DE19717229A1 - High speed production of coloured image - Google Patents

Abstract

In the production of coloured images from colour photographic material containing light-sensitive silver halide (AgX) emulsion layer(s) by selective exposure, development and removal of silver and residual AgX, the material used has emulsion layer(s) containing a yellow coupler, (a) in which >= 95 mole% of the AgX is silver chloride (AgCl) and (b) which is sensitised spectrally with a benzothiazolyl-benzoxazolyl or bis-benzothiazolyl monomethine cyanine of formula (I), and (c) the residence time in the colour developer is <= 40 seconds; in which R<1> = 2- or 3-thienyl; R<2>, R<3> = alkyl, sulphoalkyl, carboxyalkyl, -(CH2)n-SO2-NH-SO2-Alkyl, -(CH2)n-SO2-NH-CO-Alkyl, -(CH2)n-CO-NH-SO2-Alkyl; -(CH2)n-CO-NH-CO-Alkyl; n = 1-6; R<4>, R<5> = hydrogen (H), halogen, alkyl, methoxy, aryl, 2- or 3-furanyl, 2- or 3-thienyl, 1-, 2- or 3-pyrrolyl, 1-indolyl, N-carbazolyl or 2-isoindolyl; or R<4>R<5> = a group completing an optionally condensed benzene ring or naphthalene ring system; Z = oxygen (-O-) or sulphur (-S-); X = a counter-ion to balance the charge, if necessary.

Description

The invention relates to a processing method for producing colored images, esp special print images, using a color photographic recording material with at least one photosensitive silver halide emulsion layer coated with a Sensitizing dye is sensitized to blue light.

To produce colored print images is usually a multi-layer farbfotografi used sches material on a preferably light-reflecting substrate at least one blue-sensitive silver halide emulsion layer having a yellow coupler, at least one green-sensitive silver halide emulsion layer having a magenta coupler, at least one red-sensitive silver halide emulsion layer having a Cyan coupler and optionally contains other non-photosensitive layers.

Modern color photographic materials for the production of print images usually contain silver halide emulsions with a very high proportion of silver chloride; This brings due to the faster developability of silver chloride emulsions before significant parts in terms of a shorter processing time (short process). On the other hand, however, silver chloride emulsions show too low intrinsic sensitivity in the blue spectral range as compared to silver bromide or silver bromide iodide emulsions, therefore, in color photographic materials with high silver chloride content, not only the green and red sensitive layers but also the blue sensitive layers are made use of suitable sensitizing dyes spectrally sensitized. It is known that comparatively short-wave sensitization (λ _max <480 nm) results in color rendering benefits (yellow / red separation) but results in short-wavelength sensitizing dyeing materials which normally have lower sensitivity, cf. EP-A-0 683 427; EP-A-0 709 726. One reason for the reduced sensitivity of photographic materials sensitized with shorter wavelength sensitizing sensitizing dyes may be that the light sources used in the printers for exposure emit significantly less energy at wavelengths below 480 nm radiate.

Modern processing processes are towards shorter processing time and lower regeneration rates of the treatment baths, especially the color developer bades. Lower regeneration rates mean more concentrated baths with higher ones Exposure to decomposition products and contaminants from the paper or through a dragged substances from already processed treatment baths. A total of This leads to problems with processing stability. Ideally, a paper must be in a "normal" and according to the outlined trend "critical" process deliver equally good results; but in reality deviations from one lead "Normal state" of the treatment baths often lead to fluctuations in the result of Ver processing.

The invention is based on the object of a processing method for the production colored images, in particular print images to indicate, in which a shortened process when uniformity of the processing results, color images can be obtained in terms of yellow part color image, high sensitivity and low fog, as well have a good color rendering with regard to the yellow / red separation.

It was found that using a color photographic recording mate with at least one light-sensitive silver halide emulsion layer, the Sil at least 95 mol% of silver chloride and a Sensibi lisierungsfarbstoff the following formula I is spectrally sensitized by imagewise Exposure and processing in a process involving a color development step and one or more treatment steps to remove the formed silver and the residual silver halide, wherein the residence time in the color developer is not is more than 40 s, largely independent of fluctuations in the conditions of the Processing method color images (prints) are obtained, which are characterized by high Emp sensitivity (gradation) and reduced yellow haze at a more uniform er distinguishing results.

