DE19927600A1 - Alkaline color photographic aqueous developer solution based on color developer substance and antioxidant contains open-chain carbonamide or sulfonamide as water-soluble organic ancillary solvent - Google Patents

Abstract

In a color photographic aqueous developer solution containing a color developer substance and an antioxidant, which is adjusted to pH 9-12, an open-chain carbonamide or sulfonamide is used as water-soluble organic ancillary solvent.

Description

The invention relates to a ready-to-use color photographic developer solution.

As ready-to-use color photographic developer solution called the aqueous Solution through which the exposed color photographic material is passed to to produce a color at the exposed areas. Thereby the color developer becomes sub punch and possibly other substances of the color developer solution consumed or abducted and must be supplemented in continuous operation.

The solution with which this supplement is made is called a regenerator (English: replenisher). It usually contains the necessary substances in a larger amount centering as the ready-to-use developer solution itself.

The color developer for color photographic paper is standard CD 3 with the formula

although good in the acidic and strongly alkaline range, in the photographically relevant Range of pH 9 to 12 but is poorly soluble.

In order to increase the solubility of the CD 3, water-soluble and in essence union photographic inactive organic solvents added, z. For example, alcohols, poly alcohols, glycols, polyglycol, p-toluenesulfonic acid, ethanolamines and caprolactam.

However, these solvents affect the development in the high densities, z. B. the maximum densities.

It has now been found that aliphatic carbonamides and sulfonamides also the Improve CD 3 solubility, but do not interfere with sensitometry. With the addition of open-chain carbonamides and sulfonamides the maximum densities become fully developed.

Suitable compounds are:

These solvents may be used individually, in admixture with each other or in admixture with other organic solvents are used, with open-chain carbon and Sulfonamides but make up at least 50 vol .-%.  

Suitable water-soluble solvents which may be used together with the carboxylic and sulfonic acid amides are e.g. B. carboxylic and urea derivatives such as N, N'-dimethyl urea, tetramethylurea, dimethylethyleneurea;
aliphatic and cyclic alcohols, e.g. For example isopropanol; tert-butyl alcohol, cyclohexanol, cyclohexanemethanol, 1,4-cyclohexanedimethanol;
aliphatic and cyclic polyalcohols, e.g. Glycols, polyglycols, polywaxes, trimethyl-1,6-hexanediol, glycerol, 1,1,1-trimethylolpropane, pentaerythritol, sorbitol;
aliphatic and cyclic ketones, e.g. Acetone, ethyl methyl ketone, diethyl ketone, tert-butyl methyl ketone, diisobutyl ketone, acetylacetone, acetonylacetone, cyclopentane, acetophenol;
aliphatic and cyclic carboxylic acid esters, e.g. B. triethoxymethane, methyl acetate, allyl acetate, methyl glycol acetate, ethylene glycol diacetate, glycerol 1-acetate, glycerol diacetate, methylcyclohexyl acetate, salicylic acid methyl ester, Salicylsäurephe nylester;
aliphatic and cyclic phosphonic acid esters, e.g. Methylphosphonic acid dimethyl ester, diethyl allylphosphonic acid;
aliphatic and cyclic oxy-alcohols, eg. 4-hydroxy-4-methyl-2-pentanone, salicylaldehyde;
aliphatic and cyclic aldehydes, e.g. Acetaldehyde, propanal, trimethylacetaldehyde, crotonaldehyde, glutaraldehyde, 1,2,5,6-tetrahydrobenzaldehyde, benzaldehyde, benzenepropane, terephthalaldehyde;
aliphatic and cyclic oximes, e.g. Butanone oxime, cyclohexanone oxime;
aliphatic and cyclic amines (primary, secondary or tertiary), e.g. Ethylamine, diethylamine, triethylamine, dipropylamine, pyrrolidine, morpholine, 2-aminopyrimidine;
aliphatic and cyclic polyamines (primary, secondary or tertiary), e.g. Ethylene diamine, 1-amino-2-diethylaminoethane, methyl-bis (2-methylamino-ethyl) amine, permethyl-diethylenetriamine, 1,4-cyclohexanediamine, 1,4-benzenediamine;
aliphatic and cyclic hydroxyamines, e.g. For example, ethanolamine, 2-methylethylamine, 2-methylaminoethanol, 2- (dimethylamino) ethanol, 2- (2-dimethylamino-ethoxy) -etha nol, diethanolamine, N-methyldiethanolamine, triethanolamine, 2- (2-aminoethyl amino) ethanol , Triisopropanolamine, 2-amino-2-hydroxymethyl-1,3-propanediol, 1-piperidineethanol, 2-aminophenol, barbituric acid, 2- (4-aminophenoxy) ethanol, 5-amino-1-naphthol.

In particular, 50 to 95 wt .-%, preferably 60 to 90 wt .-% of the sum from water and water-soluble solvent water.

The processing conditions, suitable antioxidants, suitable Puf substances, suitable anti-scale agents, suitable whiteners, auxiliary developers, Wetting agents, development accelerators and antifoggants are described in Research Dis closure 37 038 (February 1995) on pages 102 to 107.

