the regenerator reservoir and there automatically with Water is replenished to the regenerator volume of 4.5 liters. If the replenishment rate is eg 60 ml / m ^{2 of} material, a maximum of 75 m ^{2 of} paper can be processed before the regenerator volume has been used up and a new container has to be docked to the device. A higher range, ie a larger amount of processed material, is not possible.

However, an increased range can be achieved if the regeneration rate is reduced. For a given regenerator volume of 4.5 l, to increase the reach of a pack to 100 m ^2, the color developer recovery rate would theoretically have to be reduced to 45 ml / m ² . With such a low regeneration rate, however, there is the danger that due to the liquid carryover by the material from the color developer tank and the additional evaporation in the processing tank, the liquid level in the color developer tank steadily drops and the tank thereby runs dry or its minimum level is exceeded.

Further, when sizing refill packs, it is necessary to take into account the constraint that the replenishment rates for the processing baths are usually not the same and, in particular, that the replenishment rates can not usually be adjusted independently of each other. For example, a commercially available processing machine for photographic paper has a 4.51 regenerator container for the color developer solution, a 7.5 liter replenisher container for the bleach-fix solution, and a 4.51 replenisher container for the stabilizer solution. 1 _^2/3:: In order for the vessel always at the same time can be refilled, the ratio of the replenishment of color developer solution, bleach-fixing and stabilizing to 1 on the device side 1 set. If, for example, a regeneration rate for the color developer of 60 ml / m ^{2 is} set manually, this results in a regeneration rate for the bleach-fix solution of 100 ml / m ² and a recovery rate for the stabilizing solution of likewise 60 ml / m ² . The amounts of chemicals in a refill container must thus allow precisely the appropriate concentrations in the regenerator containers required for the coupled replenishment rates.

The well-known, usually cuboid containers (boxes) often have a small depth (shortest side of the base). Although the reasons for this Dimensioning in detail are not known, it can be assumed that the inexpensive availability of standard bottles and filling machines as well as the easier handling (easier holding) are responsible. Such However, cartons are very unstable when stored and tilt both filled as well as dumped easily. By a filled, several kilograms heavy Carton can cause serious damage when overturned and in the worst case even the chemicals can leak. Because a deflated cardboard is not complete idle, can also leak after overturning chemical residues. Around To partially compensate for this disadvantage, are in such containers used high standard bottles often filled only incomplete to the The center of gravity of the cardboard boxes used to shift down and thus to achieve an improved mechanical stability in the upright storage. Often an incomplete filling also results from the different, maximum possible chemical concentrations in the individual bottles and the mentioned boundary conditions with respect to the regeneration rates.

However, this results in considerable disadvantages, such as an increased air oxidation of the concentrate and a reduced range of the concentrate scheduled regenerator. The refilling containers used so far have also the disadvantage that they at low Regenerierquote the color developer or for longer life of the color developer regenerator to a significant Increase the veil of the processed photographic material. In extreme cases it can in the regenerator tanks to Beerte.

An even greater reduction in range results when using smaller (less high) standard bottles, as these are usually only in rough Volume gradations are available, such as e.g. 0.5, 1.0 and 2.0 liters. When in the The following is the volume of bottles, this is the case Standard size of the bottle, which has a certain tolerance. A 1 liter Bottle has e.g. a filling volume of about 1 liter, which varies depending on the manufacturer and from bottle to bottle or production batch to production batch usually has a tolerance of +/- 50 ml.

In addition, it has proved to be unfavorable if different in one container high bottles are used. Since the bottle openings of the container up have the same height, remains behind the shorter bottles Cavity in which the bottles are pushed in when opening (piercing the seal) can be and then not be emptied. Because of the high pressure, the When it opens on the bottle, it has also proved too time-consuming proven, the bottles z. B. to secure by additional deposits in the carton.

The known Nachfüllgebinde also have an insufficient range, which such containers must be changed frequently. This requires a considerable Time spent on the operator and shortens the time in which the device can be operated unattended.

