DE19717898A1 - Colour photographic material with reduced dark fading of cyan image dye - Google Patents

Abstract

In colour photographic material with red-, green- and blue-sensitive silver halide (AgX) emulsion layer(s) associated with cyan, magenta and yellow couplers respectively and optionally light-insensitive layer(s), at least one of the layers contains furan, thiophene or pyrrole compound(s) of formula (I) or (II); in which X = oxygen (-O-), sulphur (-S-) or imino (-NRa-); Ra = hydrogen (H), alkyl or aryl; Y = *(CH2)p,-Q<1>q-CO-(Q<2>)r-, *-(CH2)p,Q<1>-SO2-(Q<2>)r- pr *-(CH2)p-O-; * = the bond to the heterocyclic ring; Q<1>, Q<2> = -O- or -NRb-; Rb = H, alkyl or aryl; R<1>, R<2> = alk(en)yl or aryl; m = 1 or 2; n = 0, 1 or 2; p, q, r = 0 or 1.

Description

The invention relates to a color photographic recording material with photosensitive Silver halide emulsion layers and associated color couplers, which in min at least one photosensitive or non-photosensitive layer a compound of a which contains formulas I and II (5-ring heterocydus). The compounds are as oil formers suitable, in particular an improvement in the dark storage stability of the chro homogeneous development of image dyes generated from cyan couplers.

It is known to produce color photographic images by chromogenic development, d. H. by exposing imagewise exposed silver halide emulsion layers in counter were suitable color couplers using suitable color-forming developer substances - so-called named color developer - developed in accordance with the silver image developing developer oxidation product (EOP) with the color coupler to form a Dye image reacts. Aromatic, primary are usually used as color developers Compounds containing amino groups, in particular of the p-phenylenediamine type, ver turns.

The stability of the color photogra in the chromogenic development of color coupler Image dyes produced in fish recording materials leave much to be desired left. On the one hand, this affects the stability against the influence of light (light fading) and on the other hand the stability against the effects of damp or dry heat (dark fading).

It is known from JP-A-06 148 836 and JP-A-06 175 315, fatty S-oxo and S, S- Dioxothiolanes as oil formers for malondiamide yellow couplers or heterocyclic cyan to use couplers. JP-A-04 009 037 describes the use of water-soluble tetra Hydrofuran derivatives in photographic material to improve processing stability act revealed. W-A-02 262 650 describes the use of fatty pyrrolidines to improve the stability of the yellow and blue-green partial image. In JP-A-63 175 853 the use of unballasted thiophene-2,5-dicarboxylic acid esters for Schleiersen kung revealed.  

It has been found that compounds of one of the formulas I and II act as oil formers for Color couplers are suitable, which in particular improve the dark storage stability of the image dyes produced in the chromogenic development from cyan couplers ken.

The invention relates to a color photographic recording material with at least one red-sensitive silver halide emulsion layer, which is associated with a cyan coupler, at least one green-sensitive silver halide emulsion layer, which is associated with a magenta coupler, at least one blue-sensitive silver halide emulsion layer, which is associated with a yellow coupler, and optionally other non-light-sensitive layers , characterized in that it contains at least one compound of the formulas I and II in at least one light-sensitive or non-light-sensitive layer,

in what mean
X -O-, - S- or NR ^a - (R ^a = H, alkyl or aryl),
Y * [(CH ₂ ) _p -Q ¹ ] _q -CO- (Q ² ) _r -, * (CH ₂ ) _p -Q ¹ -SO ₂ - (Q ² ) _r or * - (CH ₂ ) _p - O-
(the asterisk (*) denotes the bond to the heterocyclic 5-ring);
Q ¹ and Q ² (identical or different): -O- or -NR ^b - (R ^b = H, alkyl or aryl, where two radicals R ^{b can be} identical or different);
R ¹ and R ² (same or different) alkyl, alkenyl or aryl;
m 1 or 2;
n 0 (zero), 1 or 2;
p, q and r (independently of each other): 0 (zero) or 1.

