DE19543201A1 - Colour photographic silver halide material giving high speed without increased fog - Google Patents

Abstract

In colour photographic silver halide (AgX) material with sets of at least 2 blue-, green- and red-sensitive, yellow-, magenta- and cyan-coupling AgX emulsion layers of different speed, at least one fast AgX emulsion layer or adjacent light-insensitive layer contains a development activator of formula R(O-CH2CH2-S-(LINK<1>-S)x-CH2CH2-O-(LINK<2>))y-OR (I) and at least 20 vol.% of the fast AgX emulsion layer consists of a synthetic polymer. In (I), LINK<1> and LINK<2> are each a divalent linking group; R is H, acyl or optionally substituted alkyl or aryl group; x = 0, 1 or 2; and y = 1-20.

Description

The invention relates to a color photographic recording material with high Sensitivity and low fog.

The improvements are achieved when the color photographic recording material in a highly sensitive silver halide emulsion layer or For this purpose, a development activator adjacent to the non-light-sensitive layer contains and the highly sensitive silver halide emulsion layer a high Has proportion of synthetic polymer.

The particularly effective development activators include the polymers Thioether from EP-A-674 215. They increase the sensitivity of a photographic Materials, however, lead, especially when using highly reactive Color couplers, as is the case in high sensitivity photographic materials State of the art often includes an undesirable increase in Veil.

Furthermore, it is known that by incorporating synthetic polymers in photographic layers, especially latex particles, the physical Properties of materials can be improved, such as. See, for example, US-A-3,397,988 described.

Depending on the material structure, the polymer structure and the amount of latex However, sensitometric advantages for graininess, sharpness and emp sensitivity can be achieved such. B. in EP-A-271 797 and EP-A-205 075 ben.

The invention is therefore based on the object, a color photographic To provide high sensitivity recording material in which the Sensitivity does not improve with an increase in fog connected is.

It has now been found that the above object with a color photographic recording material is solved according to claim 1.  

The invention relates to a color photographic recording material at least two blue-sensitive, yellow-coupling silver halide emulsions layers of different photographic sensitivity, at least two green sensitive, purple-coupling silver halide emulsion layers differ cher photographic sensitivity and at least two red-sensitive, blue green coupling silver halide emulsion layers of different photographic Sensitivity, characterized in that it is highly sensitive in at least one Liche silver halide emulsion layer or an adjacent non-light sensitive layer a development activator of formula I.

R [O-CH₂-CH₂-S- (LINK¹-S) _x -CH₂-CH₂-O- (LINK²)] _y -OR (I)

contains, where
LINK¹, LINK² a two-value link,
RH, an optionally substituted alkyl radical, an optionally substituted aryl radical or acyl radical,
x 0, 1 or 2 and
y is 1 to 20,
and at least 20% by volume of the highly sensitive silver halide emulsion layer is made of a synthetic polymer.

In a preferred embodiment of the invention, the development corresponds activator of formula I of formula II

HO - (- CH₂-CH₂-S-CH₂-CH₂-OZO-) _y -H (II),

in which
Z is a divalent link and
y is 1 to 20.

Examples of divalent links Z are

-CH₂-CH₂-, -CH₂-CH₂-O-CH₂-CH₂-, - (CH₂-CH₂-O) _y -CH₂-CH₂-,
-CH₂-CH₂-C (CH₃) ₂-CH₂-CH₂-, -CH₂-CH₂-NH-CO-NH-CH₂-CH₂-,
-CH₂-C (R¹) (R²) -CH₂-, -CH₂-CH₂-N (COR³) -CH₂-CH₂-,
-CH₂-CH₂-NR⁴-CH₂-CH₂-, -CH₂-phen-CH₂- and
-CH₂-CH₂-NH-CO-CO-NH-CH₂-CH₂-,

in which
R¹, R², R³, R⁴ H, an optionally substituted alkyl radical or an optionally substituted aryl radical and
Phen -C₆H₄- mean.

Table 1 contains examples of preferred compounds of the formula II.

Table 1

Particularly preferred compounds of the formula II are E-3, E-7 and E-8.  

