DD285206A5 - COLOR PHOTOGRAPHIC SILVER HALOGENIDE MATERIAL WITH DIVIDED INTERMEDIATE LAYERS - Google Patents

Abstract

The present invention relates to a silver halide photographic material having at least one silver halide emulsion layer sensitive to red, green and blue light, and intermediate layers thereof free of silver halide or containing substantially non-photosensitive silver halide. At least one of the intermediate layers disposed directly between the silver halide emulsion layers of different spectral sensitization is divided into two or more intermediate layers. Each intermediate layer directly adjacent to the color separation layer contains a coupler which gives substantially the same color or the color necessary to compensate for the minor color density which the color coupler provides in the color separation layer after the reaction with developer oxidation product diffused from the color separation layer. As coloring couplers in the divided intermediate layers, color couplers, mask couplers; DIR couplers, DAR couplers and timing DIR couplers used. The incorporation of the split interlayers to control and complete the color image build-up results in improved color yield, silver saving, and image quality. divided intermediate layers; Color couplers; Masking couplers; DIR couplers; DAR couplers; TIMING-DIR couplers; compact layers; high scales; high sensitivity; improved color separation}

Description

Field of application of the invention

The invention relates to a silver halide color photographic material containing interlayers.

Characteristic of the known state of the art

It is a common practice to include interlayers between silver halide emulsion layers of different spectral sensitization. These intermediate layers are intended to suppress the diffusion of developer oxidation product from one color separation layer to the other in order to avoid color distortions. Conveniently, such intermediate layers are provided with scavengers for developer oxidation product to enhance the release effect. Known scavengers for developer oxidation product belong to the category of colorless couplers and alkylhydroquinones.

The end products of the reaction are substantially uncolored compounds which are not available for image formation. The excess developer oxidation product, which passes through diffusion from the color separation layers in the intermediate layers, must be made harmless to achieve sufficient color purity. On the other hand, in order to improve sensitivity and graininess, between layer pairs of the same spectral sensitization but with different general sensitivity, it is known to include so-called color compensation layers which may contain color couplers, mask couplers and timing-type DIR couplers (eg DE-OS 3209995 and 3209996) ).

These intermediate layers are also formed as double layers (dual-dye compensating layers).

Such layer arrangements lead to excellent results for the respective color separation unit, but between the color separation layers of different spectral sensitization, the excess developer oxidation product must be destroyed by interlayer measures.

A partial separation of the composite layers in color coupler-containing layers and in silver halide-containing layers is described in EP-PS 62202.

At least one photosensitive silver halide-containing layer, which is relatively thin and has a high packing density, is located between color coupler-containing layers which either do not contain silver halide or which contain silver halide which is relatively light-insensitive. Due to the compact design, the sharpness of the color separation unit can be improved.

Effective suppression of the diffusion of color developer oxidation product into the adjacent color separation layer with other spectral sensitization must continue to be provided by appropriate interlayer measures.

The known prior art measures for achieving a satisfactory color purity of the silver halide color photographic materials are thus based on the fact that the developer oxidation product passing through diffusion from one color separation layer into another sensitized color separation layer is destroyed by suitable intermediate layers with scavengers for the developer oxidation product and thus for the color image structure or Control of the color image construction is not available.

Object of the invention

The object of this invention is to provide color photographic silver halide materials having excellent photographic properties and good color reproduction with optimum silver use.

Explanation of the essence of the invention

The object of the invention is to provide, with the inclusion of color-forming compounds interlinked with developer oxidation product in intermediate layers, color photographic silver halide materials which are distinguished by a high color yield and image quality.

According to the invention, the object is achieved by dividing at least one of the interlayers located directly between the silver halide emulsion layers of different spectral sensitization and each containing a coupler which gives substantially the same color or the color necessary to compensate for the secondary color density which, after substantially reaction with the developer oxidation product Color coupler in the immediately adjacent silver halide emulsion layer.

As color couplers in the divided intermediate layers, color couplers, mask couplers, DIR couplers, DAR couplers and timing DIR couplers are used. The divided interlayers are either free of silver halide or they may contain substantially non-photosensitive silver halide.

The choice of the coloring coupler in,., Ι divided intermediate layers is suitably adapted to the kinetics of the color coupler in the immediately adjacent color separation layers. It is always advantageous if the color couplers couple in the intermediate layers at least as fast as the color couplers in the immediately adjacent color separation layers.

The invention is applicable in principle to all color photographic materials which operate on the principle of chromogenic coloring. The concrete specification depends on the amount of the developer oxidation product diffusing into the intermediate layer.

This excess developer oxidation product can be usefully used to save silver and additional control ds image structure or image composition itself.