The invention relates to a processing method for producing colored images using a color photographic recording material having at least one photosensitive silver halide emulsion layer by imagewise exposure and processing in a process comprising a color development step and one or more treatment steps for removing the formed silver and the remaining silver halide in that a color photographic recording material having at least one yellow coupler-containing photosensitive silver halide emulsion layer whose silver halide consists of at least 95 mol% of silver chloride and is spectrally sensitized with a sensitizing dye of the formula I, is used,

in which mean:
R ^{1 is} 2-thienyl or 3-thienyl;
R ² and R ³ (identical or different): alkyl, sulfoalkyl, carboxyalkyl, - (CH ₂ ) _n -SO ₂ -NH-SO ₂ -alkyl, - (CH ₂ ) _n -SO ₂ -NH-CO-alkyl, - (CH ₂ ) _n -CO-NH-SO ₂ -alkyl, - (CH ₂ ) _n -CO-NH-CO-alkyl, (n = 1-6);
R ⁴ and R ₅ (same or different): H, halo, alkyl, methoxy, aryl, 2-furanyl, 3-furanyl, 2-thienyl, 3-thienyl, 1-pyrrolyl, 2-pyrrolyl, 3-pyrrolyl, 1 -Indolyl, N-carbazolyl or 2-isoindolyl, or R ⁴ together with R ^5, the necessary radical to complete an optionally substituted fused benzene ring or Naphthol ring system;
Z is -O- or -S-;
X is a counter ion which may be present for charge equalization, the residence time in the color developer bath being not more than 40 s.

Examples of suitable sensitizing dyes of the formula I are given below.

Cyanine dyes, also monomethine cyanine dyes derived from thiophene-substituted benz Thiazoles are derived are known from DE-AS 10 53 309, see, for example, there the dye of Example 1. Mono derived from thiophene-substituted benzothiazoles Methycyanine dyes are further mentioned in EP-A-0 683 426 and EP-A-0 683 427, see there the dyes I-1, I-9, I-10 and I-11; for these dyes, however, no Usage indicated, no results will be communicated and the stated color Substances are also not subject of the claims of EP-A-0 683 427. Claim 1 of EP-A-0 683 426 relates to a silver halide photographic silver halide element genidemulsion, which with a Blausensibilisierungsfarbstoff a formula I (hereunder fall among others, the dyes I-1, I-9, I-10 and I-11 mentioned therein) is sensitized and a thiosulfate, a sulfinate and an "alkynylamine".

According to the present invention, a color photographic recording material with at least one photosensitive silver halide emulsion layer is used whose Silver halide of at least 95 mol%, preferably not less than 99 mol%,  consists of silver chloride and spectrally with a sensitizing dye of the formula I. sensitized. Not only does this material have high (blue) sensitivity and better Color reproduction on, but it is characterized in particular by (in comparison with Materials with similar but not covered by the formula I sensitizing color spectrally sensitized) that these advantageous results in so-called Short processes are obtained. The processing method of the invention comprises after the imagewise exposure, a color development step, one or more be action steps for removing the formed silver and the remaining silver halo nids (bleach and fix or bleach-fix), and a rinse or stabilizer step. In the interest of an overall abbreviated processing process, the individual treatment steps take as little time as possible; in particular takes the color development step, the residence time in the color developer bath, in which for the prescribed processing process temperature, z. At 38 ° C, no longer than 40 seconds.

In a preferred embodiment of the invention, the treatment baths are continuously refreshed or regenerated. It proves to be particularly advantageous that in the processing method according to the invention without affecting the United processing results can be worked with relatively low Regenerierquoten. In particular, in particular embodiments of the invention, the regeneration rate of the color developer bath is not greater than 100 ml / sqm of processed material. When other sensitizing dyes than those of formula I are used for the blue sensitization, e.g. B. the dye VBS-3 (= dye I-8 from EP-A-0 683 426),

then, in the short process, larger deviations compared to the normal process observed in terms of sensitivity (gradation), color reproduction and the Yellow veil.

As further advantageous turns out (see Example 3) that with the Sensitization obtained according to the invention are the more pronounced, depending smaller the grain size of those used in the blue-sensitive layer Silver halide emulsion. Because of the faster developability of the comparatively Fine-grained emulsions this comes the intended abbreviation of the processing procedure against. In preferred embodiments of the invention, the mean is Grain size (diameter of the same volume sphere) of the silver halide particles in the blue-sensitive layer not larger than 0.7 μm, and more preferably not larger than 0.6 μm.

In advantageous embodiments of the invention, the color photographic recording material in at least one green-sensitive silver halide emulsion layer contains a 2-equivalent magenta coupler of the pyrazoloazole type. Such couplers preferably correspond to one of the two formulas IIA and IIB

in which mean:
R ²¹ , S and T are hydrogen-alkyl, aralkyl, aryl, Aroxy, alkylthio, arylthio, amino, anilino, acylamino, cyano, alkoxycarbonyl, carbamoyl or sulfamoyl, where these radicals may be further substituted and wherein at least one of these radicals is a ballast group and where appropriate, contains a stabilizer residue;
Y is a hydrogen-free radical which can be split off during the chromogenic coupling (leaving group).