The meanings H and alkyl are preferred for R ^a and R ^b . An alkyl or alkenyl radical represented by or contained in one of the radicals R ¹ , R ² , R ^a and R ^b may be straight-chain, branched or cyclic, and may also be substituted, e.g. B. with aryloxy. Corresponding aryl radicals can also be substituted, for. B. with alkyl or alkoxy. The radicals represented by R ¹ and optionally R ² together contain not less than 8 C atoms, preferably not less than 12 C atoms, and therefore have a ballasting effect on the compounds of the formulas I and II.

In particularly preferred embodiments of the invention, the compound according to the invention corresponds to one of the formulas III, IV and V:

wherein R ¹ and n have the meanings already given for the formulas I and II
and in which mean:
X ³ , X ⁴ and X ⁵ radicals such as X;
Y ³ and Y ⁴ * -CO-O-, * -CO-NR ^c - or * -CH ₂ -L-
(the asterisk (*) denotes the bond to the heterocyclic 5-ring);
L -NR ^c -CO-, -NR ^c -CO-O-, -NR ^c -CO-NR ^c -, -NR ^c -SO ₂ -, -O-CO-, -O-CO-O- -O -CO-NR ^c or -O-SO ₂ -;
Y ⁵ * -NR ^c -CO-, * -NR ^c -CO-O-, * -NR ^c -CO-NR ^c -, * -NR ^c -SO ₂ -;
(the asterisk (*) denotes the bond to the heterocyclic 5-ring);
R ^c H or alkyl, where two radicals R ^{c may be the} same or different;
R ³² , R ⁴² and R ⁵² alkyl.

X ⁴ and X ⁵ (formulas IV and V) are preferably -O- or -S- and n is 0 (zero).

Examples of compounds according to the invention are:

Synthesis of I-1

38.6 g of furan-2-carboxylic acid, 55.8 g of dodecanol and 1 g of p-toluenesulfonic acid heated to boiling in 500 ml of toluene on a water separator. After 5 g of water are separated, the organic phase with 5% sodium hydroxide solution and water washed and then clarified with 10 g of activated carbon. After evaporating the Solvent gives 73 g of I-1 as a light yellow oil.

Synthesis of I-9

A solution of 39.4 g of 2- (aminomethyl) furan in 250 ml of acetone is added dropwise T = 0-5 ° C a solution of 38.5 g (2-ethylhexyl) chloroformate in 50 ml acetone slowly to. After stirring for 2.5 h at T = 25 ° C., 250 ml of water and 250 ml of ethyl acetate, the aqueous phase extracted twice with 100 ml of ethyl acetate and washes the combined organic phases with water. The solvent will evaporated and the crude product distilled. The one going over at 132-134 ° C / 0.5 mbar Fraction is caught. This gives 42.0 g of I-9 as a light yellow oil.

Synthesis of II-3

To a solution of 20.4 g (2-hydroxymethyl) tetrahydrofuran in 40 ml pyridine and 160 ml of acetone become 49.2 g at T = 0-5 ° C. Myristic acid chloride added dropwise. To 5 h at T = 20 ° C, 250 ml of water and 500 ml of ethyl acetate are added. The orga African phase is washed with 10% hydrochloric acid and water. The solvent is evaporated and the crude product distilled. The at 158-62 ° C / 0.5 mbar above outgoing fraction is caught. This gives 30 g of II-3 as a light yellow oil.

The compounds according to the invention are generally used in the layers of the color photographic recording material in a concentration of 10-2000 mg / m ² per layer, preferably of 25-1000 mg / m ² per layer. The incorporation is carried out together with the relevant color coupler and, if appropriate, other additives using the customary dispersion processes.

The compounds according to the invention are particularly suitable as oil formers for paints coupler and in particular improve the dark storage stability of the the chromogenic development of image dyes generated from cyan couplers. you will be therefore preferably together with cyan couplers, especially together with phenoli cyan couplers used.