In a further preferred embodiment of the invention, the Development activator of formula I of formula III

HO - (- CH₂-CH₂-S-CH₂-CH₂-S-CH₂-CH₂-OZO-) _y -H (III),

in which
Z is a divalent link and
y is 1 to 20.

Table 2 contains examples of preferred compounds of the formula III.

Table 2

The development activators of formula I are preferably used in an amount from 0.1 to 20 mg / m² used in the color photographic material.

The preparation of the development activators of the formula I is described in EP-A-674 215 described.

For the purposes of the present invention, synthetic polymers are preferably synthetic high molecular compounds from the group of Polymerization products, polycondensation products and polyadditions products understood.

Polymerization products are preferably ethylenically unpolished polymers saturated low molecular weight compounds and polymers from low molecular weight Compounds that have a ring structure.  

Examples of ethyleneically unsaturated compounds are ethylene, butadiene, Isoprene, vinyl aromatics such as styrene, α-methylstyrene, divinylbenzene, chlorine methylstyrene, vinyltoluene, (meth) acrylic acid derivatives such as optionally substi tuated (meth) acrylic acid derivatives such as optionally substituted (meth) acrylic acid esters, (meth) acrylic acid amides, (meth) acrylic acid, vinyl esters, vinyl amides, Vinyl ethers, vinyl heterocycles and the like. a. Vinyl pyridine, vinyl imidazole, vinyl sulfones, Vinylsulfonamides, vinyl ketones, maleic acid derivatives, fumaric acid derivatives, itacon acid derivatives, (meth) allyl compounds, vinyl thioethers, vinylsilanes, vinyl chloride, Vinylidene chloride, (meth) acrylonitrile.

Examples of the classes of compounds mentioned are in the Research Disclosure 19 551 (1980) and Yocum, Nyquist "Functional Monomers", 2 vols., Dekker 1973, listed.

Low molecular weight compounds that have a ring structure are e.g. B. Ethylene oxide, propylene oxide, butylene oxide, aziridines, tetrahydrofuran, caprolactam, Epichlorohydrin.

Polycondensation products and polyaddition products are e.g. B. polyester, poly amides, polycarbonates, polysulfones, polyurethanes, polysiloxanes, polyureas, Phenol-formaldehyde resins, polyimides, polyphenylene oxide, epoxy resins, urea Formaldehyde resins. Examples of the compounds are described in Ullmanns Encyclopedia of technical chemistry, 4th ed. Vol. 19, Verlag Chemie, Weinheim 1980.

Particularly preferred synthetic polymers are those from the German patent Publication 15 22 387 known nonionic polyurethanes, which from the German Patent 15 22 393 known anionic polyurethanes, one for salt education-capable phosphonic acid, phosphoric acid ester or phosphoric acid amide Contain group and those known from German Patent 14 72 746 anionic polyurethanes.

Polymers are preferably used which are in dispersion form, i. H. have a particulate character. The mean particle size lies here in the range of 20-2000 nm, preferably in the range of 20-500 nm.  

Polymer dispersions with a core / shell structure as described in DE-A-35 16 466 are suitable.

Polymers are also preferred whose glass transition temperature T _{g is} below + 25 ° C.

Polymer dispersions which are nonionic or a are also preferred have anionic charge.

Furthermore, polymers are preferred which have a certain solvency for the show used color coupler. A solubility of color coupler in the polymer is when a polymer / coupler mixture is made by evaporating one Solution of polymer and coupler, in a differential thermal analysis Measurement has no melting enthalpy of the coupler. Polymers that more than 5% color coupler can be preferred are preferred.

The polymers are used in such a way that they restrict diffusion of the allow dye resulting from the color coupler in the color coupling.

Latices that can be loaded are preferably suitable. In particular, the in Polymers described in DE-A-30 36 846, DE-A-15 22 387, DE-A-14 72 746 suitable. Preferred examples of polymers are L1 to L180 from Research Disclosure 19 551, polymer I to polymer V from DE-A-30 36 846, polyester p. 6 Line 33 - p. 7 Line 22 of EP-A-0 069 671.

Particularly preferred polymers are given below. Some of them are loaded with couplers.