Suitable antioxidants are compounds of the formulas (I), (II) and (III).

wherein
R _{1 is} alkyl,
R _{2 is} alkyl or 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 represents} an alkyl or acyl group;

wherein
R _{4 is} an optionally interrupted by O atoms alkylene group and
m is a number of at least 2.

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:

Examples Composition of the ready-to-use color developer solution for all examples

solvent see Table 1 Diethylhydroxylamine, 85 wt.% Aqueous solution 4 ml CD 3 5 g ethylenediaminetetraacetic 2 g potash 30 g potassium chloride 2 g Water on 1000 ml AL = L <pH 10.2

The following solvents and amounts were added to the color developer tank fillings per Liters added:

Table 1

Solvent and solvent quantity in the color developers

In the respective developer formulations was exposed photographic Mate processed and then evaluated. The results for the Maximaldich th are listed in Table 2.  

Table 2

Maximum densities of Examples 1 to 7

From Table 2 can be read that the addition of non-inventive solvent the maximum density in all three colors is suppressed (comparison of examples 2 to 4 with Example 1), while with the solvents according to the invention (examples) 5 to 7 the original level of maximum density is reached again.

The color photographic material used for the experiments was constructed as follows:
On a support made of paper coated on both sides with polyethylene, the following layers were applied in the order given. The amounts given are each based on 1 m ² . For the silver halide application, the appropriate amounts of AgNO ₃ are given.

• 1st layer (substrate layer):
  0.1 g of gelatin
• 2nd layer (blue-sensitive layer):
  blue-sensitive silver halide emulsion (99.5 mol% AgCl, 0.5 mol% AgBr, average grain diameter 0.9 μm)
  0.50 g of gelatin
  0.42 g yellow coupler GB-1
  0.18 g yellow coupler GB-2
  0.50 g of tricresyl phosphate (TKP)
  0.10 Stabilizer ST-1
• 3rd layer (intermediate layer):
  1.1 g of gelatin
  0.06 g Scavenger SC-1
  0.06 g Scavenger SC-2
  0.12 g TKP
• 4th layer (green-sensitive layer):
  green-sensitive silver halide emulsion (99.5 mol% AgCl, 0.5 mol% AgBr, average grain diameter 0.47 μm)
  0.40 g of AgNO ₃
  0.77 g of gelatin
  0.21 g magenta coupler PP-1
  0.15 g magenta coupler PP-2
  0.05 g Purpukuppler PP-3
  0.06 g color stabilizer ST-2
  0.012 g Scavenger SC2
  0.23 g of dibutyl phthalate
• 5th layer (UV protection layer):
  1.15 g of gelatin
  0.03 g Scavenger SC-1
  0.03 g Scavenger SC-2
  0.5 g UV absorber UV-1
  0.10 g UV absorber UV-2
  0.35 g TKP
• 6th layer (red-sensitive layer):
  red-sensitive silver halide emulsion (99.5 mol% AgCl, 0.5 mol% AgBr, mean grain diameter 0.5 μm)
  0.30 g of AgNO ₃ with
  1.0 g gelatin
  0.40 g cyan coupler BG-1
  0.05 g cyan coupler BG-2
  0.46 g TKP
• 7th layer (UV protection layer):
  0.35 g of gelatin
  0.15 g of UV-1
  0.03 g UV-2
  0.09 g TKP
• 8th layer (protective layer):
  0.9 g of gelatin
  0.3 g of hardener HM
  0.05 g whitener W-1
  0.07 g vinyl pyrrolidone
  1.2 mg of silicone oil
  2.5 mg polymethyl methacrylate beads with average particle diameter 0.8 microns
  

The material was processed under the following conditions:

developing bath

The developing solution of Example 5 was used.

Bleach Fix

Ammonium thiosulfate solution, 58% by weight 100 ml sodium metabisulfite 5 g Ammonium iron EDTA 48% by weight 100 ml

make up to 1000 ml with water, pH to 6.0 with ammonia or acetic acid to adjust.

stabilizer

water 900 ml sodium 2 g Hydroxyethandiphosphonsäuredinatriumsalz 4 g sodium benzoate 0.5 g

Make up to 1000 ml with water and adjust the pH to 5 with acetic acid.

dry

Claims (7)

A color photographic aqueous developing solution containing a color developing agent and an antioxidant and adjusted to a pH of 9 to 12, characterized by containing as the water-soluble organic co-solvent an open-chain carbonamide or sulfonamide. 2. color photographic aqueous developer solution according to claim 1, characterized ge indicates that the open-chain carbonamide or sulfonamide of a derived secondary amine. 3. color photographic aqueous developer solution according to claim 1, characterized in that the color developing agent, the formula
has. 4. color photographic aqueous developer solution according to claim 1, characterized ge indicates that 50 to 95 wt .-% of the sum of water and organi Shem solvents are water. 5. color photographic aqueous developer solution according to claim 1, characterized ge indicates that up to 50% by volume of the open-chain carbonamide or Sul Fonamids are replaced by other water-soluble organic solvents. 6. color photographic aqueous developer solution according to claim 1, characterized ge indicates that the amount of open-chain carbonamide or sulfonamide 0.01 to 2 mol / l.   7. color photographic aqueous developer solution according to claim 1, characterized ge indicates that the molecular weight of the open-chain carbon or sulfone amids ≦ 500.