The invention is therefore based on the object, a container for refilling To provide processing chemicals that allow increased range, So rarely needs to be changed, which is stable and easy to handle, easy can be emptied (punctured), a good shelf life of the contained Chemical concentrates and the resulting regenerator solutions ensures and in the processing of color photographic material a good Image quality, in particular low minimum densities and high maximum densities allows.

It has now surprisingly been found that this with a refill for Photochemicals succeed that at least one bottle for a color developer and contains at least two bottles for a bleach-fix, wherein the refill bottle for the color developer per 11 bottle volume more than 60 g, preferably at least 65 g, more preferably at least 70 g and more preferably at least 75 g Color developing agent contains.

The invention therefore relates to a container for the simultaneous refilling of Chemicals for processing color photographic silver halide materials automatic processing apparatus, wherein the container at least one bottle with the replenisher for a color developer and at least two bottles of replenisher for a bleach-fix, characterized in that the bottle with the refill solution for the color developer per 11 bottle volumes more than 60 g Color developing agent contains.

The refill systems used contain color developer concentrates in which the Color developer substance at least in a concentration of 0.11 mol / l is. Preferably, the concentration of the color developing agent is at least 0.13 mol / l, and more preferably at least 0.15 mol / l.

In the prepared regenerator solutions the concentration is Color developer solution at least 0.03 mol / l and more preferably at least 0.04 mol / l.

In the color photographic silver halide materials, for the processing of which in It is possible for the chemicals according to the invention to be provided with chemicals are any, color coupler containing materials, it is preferred However, they are colored paper, especially those containing chloride-rich silver halide emulsions. which is suitable for the Process AP 94.

The container according to the invention can next to the refill bag for the developer and the two refill bottles for the bleach-fixer even more refill bottles contain. Preferably, the container still contains a refill bottle for the Stabilizing.

In a preferred embodiment of the invention, the container contains Refill solutions for the processing of color paper, in particular AgClreichem Color paper and in particular it is the refill solutions to those for an AP 94 or RA 4 compatible process.

For the color developer replenisher, the known color developer compositions used, as long as they have a concentration of at least 60 g Allow color developer per 11 bottle volumes. The color developing agent is in known manner depending on the material to be processed.

In a particularly preferred embodiment, the Color developing agent to 4- (N-ethyl-N-2-methylsulfonylaminoethyl) -2-methylphenylendiaminesesquisulfat (CD-3).

In a particularly preferred embodiment of the invention is a refill container, which is exactly one bottle with the refill solution for a Color developer, exactly two bottles of replenisher for a bleach-fix and contains exactly one bottle with the replenisher for a stabilizer and that for the processing of color photo paper is used.

In this case, the color developer replenisher must be one-piece Color Developer Concentrate act that can be both single phase and multiphase can.

The replenisher of the invention for a color developer (Developer concentrate) contains, in addition to the color developing agent, the usual chemicals required for the development of a color photographic material, in particular an antioxidant, a wetting agent, a limescale inhibitor, a Whiteners, a complexing agent, a buffer system and alkali. In a special preferred embodiment of the invention, the concentrate contains a Anti-foaming agent. The desired final volume is achieved by adding water adjusted, for which preferably demineralized water is used.

In a preferred embodiment of the invention, the color developer concentrate a multiphase, especially biphasic concentrate, which is prepared as described in DE 100 05 498, and preferably to a Any time during manufacture a wetting agent can be added.

The concentrate preferably contains no undissolved constituents and is in particular during storage at least 1 month without precipitation, particularly preferably at Storage below 0 ° C, especially between 0 ° C and -7 ° C.

The concentrate also contains a preferred embodiment Minimum amount of one or more water-soluble organic solvents.

In a preferred embodiment, the organic solvent contains a mixture of polyethylene glycols of different molecular weight of monoethylene glycol to polyethylene glycol having an average molecular weight of 20,000, For example, a mixture of diethylene glycol, polyethylene glycol with the middle Molar weight of 400 and polyethylene glycol with the average molecular weight of 1500. The average molecular weights are weight average.

This allows optimal settings for precipitation-free one-piece, if necessary even manufacture single-phase developer concentrates.