Polymer PI:
Polymer II from DE-A-30 36 846 or US-A-4 388 403.
Polymer P-2:
Polymer IV of DE-A-30 36 846.
Polymer P-3:
Polymer V of DE-A-30 36 846.
Polymer P-4:
Compound 4 of DE-PS 14 72 746.
Polymer P-5:
Compound 2 of DE-PS 14 72 746.
Polymer P-6:
Compound 5 of DE-PS 14 72 746.
Polymer P-7:

Polymer P-8:

Polymer P-9:

Polymer P-10:

Polymer P-11:

Polymer P-12:

Polymer P-13:

Polymer P-14:

Polymer P-15:

Polymer P-16:

Polymer P-17:

Polymer P-18:

Polymer P-19:

Polymer P-20:

Polymer P-21:

The polymers are defined as follows by the average molecular weight w (average weight) and the average particle size. The glass transition temperature T _g for compounds P-1 to P-21 is below + 25 ° C.

The proportion of the layer of synthetic polymer is preferably at least 35 vol .-%, a proportion of 35 to 50 vol .-% is particularly preferred.

In the material according to the invention, all green-sensitive silver are preferably halide emulsion layers arranged closer to the support than all blue sensitive union silver halide emulsion layers and all red-sensitive silver halogens nidemulsion layers arranged closer to the carrier than all green sensitive Silver halide emulsion layers. Between the blue and the green sensitivity Lich silver halide emulsion layers is usually one Yellow filter layer. This can be an effective ingredient in colloidal silver or contain a yellow dye that must be decolourable or washable. Such dyes are known in the literature, e.g. B. from US-A-4,923,788, Research Disclosure 17643 (1978) and Research Disclosure 37038 (1995).

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 sil over color bleaching process.

The photographic materials consist of a support on which at least one photosensitive silver halide emulsion layer is applied. As a carrier thin films and foils are particularly suitable. An overview of carriers materials and auxiliary layers applied to their front and back are in Research Disclosure 37254, Part 1 (1995), p. 285.  

The material according to the invention preferably has a transparent support.

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

Depending on the type of photographic material, these layers can be arranged differently. This is shown for the most important products:
Color photographic films such as color negative films and color reversal films have 2 or 3 red-sensitive, cyan-coupling silver halide emulsion layers, 2 or 3 green-sensitive, purple-coupling silver halide emulsion layers and 2 or 3 blue-sensitive, yellow-coupling silver halide emulsion layers on the support in the order given below. The layers of the same spectral sensitivity differ in their photographic sensitivity, the less sensitive sub-layers generally being closer to the support than the more sensitive sub-layers.

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

Color photographic paper, which is usually much less sensitive to light as a color photographic film, points in the order given below usually a blue-sensitive, yellow-coupling silver halo on the carrier genide emulsion layer, a green-sensitive, purple-coupling silver halide emulsion layer and a red-sensitive, cyan-coupling silver halide emulsion layer, the yellow filter layer can be omitted.

Deviations in the number and arrangement of the photosensitive layers can occur to achieve certain results. For example, you can all highly sensitive layers in one layer package and all low sensitivity layers to another layer package in a photographic film be summarized to increase the sensitivity (DE 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.

Information about suitable silver halide emulsions, their preparation, maturation, Stabilization and spectral sensitization including suitable spectrals sensitizers can be found in Research Disclosure 37254, Part 3 (1995), pp. 286 and in Research Disclosure 37038, Part XV (1995), p. 89.

Photographic materials with camera sensitivity usually contain Sil berbromide iodide emulsions, which may also contain small amounts of silver chloride can contain. Photographic copying materials contain either silver chloride bromide emulsions 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, Part 4 (1995), p. 288 and in Research Disclosure 37038, Part II (1995), p. 80. The maximum absorption of that from the couplers and the color developer oxidation Product-formed dyes are preferably in the following areas: Yellow coupler 430 to 460 nm, purple coupler 540 to 560 nm, cyan coupler 630 up to 700 nm.

In color photography films, to improve sensitivity, Graininess, sharpness and color separation are often used in compounds Reaction with the developer oxidation product release compounds, the photo are graphically effective, e.g. B. DIR couplers that have a development inhibitor columns.