Examples of color photographic materials are in the present case in particular Color positive films and color photographic paper.

The photographic materials consist of a support on which at least one light sensitive silver halide emulsion layer is applied. Suitable carriers are in special thin films and foils. An overview of carrier materials and their Front and back coated auxiliary layers are described in Research Disclosure 37254, Part 1 (1995), p. 285.

The color photographic materials usually contain at least one rotempfind green, green-sensitive and blue-sensitive silver halide emulsion layer as well optionally intermediate layers and protective layers.

Depending on the type of photographic material, these layers can be different orders be.

The possibilities of different layer arrangements and their effects on the photographic properties are described in J. Inf. Rec. Mats., 1994, Vol. 22, pages 183-193 described.

Color photographic paper, which is usually much less sensitive to light than a color photographic film, has in the order given below on the Usually each support a blue-sensitive, yellow coupling silver halide emulsion layer, a green-sensitive, magenta coupling silver halide emulsion layer, and a red-sensitive, cyan-coupling silver halide emulsion layer; the yellow filters layer can be omitted.  

Essential constituents of the photographic emulsion layers are binders, silver halide grains and color couplers.

Information on suitable binders can be found in Research Disclosure 37254, part 2 (1995), p. 286.

Information on suitable silver halide emulsions, their preparation, ripening, stabilization and spectral sensitization including suitable spectral sensitizers see Research Disclosure 36544 (Sept. 1994) and Research Disclosure 37254, Part 3 (1995), p. 286 and Research Disclosure 37038, Part XV (1995), p. 89. Photographic copying materials such as those in the processing ver used contain either silver chloride bromide emulsions with up to 80 mol% AgBr or silver chloride bromide emulsions containing over 95 mol% AgCl.

Information on the color couplers can be found in Research Disclosure 37254, Part 4 (1995), p. 288 and in Research Disclosure 37038, Part II (1995), p. 80. The maximum absorp tion of the formed from the couplers and the color developer oxidation product Dyes are preferably in the following ranges: yellow couplers 430 to 460 nm, Magenta couplers 540 to 560 nm, cyan couplers 630 to 700 nm. The color couplers are the concerning silver halide emulsion layer units or their sublayers Lich and spectrally assigned.

Under spatial assignment is to be understood that the color coupler in a such spatial relationship with the silver halide layer in question is that an interaction between them is possible, which is a pictorial conformity between the silver image formed during development and that from the color coupler allowed color image permits. This is usually achieved in that the color coupler in the silver halide emulsion layer itself is contained or in a neighboring thereto optionally non-photosensitive binder layer.

By spectral assignment is meant that the spectral response of the Photosensitive silver halide emulsion concerned and the color of the  spatially assigned color coupler generated partial color image in a particular Relationship to each other, where the spectral sensitivity of each color out (red, green, blue) a complementary colored partial color image (cyan, magenta, yellow) assigned.

Information on such compounds, in particular couplers, can be found in Research Disclosure 37254, Part 5 (1995), p. 290 and Research Disclosure 37038, Part XIV (1995), p. 86.

The most hydrophobic color couplers, but also other hydrophobic components of Layers are usually dissolved in high boiling organic solvents or dispersed. These solutions or dispersions are then dissolved in an aqueous Binder solution (usually gelatin solution) and emulsified after drying of the layers as fine droplets (0.05 to 0.8 mm in diameter) in the layers in front.

Suitable high-boiling organic solvents, methods for incorporation into the Layers of a photographic material and other methods, chemical compounds into photographic layers can be found in Research Disclosure 37254, Part 6 (1995), p. 292.

The usually between layers of different spectral sensitivity angeges Non-photosensitive intermediate layers may contain agents that have a unwanted diffusion of developer oxidation products from a photosensitive in another photosensitive layer with different spectral sensitization prevent.

Suitable compounds (white couplers, scavengers or EOP scavengers) can be found in Research Disclosure 37254, Part 7 (1995), p. 292 and Research Disclosure 37038, Part III (1995), p. 84.  

The photographic material may further UV-absorbing compounds, whiteners, spacers, filter dyes, Formalinfänger, light stabilizers, antioxidants, D _min dyes, additives to improve the dye, coupler and whitening stability and to reduce the color slide, plasticizers (latices) , Biocide and other included.