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

As water-soluble organic solvents are those from the series of glycols, Polyglycols, alkanolamines, aliphatic and heterocyclic carbonamides, aliphatic and cyclic monoalcohols, wherein the weight ratio from water to organic solvent in the replenisher preferably 50:50 to 95: 5, more preferably 60:40 to 90:10 and most preferably of 65:35 to 85: 15.

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, acetophenol;
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-methylethylamine, 2-methylaminoethanol, 2- (dimethylamino) ethanol, 2- (2-dimethylaminoethoxy) 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.

Polyphase means that the concentrate contains two or more liquid phases, but no precipitation. The liquid phases are e.g. an aqueous and an organic Phase.

The molar ratio of antioxidant to developing agent in the Replenisher is preferably 0.5: 1 to 4: 1, more preferably 0.6: 1 to 3.5: 1 and more preferably 0.7: 1 to 3.0: 1.

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 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.

Examples of suitable antioxidants are

(0-3)   CH₃CH(CH₃)NHOH

n=20

n= 10

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

n = 20

n = 10

A particularly preferred antioxidant is (0-2).

When diluting the concentrate with water to make it ready to use Color developer or the regenerator disappear possibly existing Phase boundaries; the ready-to-use developer is single-phase.

In a further advantageous embodiment of the invention is a Homogeneous single-phase concentrate, which is produced in particular as in US 6,077,651, and at any time in the production preferably a wetting agent is added.

These single phase concentrates have a pH of about 7 to about 13 and contain a comparatively high proportion of water-miscible hydroxyl groups carrying, in particular straight-chain organic solvents a molecular weight of about 50 to 200 and a buffer substance soluble therein. Preferably, the weight ratio of water to the organic Solvent between 15:85 and 50:50.

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 such. For example, sodium carbonate and potassium carbonate are preferred.

In the preparation of the one-part single-phase concentrate is an aqueous Solution containing the sulfate of the color developer and optionally further additives contains, mixed with an alkali metal base and then by adding the organic solvent precipitated alkali metal sulfate. The alkali metal sulfate is by any suitable separation technique, e.g. 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 replenisher for a bleach-fix can be a one-part Bleach-fix concentrate, which is divided between the two bottles, however, it is preferably a two-part bleach-fix concentrate the parts (BX-1) and (BX-2), wherein (BX-1) is substantially a thiosulfate salt and a stabilizer therefor, especially a sulfite salt, and (BX-2) substantially contains a Fe (III) complexing agent, whereby decomposition reactions largely can be avoided. The pH of (BX-1) is preferably 5 to 7 and that of (BX-2) preferably 2 to 7, especially 3 to 7.

The known bleach-fix bath concentrates can be used for the invention become.

Bleach-fix baths (BX-baths) are used in color photographic processing used to the resulting from the development of metallic silver to a soluble form (bleaching) and in this form together with not developed silver halide by complex formation from the material to solve (Fixing). BX-baths, as they are eg. As described in EP 569 852 A1, and thus also the bleach-fixer concentrates contain a number of these tasks necessary chemicals, namely an iron (III) complex salt as oxidizing agent, a thiosulfate as a fixing agent and a sulfite, disulfite or a sulfamic acid as Stabilizer for thiosulphate.

Fe (III) complex salts suitable for photographic bleach and bleach-fix baths, are known from a variety of documents (e.g., EP 329 088, 584665, 507 126, 556 782, 532 003, 750 226, 657 777, 599 620, 588 289 723 194, 851287, 840 168, 871 065, 567 126, 726 203 and US 5,670,305).

The complexing agents are also suitable for the Fe (II) complex salts.

Preferred complexing agents for Fe (III) are: ethylenediaminetetraacetic acid (EDTA), 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, Imino-succinic propionic acid, 2-hydroxypropyliminodiacetic acid.

There are also mixtures of these complexing agents used and it is preferred between 0.1 to 1 mol / l of Fe (III) complexing agents used.