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

Mostly hydrophobic color couplers, but also other hydrophobic components of the layers, are usually in high-boiling organic solvents dissolved or dispersed. These solutions or dispersions are then in one emulsified aqueous binder solution (usually gelatin solution) and lie after drying the layers as fine droplets (0.05 to 0.8 µm through knife) in the layers.  

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

The usually between layers of different spectral sensitivity arranged non-light-sensitive intermediate layers can contain agents which an undesirable diffusion of developer oxidation products from a photosensitive to another photosensitive layer with different prevent spectral sensitization.

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

The photographic material can also contain UV light-absorbing compounds, whiteners, spacers, filter dyes, formalin scavengers, light stabilizers, antioxidants, D _min dyes, additives to improve the stability of dyes, couplers and whites as well as to reduce the color fog, plasticizers (latices), Contain biocides and others.

Suitable compounds can be found in Research Disclosure 37254, Part 8 (1995), P. 292 and in Research Disclosure 37038, parts IV, V, VI, VII, X, XI and XII (1995), p. 84 ff.

The layers of color photographic materials are typically hardened, i.e. H., the binder used, preferably gelatin, is by suitable cross-linked chemical processes.

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

After imagewise exposure, color photographic materials become their character ter processed according to different processes. Details of the Procedures 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. Published together with exemplary materials.

example 1

A color photographic recording material for color negative color development was produced (layer structure 1A) by placing on a transparent layer support the following layers of cellulose triacetate in the order given were applied. The quantities given relate to 1 m². For the Silver halide application, the corresponding amounts of AgNO₃ are given; the Silver halides with 0.5 g of 4-hydroxy-6-methyl-1,3,3a, 7-tetraazainden pro Mol AgNO₃ stabilized.

1st layer (antihalo layer)

0.3 g black colloidal silver
1.2 g gelatin
0.4 g UV absorber UV-1
0.02 g tricresyl phosphate (CPM)

2nd layer (intermediate layer)

0.25 g AgNO₃ a Mikrat-Ag (Br, I) emulsion, average grain diameter 0.07 µm, 0.5 mol% iodide
1.0 g gelatin

3rd layer (low red sensitive layer)

2.7 g of AgNO₃ a spectrally red-sensitized Ag (Br, I) emulsion with 4 mol% iodide, average grain diameter 0.5 µm
2.0 g gelatin
0.88 g of colorless coupler C-1
0.02 g DIR coupler D-1
0.05 g colored RC-1 coupler
0.07 g colored coupler YC-1
0.75 g CPM

4th layer (highly red-sensitive layer)

2.2 g of AgNO₃ a spectrally red-sensitized Ag (Br, I) emulsion, 12 mol% iodide, average grain diameter 1.0 µm
1.8 g gelatin
0.19 g of colorless coupler C-2
0.17 g CPM

5th layer (intermediate layer)

0.4 g gelatin
0.15 g white coupler W-1
0.06 g of aluminum salt of aurintricarboxylic acid

6th layer (low green sensitive layer)

1.9 g AgNO₃ a spectrally green-sensitized Ag (Br, I) emulsion, 4 mol% iodide, average grain diameter 0.35 µm
1.8 g gelatin
0.54 g of colorless coupler M-1
0.24 g DIR coupler D-1
0.065 g colored coupler YM-1
0.6 g CPM

7th layer (highly green-sensitive layer)

1.25 g of AgNO₃ a spectrally green-sensitized Ag (Br, I) emulsion, 9 mol% iodide, average grain diameter 0.8 µm
1.1 g gelatin
0.195 g of colorless coupler M-2
0.05 g colored coupler YM-2
0.245 g CPM

8th layer (yellow filter layer)

0.09 g of yellow colloidal silver
0.25 g gelatin
0.08 g Scavanger SC-1
0.40 g formaldehyde scavenger FF-1
0.08 g CPM

9th layer (low blue-sensitive layer)

0.9 g of a spectrally blue-sensitized Ag (Br, I) emulsion, 6 mol% iodide, average grain diameter 0.6 µm
2.2 g gelatin
1.1 g of colorless coupler Y-1
0.037 g DIR coupler D-1
1.14 g CPM

10th layer (highly blue-sensitive layer)

50.6 g of AgNO₃ a spectrally blue-sensitized Ag (Br, I) emulsion, 10 mol% iodide, average grain diameter 1.2 µm
0.6 g gelatin
0.2 g colorless coupler Y-1
0.003 g DIR coupler D-1
0.22 g CPM

11th layer (UV absorber layer)

1 g gelatin
0.3 g UV absorber UV-2
0.3 g CPM

12th layer (protective and hardening layer)

0.25 g gelatin
0.75 g of curing agent of the formula

so that the total layer structure after curing has a swelling factor of 3.5 would have.