Suitable compounds are found in Research Disclosure 37254, Part 8 (1995), p. 292 and in Research Disclosure 37038, Parts IV, V, VI, VII, X, XI and MII (1995), p. 84ff. The layers of color photographic materials are usually cured, i. h., that used binders, preferably gelatin, by suitable chemical Networked process.

Suitable hardener substances can be found in Research Disclosure 37254, Part 9 (1995), p. 294 and Research Disclosure 37038, Part XII (1995), page 86.

After imagewise exposure, color photographic materials become their character processed according to different methods. Details of the Ver Procedural and required chemicals are described in Research Disclosure 37254, part 10 (1995), p. 294 and Research Disclosure 37038, parts XVI to XMII (1995), p. 95ff published together with exemplary materials.  

example 1

A suitable for a fast processing color photographic recording material was prepared by the following layers were applied in the order given on a substrate made of paper coated on both sides with polyethylene. The quantities are in each case based on 1 m ² . For the silver halide order the appropriate amounts of AgNO ₃ are given.

Samples 1-5

Layer 1: (substrate layer)
0.20 g of gelatin.

Layer 2: (blue-sensitive layer)
blue-sensitized silver halide emulsion (99.5 mol% chloride, 0.5 mol% bromide, mean grain diameter 0.78 μm), from 0.45 g AgNO ₃ , with
1.20 g of gelatin
0.60 g yellow coupler XY-1
0.20 g white coupler XW-1
0.30 g of tricresyl phosphate (TKP).

Layer 3: (protective layer)
1.00 g of gelatin
0.06 g of 2,5-di-tert-octylhydroquinone
0.06 g TKP.

Layer 4: (green-sensitive layer)
green-sensitized silver halide emulsion (99.5 mol% chloride, 0.5 mol% bromide, mean grain diameter 0.5 μm) from 0.35 g AgNO ₃ , with
1.00 g of gelatin
0.35 g magenta coupler XM-1
0.05 g of dye stabilizer XST-1
0.10 g of dye stabilizer XST-2
0.15 g TKP.

Layer 5: (UV protection layer)
1.10 g of gelatin
0.60 g of UV absorber mixture
(85% by weight of XUV-1 and 15% by weight of XUV-2)
0.05 g of 2,5-dioctylhydroquinone
0.05 g TKP.

Layer 6: (red-sensitive layer)
red sensitized silver halide emulsion (99.5 mol% chloride, 0.5 mol% bromide, mean grain diameter 0.5 μm) from 0.30 g AgNO ₃ , with
1.00 g of gelatin
0.36 g of cyan coupler XC-1
0.36 g TKP.

Layer 7: (UV protection layer)
0.35 g of gelatin
0.15 g UV absorber mixture of (85% by weight XUV-1 and 15% by weight XUV-2)
0.02 g TKP.

Layer 8: (protective layer)
0.90 g of gelatin.
0.30 g of hardener XH-1.

Compounds used in Samples 1-5:

Samples 1-5 are of the same composition and composition as and under differ only in that each sample in the blue-sensitive layer (Layer 2) with another sensitizing dye (Comparative Sensitization Dyes VBS-1, VBS-2 and VBS-3 or inventive dyes (I) -1 and  (I) -7) was sensitized. The dyes were each in an amount of 330 .mu.mol / mol Ag used. That's the amount at which the maximum sensitivity is achieved; further increase in the amount of dye gives no sensitivity profit, but gradation flatness and increased residual staining after Verar processing.

The samples were then exposed behind a graduated gray wedge; then, from each exposed sample, one strip was processed in the process a (standard processing) described below, another strip in the below-described process b (reduced residence time in color developer bath and bleach-fix bath, and reduced color developer recovery rate).

Color developer

Color developer

The tank filling at process b (tank filling b) is identical to tank filling a, however with one exception: potassium chloride 6 g instead of 2.5 g!

Bleach-fix bath (identical for process a and process b)

tankful ammonium 75.0 g sodium bisulfite 13.5 g Ethylenediaminetetraacetic acid (ferric ammonium salt) 57.0 g Ammonia 25% 9.5 g

Make up to 1 l and pH 6.0 with water.
Regenerator identical to tank filling, but set pH 5.5. Regeneration rate 215 ml / sqm.