Polycarbonsäuren: z.B. Oxalsäure, Malonsäure, Glutarsäure, Adipinsäure, Korksäure, Fumarsäure, Maleinsäure, Itaconsäure;

(Poly)Hydroxypolycarbonsäuren: z.B. Zitronensäure, Glykolsäure, Milchsäure, Äpfelsäure, Weinsäure, Galactarsäure.

In addition, other complexing agents can be added individually or in a mixture:

Polycarboxylic acids: eg oxalic acid, malonic acid, glutaric acid, adipic acid, suberic acid, fumaric acid, maleic acid, itaconic acid;

(Poly) hydroxypolycarboxylic acids: eg citric acid, glycolic acid, lactic acid, malic acid, tartaric acid, galactaric acid.

Of these additional complexing agents are preferably 1 to 200 mmol, in particular 5 to 50 mmol / l concentrate used.

Suitable sulfites are e.g. Ammonium sulfite, ammonium hydrogen sulfite, sodium sulfite, Sodium disulfite, sodium bisulfite, potassium sulfite, potassium bisulfite, potassium bisulfite. Suitable sulfinic acids are e.g. Hydroxymethanesulfinic acid, formamidinesulfinic acid, Benzenesulfinic acid, p-toluenesulfinic acid, methanesulfinic acid, o-amidosulfinic acid.

The bleach-fix concentrate according to the invention can be a phosphate, polyphosphate, Polyphosphonate, nitrate or bromide included. As phosphates, the alkali metal salts and / or ammonium salts, 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 or the free Phosphoric acid.

As polyphosphates and phosphonates, e.g. Sodium hexametaphosphate, sodium tetraphosphate, Hydroxyethanediphosphonic acid, N (-2-carboxyethyl) -1-aminoethane-1,1-diphosphonic acid, N, N-bis (carboxymethylene) -1-aminoethane-1,1-diphosphonic acid, Morpholinomethane diphosphonic acid, nitrilotrismethylene phosphonic acid, Ethylenediamine tetramethylenephosphonic acid, hexamethylenediamine tetramethylene phosphonic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 2-carboxyethanephosphonic acid be used. Also suitable are free polyphosphoric acids.

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

The phosphates, polyphosphates and polyphosphonates, nitrates and bromides become the concentrate preferably in an amount of 0.01 to 2.5 mol / l, in particular 0.05 to 1 mol / l added.

Particularly suitable fixing agents are sodium, potassium and ammonium thiosulfate.

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

Preferred buffer substances are dicarboxylic acids, eg. Malonic acid, succinic acid, Adipic acid.

The pH is in particular 4 to 9.

An example of particularly suitable in the context of the present invention Replenisher (BX-1) and (BX-2) for a bleach-fixer is hereafter given.

(BX-1):

For 1 liter of concentrate
500 g of ammonium thiosulfate and
120 g of sodium bisulfite
Dissolve in water, make up to 1 liter with water and adjust the pH to 5.5 with ammonia or acetic acid.

(BX-2):

For 1 liter of concentrate
500 g of ammonium iron (III) ethylenediaminetetraacetate (EDTA)
dissolve in water, make up to 1 liter with water and adjust the pH to 6.8 with acetic acid.

As replenisher for a stabilizer according to the invention the usual Compositions are used, for. B. the stabilizing solution 94 SB-R.

An example of a particularly suitable in the context of the present invention Replenisher (SB) for a stabilizer is given below.

(SB):

For 1 liter of concentrate
80 g of sodium sulfite,
60 g of ethylenediaminetetraacetic acid (EDTA acid),
50 g of 1-hydroxyethane-1,1-diphosphonic acid (HEDP acid),
80 g of potassium hydroxide and
5g of Proxel GXL
Dissolve in water, make up to 1 liter with water and adjust the pH to 8 with potassium hydroxide solution.

In order to achieve the object according to the invention, it has proved to be preferable exposed when the bottles in the refill container are rectangular and a Ratio of height (H) of the bottles to the widest base (S) of 1.5 to 3 have, with the height from the bottom of the bottle to below the neck of the bottle is measured. This has proven to be a particularly good compromise between Stability and handling proved.