Substances used in example 1:

After exposing a gray wedge, the development according to "The British Jour nal of Photography ", 1974, pages 597 and 598.

In the layer structures 1B to 1F, a synthe was added to the fourth layer table polymer in an amount of 1.7 g / m² (approx. 40 vol .-%) and / or a Ent winding activator in an amount of 1.5 mg / m². The connections and the results are shown in Table 3.  

Table 3

As can be seen, the material according to the invention improves Sensitivity with almost unchanged veil.

Example 2

The layer structure 2 A corresponds to the layer structure I A from example 1. In the Layer structures 2 B to 2 D became an additional synthetic layer Polymer in an amount of 0.75 g / m² (approx. 41 vol.%) And / or in the 11th Layer given a development activator in an amount of 2 mg / m². The Compounds and the results are shown in Table 4.  

Table 4

As can be seen, the material according to the invention improves Sensitivity without an increase in fog.

Claims (6)

1. Color photographic recording material with at least two blue-sensitive, yellow-coupling silver halide emulsion layers of different photographic sensitivity, at least two green-sensitive, purple-coupling silver halide emulsion layers of different photographic sensitivity and at least two red-sensitive, blue-green coupling silver halide emulsion layers of different photographic sensitivity, characterized in that it is present in at least one highly sensitive silver layer an adjacent non-photosensitive layer contains a development activator of the formula IR [O-CH₂-CH₂-S- (LINK¹-S) _x -CH₂-CH₂-O- (LINK²)] _y -OR (I), where
LINK¹, LINK² a two-value link,
RH, an optionally substituted alkyl radical, an optionally substituted aryl radical or acyl radical,
x 0, 1 or 2 and
y is 1 to 20,
and at least 20% by volume of the highly sensitive silver halide emulsion layer is made of a synthetic polymer. 2. Color photographic recording material according to claim 1, characterized in that the development activator of formula I of formula II HO - (- CH₂-CH₂-S-CH₂-CH₂-OZO-) _y -H (II), wherein
Z is a divalent link and
y is 1 to 20,
corresponds. 3. Color photographic recording material according to claim 1, characterized in that the development activator of formula I of formula III HO - (- CH₂-CH₂-S-CH₂-CH₂-S-CH₂-CH₂-OZO-) _y -H (III), in which
Z is a divalent link and
y is 1 to 20,
corresponds. 4. Color photographic recording material according to one of claims 2 or 3, characterized in that the divalent link Z -CH₂-CH₂-, -CH₂-CH₂-O-CH₂-CH₂-, - (CH₂-CH₂-O) _y -CH₂- CH₂-,
-CH₂-CH₂-C (CH₃) ₂-CH₂-CH₂-, -CH₂-CH₂-NH-CO-NH-CH₂-CH₂-,
-CH₂-C (R¹) (R²) -CH₂-, -CH₂-CH₂-N (COR³) -CH₂-CH₂-,
-CH₂-CH₂-NR⁴-CH₂-CH₂-, -CH₂-phen-CH₂- or
-CH₂-CH₂-NH-CO-CO-NH-CH₂-CH₂-, where
R¹, R², R³, R⁴ H, an optionally substituted alkyl radical or an optionally substituted aryl radical and
Phen -C₆H₄- mean. 5. Color photographic recording material according to claim 1, characterized characterized in that the development activator of formula I in a Quantity of 0.1 to 20 mg / m² used in the color photographic material becomes.   6. Color photographic recording material according to claim 1, characterized characterized in that the layer consists of at least 35% by volume synthetic polymer.