Stabilizing bath (identical for process a and process b)

sodium 2.0 g sodium 2.0 g sodium benzoate 1.0 g HEDP acid (60%) 4.0 ml

Make up to 1 liter and pH 5.0 with water.
Regenerator identical to tank filling.
Regeneration rate (process a): 250 ml / qm
Regeneration rate (process b): 180 ml / qm.
The results are shown in the form of the following parameters in Table 1:
S _max

: Sensitization maximum, [nm];
Sensitivity (when developed in process a, exposure by step wedge, filtration constant, arbitrary units, a difference of 0.1 corresponds to 1 DIN difference;
ΔC: color saturation difference (chroma, CieLab system) between original (field "yellow" of the Macbeth color chart) and the print;
ΔEmpf .: (Recommended when developing in process a) - (Recommended when developing in process b)
ΔG: (gradation in development in process a) - (gradation in development in process b); Gradation = secant slope of the sensitometric curve between density = 1.0 and density = 1.8;
Dmin: minimum density (gb) when developing in process b.

Table 1

It can be seen from the table that (as expected) a short-wave Blausensi Advantages for color rendering (here, for example, the yellow-red reproducing). In contrast to the comparison, the sensitization according to the invention dyes but at the same time a sufficiently high sensitivity. Furthermore are at Materials with sensitivity sensitization and gradation according to the invention less processing dependent and the minimum density (gb) is lower.

Example 2

A color photographic recording material suitable for a fast processing process was prepared (Samples 6-10) which was in layered form and composition identical to Samples 1-5 described in Example 1, but with the following changes:
In layer 2, the yellow coupler XY-2 was used in the same amount instead of the yellow coupler XY-1. In layer 4, instead of the magenta coupler XM-1, the magenta coupler XM-2 was used in the same amount and the silver coverage in this layer was only 0.2 g AgNO ₃ .

The processing was carried out as indicated in Example 1. The results are in table 2 shown.

Table 2

Example 3

A color photographic recording material suitable for a rapid processing process was prepared (Samples 11-18) which in layered form and composition matches Samples 3 and 4 described in Example 1, but with the following changes:

In layer 2, the yellow coupler XY-2 was replaced by the yellow coupler XY-1 in the same Quantity used. In addition, in layer 2, the average grain size and the Amount of sensitizing dye changed as shown in Table 3.

The processing was carried out as indicated in Example 1. The results are in table 3 shown.

Table 3

It can be seen from the table that the advantages of Sensibili invention tion are particularly pronounced at smaller particle sizes.

Claims (4)

A process for producing colored images using a color photographic material having at least one photosensitive silver halide emulsion layer by imagewise exposure and processing in a process comprising a color development step and one or more treatment steps for removing the formed silver and residual silver halide, characterized in that a color photographic recording material is used with at least one yellow coupler-containing photosensitive silver halide emulsion layer whose silver halide consists of at least 95 mol% of silver chloride and is spectrally sensitized with a sensitizing dye of the formula I,
in which mean:
R ^{1 is} 2-thienyl or 3-thienyl;
R ² and R ³ (identical or different): alkyl, sulfoalkyl, carboxyalkyl, - (CH ₂ ) _n -SO ₂ -NH-SO ₂ -alkyl, (CH ₂ ) _n -SO ₂ -NH-CO-alkyl, (CH ₂ ) _n -CO-NH-SO ₂ -alkyl, - (CH ₂ ) _n -CO-NH-CO-alkyl, (n = 1-6);
R ⁴ and R ⁵ (same or different): H, halo, alkyl, methoxy, aryl, 2-furanyl, 3-furanyl, 2-thienyl, 3-thienyl, 1-pyrrolyl, 2-pyrrolyl, 3-pyrrolyl, 1 -Indolyl, N-carbazolyl or 2-isoindolyl, or R ⁴ together with R ^5, the necessary radical to complete an optionally substituted fused benzene ring or Naphtholringsystems;
Z is -O- or -S-;
X is a counter ion which may be present for charge compensation,
wherein the residence time in the color developer is not more than 40 s. 2. Processing method according to claim 1, characterized in that the Rege nerierquote the color developer bath is not greater than 100 ml / sqm of processing teten material. 3. Processing method according to one of claims 1 and 2, characterized gekenn draws that the mean grain size (diameter of the same volume sphere) the silver halide particle in the blue-sensitive layer is not larger than 0.7 μm. 4. Processing method according to one of claims 1 to 3, characterized in that the color photographic recording material in at least one green sensitive silver halide emulsion layer contains a 2-equivalent magenta coupler of the two formulas IIA and IIB
in which mean:
R ²¹ , S and T are hydrogen, alkyl, aralkyl, aryl, Aroxy, alkylthio, arylthio, amino, anilino, acylamino, cyano, alkoxycarbonyl, carbamoyl or sulfamoyl, where these radicals may be further substituted and wherein at least one of these radicals is a ballast group and where appropriate, contains a stabilizer residue;
Y is a hydrogen-free radical which can be split off during the chromogenic coupling (leaving group).