Color couplers for producing the partial color image cyan are usually couplers of the phenol-α-naphthol or pyrrolotriazole type; suitable examples are

Examples of color photographic materials are color negative films, color reversal films color positive films, color photographic paper, color reversal photographic paper color sensitive Materials for the color diffusion transfer process or the silver color bleaching process. An overview of typical color photographic materials as well as preferred versions Forms of processing and processing can be found in Research Disclosure 37038 (February 1995), Research Disclosure 38957 (September 1996).

The photographic materials consist of a support on which at least one light sensitive silver halide emulsion layer is applied. Are suitable as carriers special thin films and foils. An overview of carrier materials and on their Auxiliary layers applied to the front and back are in Research Disclosure 37254 part 1 (1995), p. 285 and Research Disclosure 38957, Part XV. (1996), p. 627.

The color photographic materials usually contain at least one red sensitivity Liche, green-sensitive and blue-sensitive silver halide emulsion layer and ge if necessary, intermediate layers and protective layers.

Depending on the type of photographic material, these layers can be applied differently to be in order. This is shown for the most important products:  

Color photographic films such as color negative films and color reversal films show in the the order given below on the support 2 or 3 red-sensitive, blue-green coupling silver halide emulsion layers, 2 or 3 green sensitive, purple domes de Silver halide emulsion layers and 2 or 3 blue-sensitive, yellow-coupling Sil overhalide emulsion layers. The layers of the same spectral sensitivity differ in their photographic sensitivity, the less sensitive Chen sub-layers are usually arranged closer to the carrier than the higher sensitivity partial layers.

There is usually one between the green-sensitive and blue-sensitive layers Yellow filter layer attached, which prevents blue light from penetrating into the one below Layers.

The possibilities of different layer arrangements and their effects the photographic properties are described in J. Inf Rec. Mats., 1994, Vol. 22, pages 183- 193 and Research Disclosure 38957, part in. (1996), p. 624.

Color photographic paper, which is usually much less sensitive to light than one color photographic film, shows in the following order Carriers usually each have a blue-sensitive, yellow-coupling silver halide emulsion layer, a green-sensitive, purple-coupling silver dialogen emulsion layer and one red-sensitive, cyan-coupling silver halide emulsion layer; the yellow filter layer can be omitted.

Deviations in the number and arrangement of the light-sensitive layers can lead to Achieve certain results. For example, everyone can be high sensitive layers to form a layer package and all low-sensitivity layers another layer package can be summarized in a photographic film in order to Increase sensitivity (DE-A-25 30 645).

Essential components 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 and Research Disclosure 38957, Part II.A (1996), p. 598.

Information about suitable silver halide emulsions, their preparation, maturation, stabilization sation and spectral sensitization including suitable spectral sensitizers can be found in Research Disclosure 36544 (Sept. 1994), Research Disclosure 37254, Part 3 (1995), p. 286, Research Disclosure 37038, Part XV (1995), p. 89 and in Research Disclosure 38957, Part V. A (1996), p. 603.

Photographic materials with camera sensitivity usually contain silver bromide iodide emulsions, which may also contain small amounts of silver chloride can. Photographic copying materials contain either silver chloride bromide emulsion with up to 80 mol% AgBr or silver chloride bromide emulsions with over 95 mol% AgCl.

Information on the color couplers can be found in Research Disclosure 37254, Research Disclosure Part 4 (1995), p. 288, Research Disclosure 37038, Part II (1995), p. 80 and Research Disclosure 38957, Part X. B (1996), p. 616. The maximum absorption of the dyes formed from the couplers and the color developer oxidation product preferably in the following ranges: yellow coupler 430 to 460 nm, magenta coupler 540 to 560 nm, cyan couplers 630 to 700 nm. The color couplers are the relevant ones Silver halide emulsion layer units or their sublayers spatially and spectrally assigned.

Spatial assignment is understood to mean that the color coupler is in one such spatial relationship to the silver halide layer in question that an interaction between them is possible that is a pictorial match between the silver image formed during development and that from the color coupler color image generated. This is usually achieved by the color coupler in the silver halide emulsion layer itself or in an adjacent one possibly non-photosensitive binder layer.  