The increase of the thickness of the material by the additional interlayer division can be advantageously compensated for by reducing the thickness of the color separation layers by removing couplers from the respective color separation layers. There is a relatively large supply of diffusing developer oxidation product

z. As in Colorncgativaufnahmematerialien, since it is assumed to achieve high recording sensitivities of an over-equimolar silver supply in relation to the color coupler and by introducing the reactive color coupler, it is possible to completely decouple the layer arrangements of different spectral ranges.

The invention is not limited by the use of necessary photochemical additives in the material, such as gelatin substitutes, curing, wetting and dispersing agents, chemical and spectral sensitizers, stabilizers and clearing agents, antioxidants, UV absorbers, pH and viscosity control compounds, etc.

In addition, the composition of the silver halide, its crystal structure and habit, the film base used, the composition of the binder and the use of other auxiliaries needed to prepare photographic silver halide multilayer materials have no influence on the silver halide color photographic material of the present invention.

The compounds used for the examples in addition to the usual casting additives are listed below:

Purple mask coupler K 1: CH 2 -O- / Vn = N-CH C-NHCO-

^{3 K}} J 6

NH

UV absorber UV 1:

^c 4 ^H g (O

UV absorber UV 2:

C ₂ H ₅ '

Blue-green mask coupler K 2:

OH

-CONH- (CH ₂ J ₄ -O-

Cyan coupler l <3: OH

WCONH- (CH ₂ J ₄ -O-

Teal DIR coupler K 4: OH

ώ '(3

Purple coupler K 5: C-NH-CO- "

Il V = ^

NH-CO-CH ₂ -O- / ^

(T)

Cl

Purple DIR coupler 6

-ti.

N_N

^ C-S-CH / I

C ₅ H _1JL (t)

NH-CO-CHrO- ff VC ₁ -H ₁ 1 ( ^t )

DIR coupler K 7:

NHCOCH,

Blue-green coupler K 8: OH

Cl - ^ * ">, - NHCOCH-O-

C ₂ H ₅

Cl

Teal DAR coupler l <9:

OH / ^C 5 ^H ll ^(t)

(T)

0-CH ₂ -CO-NH- ^ ^ NH-NH-C

Yellow color coupler K 10:

/ I V-NH-CO-CH ₂ -O-

ί ^ -NH-CO-CH ₂ -COCH ₂ ,

Timing DIR couplers

The incorporation of the couplers into the layers is carried out in the customary manner in the form of individual dispersants, solutions, latex loadings or in the form of mixed dispersions with individual couplers or coupler mixtures.

Yellow color coupler K 11:

NH-CO- (CH ₂ J ₃ -O-

CH ₃ -C-CO-CH-CO-NH- *

Cl

COOH

DIR coupler K 12:

κ- \

-?

OH

C \ CH

NHCO-C-CH,

CH-

Yellow DAR coupler K 13: CH,

Cl

CH _x -C-CO-CH-NH- (/ \

I I KJ

CH-

5 ^H ll ^(t) NH-C0- (CH ₂ ) ₃ -O- y C ₅

CO- NH- V V NH-NH-C

Sensitizing Dye I

^2H 5

(F> ^ - CH = C-CH = J

U \

-CH-

C ₂ H ₅

Sensitizing Dye II:

! N

^C 2 ^H 5

? 2 ^Η 5

>. -CH = CH-

CH =

CN

C ₂ H ₅

SO-

Sensitizing dye III

C ₂ H ₅

11 · J-CH = C-CH = I Jl

O ₃ H

Sensitizing dye IV:

Compound H 1:

(MH ₁₇ C ₈ -

OH hardening agent HM 1:

CH ₂ = CH-SO ₂ -CH ₂ -CH ₂ -SO ₂ -CH = Ch ₂

embodiments

example 1

Layer structure I

On an auxiliary layered celulosetriacetate film base, the following layers of the composition shown are applied to a high sensitivity color negative recording material. Based on the composition of the photosensitive layers, the information for the couplers and the spectral sensitizing dyes is in moles per mole of silver. All other components are shown in g / m ² . The ingredients in the less light-sensitive layers as well

in the intermediate layers are given in g / m ² .