In addition, it is particularly advantageous if the bottles, especially those with the Color developers are filled as high as possible, especially if they are each too at least 90 vol .-% and more preferably at least 95 vol .-% are filled.

To the above-described diverse boundary conditions with respect to the individual Regeneration rates and the adjustable concentrations in the refill solutions To take account, it has proved to be advantageous if the bottle size for the color developer replenisher is about 11. In addition, it is preferred if the Bottle size for one of the at least two refill solutions for the bleach-fix bath is about 21 and for the other of the at least two refill solutions for the Bleach-fix bath is about 11.

In a particularly preferred embodiment of the invention that contains Refill pack a 1 liter bottle with a refill solution for a color developer (Color developer bath), a 2 liter bottle with the (BX-1) part of a refill solution for a bleach-fix, a 1 liter bottle with the (BX-2) part of a refill solution for a Bleach-fix bath and a 1 liter bottle with a replenisher for a stabilizer.

Another object of the invention is a method for processing a color photographic silver halide material using an automatic Processing apparatus, wherein the silver halide material, a color developer solution, passes through a bleach-fix solution and a stabilizer solution, the color developer solution at least one color developer replenisher container and the bleach-fix solution regenerated from at least one bleach-fixing regenerator container by metering and the replenisher containers are refilled via a chemical container, characterized in that the chemical container is a inventive container is.

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 102-107.

In order to achieve an increased range (processed material per refilling container), the lowest possible regeneration rates are set during processing. Preferably, the color developer solution is regenerated per m ^{2 of} processed material with less than 60 ml of color developer replenisher solution (replenishment rate less than 60 ml / m ² ), and more preferably the replenishment rate is less than 55 ml / m ² .

The container is preferably designed so that at least 80 m ² material, preferably at least 90 m ² material can be processed with the contents of a Nachfiillgebindes.

The bleach-fixing solution is also regenerated according to the invention with the lowest possible regeneration rates, but here the coupling of the regeneration rates described above must be taken into account. Preferably, the rate of regeneration of the bleach-fix solution is less than 100 ml / m ² , more preferably less than 90 ml / m ² and most preferably less than 80 ml / m ² .

To the disadvantages described in the introduction low regeneration rates, such. As the emptying of a tank, to prevent in a particularly preferred embodiment of the invention in addition to the color developer regenerator in addition, a defined amount of water per m ² processed photographic material in the color developer tank dosed. As a result, for example, a regeneration rate of 45 ml / m ^{2 can be increased} from the regenerator to a total addition of 45 ml / m ² + x ml / m ² extra water and the range of a container remain unchanged at 100 m ² . The additional water dosage takes place, for example, from a water reservoir in the device via separate pumps. This procedure ensures that the color developer tank does not run dry even with high evaporation, and nevertheless an increased range can be achieved by a reduced color developer regeneration. x is, for example, from 0 to 50 for the color developer regeneration and, for example, from 0 to 400 for the stabilizer bath regeneration. Preferably, x is selected such that in the case of color developer regeneration additionally 5 to 50% extra water, in particular 10 to 25%, is used. , in each case based on the dosage of the color developer replenisher solution, are metered. For the stabilizer bath regeneration, x is preferably chosen so that in addition 50 to 400% of extra water, in particular 100 to 300%, in each case based on the dosage of the stabilizer regenerator solution, are added.

The same principle may also be preferred for the remaining processing solutions be used.

In order to obtain less residual solutions, it has proven to be beneficial, after enema the refill solutions the color developer replenisher container with water and the Bleach-fixer tank at least partially with the overflow of Top up stabilizer solution.

The invention is particularly suitable for rapid processing processes in which the Development time preferably less than 45 s, more preferably less than 40 s and more preferably less than 35 s.

Another object of the invention is the use of a container for Refilling the regenerator container of an automatic processing device for color photographic silver halide materials, characterized in that they are a container according to claim 1, wherein it is preferred if the bottles in the container round screw caps and have a seal, the bottles through a carton are held together, from which the screw caps on the same Height protruding and after inserting into the device on the wide edge of the Screw caps or at the located between the screw caps Cardboard surface to be kept upside down.