Spectral assignment means that the spectral sensitivity of the be matching light sensitive silver halide emulsion and the color of the spatially assigned color coupler generated partial color image in a certain relationship stand with each other, whereby the spectral sensitivity of each individual color separation (red, Green, blue) assigned a complementary-colored partial color image (cyan, magenta, yellow) is.

Color photographic films are used to improve sensitivity, graininess, Sharpness and color separation are often used when reacting with the compounds Developer oxidation product release compounds that are photographically active z. B. DfR couplers that release a development inhibitor. Information about such connections genes, in particular couplers, can be found in Research Disclosure 37254, Part 5 (1995), p. 290, Research Disclosure 37038, Part XIV (1995), p. 86 and Research Disclosure 38957, Part X. C (1996), p. 618.

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

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

Which are usually arranged between layers of different spectral sensitivity Non-light-sensitive intermediate layers can contain agents desired diffusion of developer oxidation products from a photosensitive in another photosensitive layer with different spectral sensitization ver prevent.  

Suitable connections (white coupler, scavenger or EOP catcher) can be found in Research Disclosure 37254, Part 7 (1995), p. 292, Research Disclosure 37038, Part III (1995), p. 84 and Research Disclosure 38957, Part X.D.

The photographic material can also contain UV light-absorbing compounds, white toners, spacers, filter dyes, formalin scavengers, light stabilizers, antioxidants, D- _min dyes, additives to improve the stability of dyes, couplers and whites and to reduce the color fog, plasticizers (latices ), Biocide and others contain. Suitable compounds can be found in Research Disclosure 37254, Part 8 (1995), p. 292, Research Disclosure 37038, Parts IV, V, VI, VII, X, XI and XIII (1995), p. 84 ff and Research Disclosure 38957, Parts VI, VIII, IX, X. (1996), pp. 607, 610 ff.

The layers of color photographic materials are typically hardened, i.e. i.e., the ver Binder used, preferably gelatin, is made by suitable chemical methods networked. Suitable hardener substances can be found in Research Disclosure 37254, Part 9 (1995), p. 294, Research Disclosure 37038, Part XII (1995), page 86 and Research Disclosure 38957, Part II. B (1996), p. 599.

After image-wise exposure, color photographic materials become their character processed according to different procedures. Details of the procedure and chemicals required for this are in Research Disclosure 37254, Part 10 (1995), p. 294 and in Research Disclosure 37038, parts XVI to XXIII (1995), p. 95 ff and Research Disclosure 38957, Parts XVIII, XIX, XX. (1996), pp. 630 ff together with exemplary materials published.  

Examples example 1

A multilayer color photographic recording material was produced (sample 1) by applying the following layers in the order given to a support made of paper coated on both sides with polyethylene. All amounts refer to 1 m ² , the amount of silver is given as AgNO ₃ :

Sample 1

Layer 1 (substrate layer)
0.10 g gelatin

Layer 2 (blue sensitive layer):
blue-sensitive silver halide emulsion (99.5 mol% chloride,
0.5 mol% bromide, average grain diameter 0.9 m) from 0.50 g
AgNO ₃ , with
1.25 g gelatin
0.42 g yellow coupler XY-1
0.18 g yellow coupler XY-2
0.50 g tricresyl phosphate (TKP) - (oil former)
0.10 g stabilizer XST-1
0.70 mg blue sensitizer XBS-1
0.30 mg stabilizer XST-2

Layer 3 (intermediate layer)
1.10 g gelatin
0.06 g Oxform catcher XSC-1
0.06 g Oxform catcher XSC-2
0.12 g TKP- (oil former)

Layer 4 (green sensitive layer)
green-sensitive silver halide emulsion (99.5 mol% chloride, 0.5 mol% bromide, average grain diameter 0.47 m) from 0.40 g
AgNO ₃ , with
0.77 g gelatin
0.41 g XM-1 magenta coupler
0.06 g stabilizer XST-3
0.12 g Oxform catcher XSC-2
0.34 g dibutyl phthalate (DBP) - (oil former)
0.70 mg green sensitizer XGS-1
0.50 mg stabilizer XST-4