First layer: antihalation layer

blue, colloidal silver 0.28

Gelatin 0.9

Purple mask coupler K1 0,06

UV absorber UV-1 0.3

UV absorber UV-2 0.2

Second layer: intermediate layer Z1

fine-grained silver bromide iodide 0.17

(average particle size 0.07 μ, 2.5 mol% silver iodide)

Gelatin 1.0

Blue-green mask coupler K2 0.02

Third layer: low-sensitivity red-sensitive silver halide emulsion layer

Silver bromide iodide emulsion (silver iodide: 4 mol%, 1.6

average particle size: O ^)

Gelatin 0.7

Sensitizing dye ι Blue-green mask coupler K i Blue-green coupler K3 Blue-green DIR-Kupuler K

Fourth layer: intermediate layer Z 2

Gelatin compound H

fifth layer: low-sensitivity green-sensitive silver halide emulsion layer silver bromide iodide: "mulsion (silver iodide: 4 mol%, average particle size: 0.4 μ)

Gelatine Purple Mask Coupler K1 Purple coupler K Purple DIR coupler K8 DIR coupler K7 Sensitizing dye II Sensitizing dye III

Sixth) Layer: Interlayer 7! 3

Gelatin compound H1

Seventh layer: Highly sensitive red-sensitive silver halide emulsion layer Silher bromide iodide emulsion silver iodide: 8 mol%, average particle size: 1.2 μ)

Gelatin Sensitizing dye I Blue-green mask coupler K Blue-green coupler K8 Blue-green DAR coupler K DIR coupler K7

Eighth layer: intermediate layer Z4

fine-grained silver chlorobromide (average particle size: 0.32 μ, 20 mol% silver bromide)

gelatin

Ninth layer: Highly sensitive green-sensitive silver halide emulsion layer Silver bromide iodide emulsion (silver iodide: 8 mol%, average particle size: 1.2 μ)

Gelatin Sensitizing dye II Sensitizing dye III magenta coupler K1 magenta coupler K DIR coupler K7

Tenth layer: intermediate layer Z 5

Gelatine compound H1 Eleventh layer: Yellow filter layer yellow, colloidal SiiW compound H1 gelatin

Twelfth layer: intermediate layer Z 6

Gelatin compound H1

Thirteenth layer: low-sensitivity blue-sensitive silver halide emulsion layer Silver bromide iodide emulsion (silver iodide: 4 mol%, average particle size: 0.6 μ)

Gelatin Sensitizing Dye IV Yellow Color Coupler K10 Yellow Color Coupler KH DIR Coupler K12

Fourteenth layer: intermediate layer Z 7

fine-grained silver bromide iodide (average particle size 0.15 μ, 2.5 mol% silver iodide)

gelatin

Fifteenth layer: Highly sensitive blue-sensitive silver halide emulsion layer Silver bromide iodide emulsion (silver iodide: 8 mol%, average particle size: 1.2 μ)

Gelatin Sensitizing Dye I 'Yellow Color Coupler K10 Yellow Color Coupler KH Yellow DAR Coupler K13 DIR Coupler K12

Sixteenth layer: intermediate layer Z8

Gelatine UV absorber UV-1 UV absorber UV-2

7-10 " ⁴ 0.010 0.20 0.015

1.0 0.03

1.5 1.0 0.02 0.30 0.003 0.006 2-10 " ⁴ 1.5-10 *

1.0 0.03

1.4 1.0 7 ΊΟ- ¹ 0.004 0.04 0.004 0.003

0.5 1.0

2-10 1.4 1.0 ^"4 1.5 x 10 ~ ⁴ 0.006 0.08 0.006

1.0 0.08

0.18 0.1 1.1

1.0 0.08

1.3 1.0 6 · 10 " ⁴ 0.3 0.12 0.006

0.25 1.0

1.0 1.0 6-10- ⁴ 0.06 0.02 0.006 0.006

0.8 0.3 0.2

Seventeenth layer: intermediate layer Z ü

fine-grained silver bromide iodide (average particle size: 0.07 μ, 2.5 mol% silver iodide)

Gelatine Γ, 7

Polymethyl methacrylate particles (average particle size: 1.5 μ) 0.2

Eighteenth layer: Cure coating layer

Hardener: HM 1 0.38

This color negative material is referred to as material A and indicates the state of the art (comparison). An inventive color negative recording material B has the analog layer structure as the comparison material A. In contrast, however, the fourth layer (intermediate layer Z 2) was formed as a double layer and in the half-layer 4 A, immediately adjacent to the third layer (low-sensitivity red-sensitive silver halide emulsion layer) and in the half-layer 4B immediately adjacent to the fifth layer (low-sensitivity green-sensitive silver halide emulsion layer) is divided.