To ensure safe insertion of the inventive container in a processing device to allow the containers are preferably equipped with features by the the containers are positioned in the device or by the one confusion is excluded. For safe positioning, the bottles have z. B. to the Necks and / or at the closures to the bottle bottom plane-parallel surfaces, with which they rest on holders in the device. At the plane-parallel surfaces the bottlenecks may be, in particular, circumferential grooves (rejuvenations) act in the bottleneck, which is exactly in corresponding gripping forks of the Processing device fit and so a precise docking of the container to the Allow processing device. The gripping forks are preferred as semicircle or U-shaped recesses formed in a continuous plate, wherein the Recesses correspond to the bottle necks and in particular so are dimensioned that the bottlenecks of the container fit exactly, but not too be kept tight. It is advantageous after docking for each bottle of Canned at least 35%, in particular at least 40% of the circulating Bottom neck groove (groove) on the U-shaped recesses of the gripping forks. As material for the bottles, plastics are particularly good for this purpose suitable, in particular moldable plastics such as polyethylene (PE), polypropylene (PP), polyethylene terephthalate (PET) or polyvinyl chloride (PVC); Mixtures from the plastics mentioned; or copolymers of the said polymers underlying monomers. For the forks are stainless materials such as Plastics, non-ferrous metals and stainless steels, as well as with stainless materials coated materials, e.g. B. stainless steels coated steels prefers. It is also possible to equip the processing device with gripping forks, their recesses are wide enough to pass the closures of the bottles. The gripping fork can in this case also as Aufsetzfläche for the container carton serve.

In particular, in the variant in which the bottle necks of the bottles a groove has, which is accurately inserted into the fork of the processing device, it has proved to be safe for safe and quick handling when a Attachment surface for the container is folded out of the device. It is advantageous if the contact surface is arranged horizontally after unfolding, so that the Container can be easily put on from above.

Preferably, the gripping forks are at right angles firmly with the hinged attachment surface connected and show in the unfolded state upwards. If appropriate Arrangement of bottle necks in the box, z. B. as described below, can the container so easy, accurate and confusion-proof in the Processing device can be used. To further simplify handling, fills the unfolded horizontal Aufsetzfläche preferably not the entire surface under the carton, but in particular has lateral recesses, which make it possible to reach under the carton.

To avoid confusion z. B. between paper or film chemicals and / or to avoid reversed insertion into the processing device the containers of the invention are preferably equipped with stickers, through which the nature of the container and the correct insertion position is clear. It is beside it but advantageous, for. B. by length and / or width stops on the container holder in the device and / or by at least one asymmetrically mounted groove in the container and a corresponding pin on the device confusion safely excluded. As a particularly advantageous it has been found, the arrangement to make the bottlenecks asymmetrical, so that a reverse insertion not possible. These can be used in bottles of different sizes, the bottlenecks Usually centered, but the neck of a bottle can also itself be asymmetric with respect to the bottle. By a suitable arrangement of the bottles with different volumes as well as the position of the bottlenecks can both a confusion of chemical containers as well as their reversed Insert safely be avoided.

The bottle caps are preferably screw caps, the in particular to secure a preferably welded seal and in continuation of the Bottleneck release a passage through the device-side means the Seal can be pierced. As mentioned above, it is for a sure Docking, puncture and emptying are particularly preferred when the bottles of the Bundles have the same height. The gripping forks turn the bottles already held in the right position for piercing. To the process still more secure and in particular the passage opening exactly above the To arrange push-through tool, has the closure of the container bottles on upper edge of a narrow ring (centering ring), whose inner diameter is the same or slightly larger than the diameter of the piercing opening. side of the device can use the bottle necks when folding the with a novel inventive Container provided Aufsetzfläche be accurately positioned. On the device side can for each centering ring on the push-through tool narrow spacers be provided, to which the centering rings in the folded state of Attach attachment surface.

After folding the Aufsetzfläche the container is preferably vertical and arranged with the bottlenecks (the pouring openings) down, whereby the Emptying after piercing is done automatically by gravity.