Layer 5 (UV protective layer)
0.95 g gelatin
0.30 g UV absorber XUV-1
0.20 g XUV-2 UV absorber
0.03 g Oxform catcher XSC-1
0.03 g Oxform catcher XSC-2
0.30 g XOF-1 - (oil generator)

Layer 6 (red sensitive layer)
red-sensitive silver halide emulsion (99.5 mol% chloride, 0.5 mol% bromide, average grain diameter 0.5 µm) from 0.30 g AgNO ₃ , with
1.0 g gelatin
0.46 g cyan coupler XC-1
0.46 g TKP- (oil former)
0.03 mg red sensitizer XRS-3
0.60 mg stabilizer XST-5

Layer 7 (UV protective layer)
0.30 g gelatin
0.10 g LV absorber XUV-3
0.10 g XOF-2 - (oil generator)

Layer 8 (protective layer)
0.90 g gelatin
0.05 g white toner XWT-1
0.07 g stain (PVP)
1.20 mg silicone oil
2.50 mg spacer (polymethyl methacrylate, average particle size 0.8 µm)
0.30 g of XH-1 curing agent

Samples 2-15

Samples 2-5, 7-10 and 12-15 are made like Sample 1, but with the Difference that the oil formers in layers 2-7 were replaced in equal quantities by oil formers according to the invention as shown in Table 1. For layers 2, 4 and 6, however, this only applies subject to the following information regarding further differences in samples 6-15. Other differences:

Layer 2, samples 6-15:

• a) the yellow coupler (XM-1 / XM-2) was exchanged for 0.55 g yellow coupler XY-3 (samples 6-10) or 0.60 g yellow coupler XY-4 (samples 11-15)
• b) the stabilizer XST-1 was replaced by 0.11 g of stabilizer XST-10  (Samples 6-10) or 0.20 g stabilizer XST-7 (samples 11-15)

Layer 4, Samples 6 - 15:

• a) the magenta coupler XM-1 was exchanged for 0.24 g magenta coupler XM-2 (samples 6-10) or 0.12 g magenta coupler XM-3 (samples 11-15)
• b) the oil generator DBP was replaced by 0.48 g oil generator DBP / XOF-3 (1: 1) (sample 6) or 0.36 g oil generator XOF-1 / XOF-2 / TKP (2: 1: 1) (sample 11)
• c) the silver coating of 0.40 g AgNO ₃ was reduced to 0.28 g (samples 6-10) or 0.23 g (samples 11-15)
• d) the Oxform catcher XSC-2 was replaced by 0.12 g stabilizer XST-6 (samples 6-10) or 0.03 g stabilizer XST-7 (samples 11-15)
• e) the stabilizer XST-3 was replaced by 0.18 g stabilizer XST-8 (Samples 6-10) or 0.03 g stabilizer XST-9 (samples 11-15)

Layer 6, Samples 6-15:

• a) (Samples 6-10): the cyan coupler XC-1 was exchanged for 0.44 g a (80:20) mixture of cyan coupler XC-1 and cyan coupler XC-2 (Samples 11-15) of the cyan coupler XC-1 was exchanged for 0.38 g a (20:80) mixture of cyan coupler XC-1 and cyan coupler XC-3
• b) the oil producer TKP was exchanged for oil producers in equal quantities DBP / XOF-3 (1: 1) (sample 6) or oil former XOF-2 (sample 11)

Compounds used in Example 1:

The color photographic recording material is exposed to white light through a step wedge. The exposed material is processed according to the following scheme:

Color developer solution (CD)

Tetraethylene glycol 20.0 g N, N-diethylhydroxylamine 2.0 g N, N-bis (2-sulfoethyl) hydroxylamine disodium salt 2.5 g (N-ethyl-N- (2-methanesulfonamido) ethyl) -4-amino-3-methylbenzenesulfate 5.0 g Potassium sulfite 0.2 g Potassium carbonate 30.0 g Polymaleic anhydride 2.5 g Hydroxyethane diphosphonic acid 0.2 g White toner (4,4'-diaminostilbene type) 2.0 g Potassium bromide 0.02 g

make up to 1000 ml with water, pH value with KOH or H ₂

SO _4th

adjust to pH = 10.2.