In addition, the proportion of cyan coupler K3 in the third layer was reduced to 0.17 mol per mol of silver, and in the fifth layer, the proportion of magenta coupler K5 was reduced to 0.26 mol per mol of silver. The interlayer layers 4A and 4B have the following composition

Interlayer interlayer 4 A

Gelatin 0.5

Blue-green coupler K 5 0.8

Interlayer interlayer 4B

Gelatin 0.5

Purple coupler K 5 0.1

Another inventive color negative recording material C has the analogous structure as the material B. In contrast, the eighth layer (intermediate layer Z4) was formed as a double layer and in the half-layer 8 A immediately adjacent to the seventh layer (high-sensitivity red-sensitive silver halide emulsion layer) and in the Half-layer 8 B immediately adjacent to the ninth layer (high-sensitivity green-sensitive silver halide emulsion layer) is divided. In addition, the cyan mask coupler K2 in the seventh layer and the DIR coupler K7 in the ninth layer were omitted. The half-layers 8A and 8B have the following composition:

Half-layer interlayer 8 A

fine-grained silver chloride bromide 0.25

(average particle size: 0.32 μ, 20 mol% silver bromide)

Blue-green mask coupler K 2 0.03

Gelatin 0.5

Interlayer interlayer 8B

fine-grained silver halide bromide (average particle size 0.32 μ, 20 mol% silver bromide)

Timing DIR coupler 0.03

Gelatin 0.5

Exposure of sensitometric strips made of materials A, B and C was carried out with ISO daylight behind a silver grayscale wedge (factor 2) with exposure modulation 0.3 log units from step to step. The exposed materials were processed at 38 ^° C. according to the following procedure:

Color development 3min15sec

Bleaching 6min30sec

Watering 3min15sec

Fix 6min30sec

Watering 3min15sec

Stabilize 3min15sec

dry

Color developer:

Hydroxylamine sulfate 2.0 g

Sodium sulfite 4.0g

Potassium bromide 1,8g

4-amino-3-methyl-N-ethyl-N- (2-hydroxyethyl) -aniline-sulfate

Potassium carbonate 37.5g

KOH 1.0 g

Fill with water pH = 10,0010.05

Bleaching Solution

Ammonium bromide 160g

Ethylenediaminetetraacetic acid 120 g

NaFe salt (EDTA, NaFe salt)

Ethylenediaminetetraacetic acid di-Na-salt (EDTA, disodium salt)

Ammonium hydroxide solution (28%) 25 ml

Acetic acid 15 ml

Fill with water to 1 pH = 6.00 ± 0.2

fixing solution:

Ammonium thiosulfate solution (60%) 250ml

Sodium sulfite 4.0 g

Sodium bisulfite 4.6 g

Ethylenediaminetetraacetic acid di-Na salt 1.6g

Fill with water to 1 pH = 6.5 ± 0.2

Stabilizing Solution

Formaldehyde solution (37%) with water to make up to 11 ml

The processed sensitometer tires were measured on the Macbeth densitometer behind Status M filters with red and blue light. The results of the photographic evaluation are shown in the table.

table

Gradation E ,,,. D _min D _max KS RMS

Material [g] [%] [%] [%] [% ]

100 100

103 98

105 98 97

Granularity is the inhomogeneity of the density of a uniformly exposed, processed photographic material. It is given as the 100 times the standard deviation S of the optical density D as so-called RMS granularity. Small RMS values characterize fine grained emulsion layers. In the table, the acutance 'KS characterizes the halation of photosensitive photographic color negative recording materials when a defined exposure is made over the entire spectral sensitization range. It is the hundredfold decadic logarithm of the ratio of two different exposures. A larger number means better contour sharpness.

It can be seen from the data that the materials B and C according to the invention are distinguished from the comparison material A by improved sensitivity, maximum density, graininess and contour sharpness.

A upper- 0.69 100 0.85 100 (Comparison) Mittelguß 0.67 100 0.65 100 bottom pouring 0.66 100 0.35 100 B upper- 0.68 100 0.82 100 (Invention) Mittelguß 0.66 105 0.63 105 bottom pouring 0.62 105 0.33 105 C upper- 0.68 100 0.80 100 (Invention) Mittelguß 0.65 105 0.62 108 Untorguß 0.64 105 0.31 105

Claims (3)

Claims 1. A silver halide color photographic material having at least one red, green and blue light sensitive silver halide emulsion layer and associated intermediate layers free of silver halide or substantially non-photosensitive silver halide disposed on a support, characterized in that at least one of those directly different between the silver halide emulsion layers spectral sensitization disposed interlayer and each containing a coupler, which results in substantially the same color after the reaction with the developer oxidation product or the required color for compensating the secondary color density, which provides the color coupler in the immediately adjacent silver halide emulsion layer. 2. Color photographic silver halide according to claim 1, characterized in that as couplers in the divided intermediate layers color couplers, mask couplers, DIR couplers, DAR couplers and timing DIR couplers are included. The silver halide color photographic material as claimed in claims 1 and 2, characterized in that said divided intermediate layers are free of silver halide or substantially non-photosensitive silver halide.