The puncture is carried out automatically on the device side or manually as required. The tools used are usually sharp and come with considerable force is applied to ensure the puncture safely. An exact one Positioning of the penetration opening is therefore essential.

Further preferred embodiments of the invention are the subclaims remove.

Examples example 1

Different color developer concentrates were prepared which are used during preparation to the same regenerator volume of 4.5 liters (L) were filled. Of the Oxidation protection content was adjusted so that despite different Bottle filling after application to 4.5 L regenerator volume theoretically same oxidation protection content should result in all regenerators.

The concentrates were 2 weeks in PE bottles in the heating cabinet at 60 ° C. stored. Each fresh, as well as after 1 and 2 weeks of storage were from the Concentrates each 4.5 liters of regenerator set in which the oxidation protection content was determined analytically.

The developer concentrate 1 used had the following composition: DEHX (antioxidant) 30 g CD-3 70 g diethylene glycol 60 ml Polyethylene glycol, Mw 400 100 ml whiteners 10 g EDTA 30 g potassium carbonate 120 g KOH 50 g make up to 1 liter with water;
the pH of about 14 is self-evident.

The developer concentrate 2 used had the following composition: DEHX (antioxidant) 37.5 g CD-3 87.5 g diethylene glycol 75 ml Polyethylene glycol, Mw 400 125 ml whiteners 12.5 g EDTA 37.5 g potassium carbonate 150 g KOH 62.5 g make up to 1 liter with water; the pH of about 14 is self-evident.

The developer concentrate 3 used had the following composition: DEHX (antioxidant) 50 g CD-3 117 g diethylene glycol 100 ml Polyethylene glycol, Mw 400 167 ml whiteners 16,7 g EDTA 50 g potassium carbonate 200 g KOH 83 g make up to 1 liter with water; the pH of about 14 is self-evident. developer concentrate bottling Oxidation protection content in the regenerator (g / l) 1 100% fresh 6.5 1 100% after 1 week storage 6.1 1 100% after 2 weeks storage 5.5 2 80% fresh 6.6 2 80% after 1 week storage 5.4 2 80% after 2 weeks storage 3.9 3 60% fresh 6.6 3 60% after 1 week storage 4.7 3 60% after 2 weeks storage 2.7

As can be clearly seen from Table 1, the oxidation protection in the concentrate The less the bottle is filled with liquid volume, the faster it is degraded.

Example 2

Developer tank fillings were prepared from the developer concentrates 1-3 prepared and stored under Example 1 after storage for 2 weeks at 60 ° C. by adding in each case 6.5 l of regenerator with 1.2 l of 94 CD-LR starter and making up to 18 l. The pH of the tank solutions was 10.2. In these tank solutions of the developer concentrates 1-3 thus prepared, unexposed type 11 paper was processed. After processing, the image whites were determined sensitometrically. developer concentrate bottling D-min * 1000 after storage of the concentrates gb pp bg 1 100% after 2 weeks storage 117 127 124 2 80% after 2 weeks storage 125 133 126 3 60% after 2 weeks storage 131 138 127

As can be seen from Table 2, the images are white after storage of the concentrates the worse, the less filled the used concentrate bottles were.

Example 3

The developer concentrate described in Example 1 was varied by: different ratios of antioxidant (DEHX) and Color developer (CD-3) were used. Thereby, the amount of CD-3 each became kept constant and the oxidation protection amount varies. The bottles were each fully filled.

Subsequently, in each case a developer tank filling was produced by the process listed under Example 2, were processed in the step-wedge exposed with a gray wedge. In each case the fog values and the maximum densities were determined. The results are shown in Table 3. Ratio DEHX / CD-3 Dmin * 1000 Dmax gb pp bg gb pp bg 0.3 142 138 128 2.19 2.29 2.52 comparison 0.7 121 131 125 2.18 2.38 2.52 invention 2.0 118 128 124 2.15 2.36 2.51 invention 3.5 116 126 123 2.11 2.35 2.50 invention 4.5 115 125 123 1.67 2.24 2.47 comparison

As shown in Table 3, the fog becomes higher DEHX / CD-3 improves, at a ratio below 0.5 an unacceptable occurs Deterioration mainly of yellow-veil. At a ratio over 4.0 But occurs a very significant reduction mainly the yellow maximum densities on, so that optimal image-wise results only in the claimed conditions can be achieved.