Bleach-fix solution (BX)

Ammonium thiosulfate 75.0 g Sodium bisulfite 13.5 g Ethylenediaminetetraacetic acid (iron ammonium salt) 45.0 g

make up to 1,000 ml with water, pH value with ammonia (25%) or acetic acid adjust to pH 6.0.

Then the yellow, magenta and cyan densities are measured (Table 1). In addition, the samples are 40 days at 85 ° C and 50% rel. Moisture stored neutral. The percentage decrease in the maximum cyan density (D _max ) (Table 1) is then determined.

(V: comparison, E: according to the invention)

(V: comparison, E: according to the invention)

The following were used as comparison compounds:

As Table 1 shows, the compounds according to the invention are like the comparison compounds TKP, DBP, XOF-1 to XOF-4 are suitable as oil formers for color couplers, but they do unlike the comparison compounds TKP, DBP, XOF-2, XOF-3, V-2 a clear one Improvement of the dark storage stability of the cyan colored pencils. The comparison association V-1 and V-3 are unsuitable as oil formers for photographic components.

Claims (6)

1. Color photographic recording material with at least one red-sensitive silver halide emulsion layer, which is assigned a cyan coupler, at least one green-sensitive silver halide emulsion layer, which is associated with a magenta coupler, at least one blue-sensitive silver halide emulsion layer, which is associated with a yellow coupler, and optionally further non-light-sensitive layers, characterized in that at least one light-sensitive or non-light-sensitive layer contains at least one compound of one of the formulas I and II
in what mean
X -O-, -S- or -NR ^a - (R ^a = H, alkyl or aryl);
Y * - [(CH ₂ ) _p , -Q ¹ ] _q -CO- (Q ² ) _r -, * - (CH ₂ ) _p , -Q ¹ -SO ₂ - (Q ² ) _r - or * - ( CH ₂ ) _p -O- (the asterisk (*) denotes the bond to the heterocyclic 5-ring);
Q ¹ and Q ² (identical or different): -O- or -NR ^b - (R ^b = H, alkyl or aryl, where two radicals R ^{b can be} identical or different);
R ¹ and R ² (same or different): alkyl, alkenyl or aryl;
m 1 or 2;
n 0 (zero), 1 or 2;
p, q and r (independently of each other): 0 (zero) or 1. 2. Recording material according to claim 1, characterized in that the Ver compound of one of the formulas I and II corresponds to one of the formulas III, IV and V.
in which mean:
R ^{1 is} alkyl, alkenyl or aryl;
n 0 (zero), 1 or 2;
X ³ , X ⁴ and X ⁵ -O-, -S- or -NR ^a - (R ^a = H, alkyl or aryl);
Y ³ and Y ⁴ * -CO-O-, * -CO-NR ^c or * -CH ₂ -L-
(the asterisk (*) denotes the bond to the heterocyclic 5-ring);
L -NR ^c -CO-, -NR ^c -CO-O-, -NR ^c -CO-NR ^c -, -NR ^c -SO ₂ -, -O-CO-, -O-CO-O-, - O-CO-NR ^c - or -O-SO ₂ -;
Y ⁵ * -NR-CO-, * -NR-CO-O-, * -NR ^c -CO-NR ^c -, * -NR ^c -SO ₂ -;
(the asterisk (*) denotes the bond to the heterocyclic 5-ring);
R ^c H or alkyl, where two radicals R ^{c may be the} same or different;
R ³² , R ⁴² and R ⁵² alkyl. 3. Recording material according to one of claims 1 and 2, characterized in that the compound corresponds to one of the formulas IV and V in which n = 0 and X ⁴ and X ^{5 are} -O- or -S-. 4. Recording material according to one of claims 1-3, characterized in net that in the layer containing the compound of one of the formulas I-V Color coupler is included. 5. Recording material according to claim 4, characterized in that the Color coupler is a phenolic color coupler. 6. Recording material according to one of claims 1-3, characterized in net that in the layer containing the compound of one of the formulas I to V, a scavenger compound and / or a UV absorber is contained.