Claims (22)

A container for simultaneously replenishing chemicals for processing silver halide color photographic material into an automatic processing apparatus, said container containing at least one bottle of color developer replenisher and at least two bottles of bleach-fix replenisher, characterized in that said bottle of said color developer replenisher contains more than 60 g of color developing agent per 11 bottle volumes. A container according to claim 1, characterized in that said three bottles all have a ratio of the height (H) to the widest base (S) of the bottles of 1.5: 1 to 3: 1. Container according to one of claims 1 or 2, characterized in that the filling volume in said three bottles is in each case at least 90% by volume, based on the volume of the bottle. Container according to claim 3, characterized in that the filling volume in the said three bottles is in each case at least 95% by volume, based on the volume of the bottle. Container according to one of claims 1 to 4, characterized in that the replenisher for the color developer contains an antioxidant and the molar ratio of antioxidant to developing agent in the replenisher for the color developer 0.5: 1 to 4: 1. Container according to claim 5, characterized in that it is the bis-sulfoethylhydroxylamin in the antioxidant. Container according to one of claims 1 to 6, characterized in that the bottle volume for the color developer replenisher is about 11. A container according to any one of claims 1 to 7, characterized in that the volume of the bottle for one of the at least two refill solutions for the bleach-fix bath is about 21 and for the other of the at least two refill solutions for the bleach-fix bath is about 11. Container according to one of claims 1 to 8, characterized in that the replenisher for the color developer contains water and an organic solvent and the weight ratio of water to organic solvent in the replenisher 50: 50 to 95: 5. Container according to one of claims 1 to 9, characterized in that the replenisher for the color developer contains water and a wetting agent. Container according to one of claims 1 to 10, characterized in that the bottles in the container round screw caps and a seal and the bottles are held together by a carton from which the screw caps protrude at the same height. Container according to claim 11, characterized in that the bottle necks of the bottles in the container have circumferential recesses. A method of processing a silver halide color photographic material using an automatic processor, wherein the silver halide material undergoes a color developer solution, a bleach-fix solution and a stabilizer solution, the color developer solution of at least one color developer replenisher container and the bleach-fix solution of at least one bleach-fixer replenisher container are regenerated by metering and replenishing the replenisher containers a chemical container are refilled, characterized in that it is a container according to one of claims 10 to 12 in the chemical container. Processing method according to claim 13, characterized in that the color developer solution per m ^{2 of} processed material is regenerated with less than 60 ml of color developer replenisher solution. Processing method according to one of claims 13 or 14, characterized in that at least 80 m ^{2 of} material can be processed with the contents of a chemical package. Processing method according to any one of claims 13 to 15, characterized in that the bleach-fixing solution is regenerated per m ^{2 of} processed material with less than 100 ml bleach-fixing replenisher solution. Processing method according to one of claims 13 to 16, characterized in that the regenerator containers are refilled after the refilling of the chemicals to a predetermined liquid level, characterized in that the color developer regenerator container with water and the bleach-fixer regenerator at least partially filled with the overflow of the stabilizing solution becomes. Processing method according to one of claims 13 to 17, characterized in that the development time is less than 40 s. Processing method according to one of claims 13 to 18, characterized in that at the same time for regeneration with color developer replenisher solution, water is metered into the color developer solution, wherein the metering rate of the amount of water is at least 10% of the metering rate of the color developer replenisher solution. Use of a container for refilling the regenerator container of an automatic processing apparatus for color photographic silver halide materials, characterized in that it is a container according to one of claims 1 to 12. Use of a container according to claim 20, characterized in that a container according to claim 11 is inserted into the processing device, that the bottles after insertion into the device at the wide edge of the screw caps or on the located between the screw tops cardboard surface upside down being held. Use of a container according to claim 20, characterized in that the peripheral recesses of a container according to claim 12 are inserted into gripping forks of the processing apparatus.