EP0997775B1 - Photographic colour silver halide material - Google Patents

Description

The invention relates to a negative developing color photographic silver halide material, whose silver halide emulsions consist of at least 95 mol% of AgCl and that with scanning exposure due to high color density and Analog exposure is characterized by contrast independent of the exposure time.

Photo paper is used for the output of "digital prints" on scanning photo imagesetters used in which the exposure unit pixel-by-pixel the image information, line by line with bundled light of high intensity (typically from gas or Diode lasers or comparable devices) and very short exposure times per pixel (in the range of nano to microseconds) on the photo material. In particular at high densities, the problem of line washing occurs. This is expressed visually by a blurred image of edges (e.g. Lettering) in the motif and is clearly illustrated by "overexposure", "bleeding", "Hem formation", "smearing", "blurring" etc. described. This limits the exploitable density range of the photo paper. Photo materials for the issue of "Digital prints" with high image quality on scanning photo imagesetters with LEDs or lasers are therefore only allowed to have a slight line washout with high color density (blackening) exhibit.

Method of measuring line washout

1. ein Linienraster mit Rasterlinien und Zwischenräumen der jeweiligen Breite b₀ [mm], der im folgenden als "Rasterstufenkeil" bezeichnet wird, sowie

2. homogen ausgefüllte Flächen ("Vollstufenkeil").

In the following, a measurement method is specified which allows the measurement of the line washout for reflective photo material (photo paper). This is based on the description of a measurement for the analog problem with a transparent photographic material (see H. Frieser, Photographische Informationsaufammlung, R. Oldenbourg Verlag, Munich (1975), p. 266ff). The determination of the washout is attributed to a macro-densitometric measurement. For this purpose, two motifs are exposed next to each other with the same step-like intensity curve (RGB values) for the exposed structures:

1. a line grid with grid lines and spaces of the respective width b ₀ [mm], which is referred to below as "grid step wedge", and

2. homogeneously filled areas ("full step wedge").

The status A densities D _{F of} the steps are determined on the full step wedge after a defined RGB exposure. The densities D _{R of} a raster line pattern exposed with precisely these RGB values are determined on the raster step wedge. According to Frieser (see above), an effective (microscopic) line broadening 0 <Δb <b ₀ can be determined on the basis of such a macro-densitometric measurement on grid line fields. This is determined by the proportions of the reflected intensity, which for each raster level result from the raster lines themselves, ie T ₀ , and from the gaps, ie T ₁ (see Figure 1).

The density of a grid level is: D R = -log (T R ) = -log (½ {T 1 [1- Δb / b 0 ] + T 0 [1 + Δb / b 0 ]})

With ideal photo material without blurring, Δb = 0 and it follows: D * R = -log (½ {T 1 + T 0 }) Because of 10 ^-Dmin = T ₁ > T ₀ , the constant density 0.3 + D _{min would set} asymptotically even with medium grid line densities.

The difference from (1) and (2), the size D _R -D * _R , represents the density difference for each step due to line washout (see Figure 2).

For T _1. > T ₀ the effective line broadening can be derived from this Δb = b 0 (1-10 D * R -D R) evaluate for each level. By gradually plotting (3) against the density of the corresponding full field D _F , the usable maximum density D _f ^using a material can be determined directly (see Figure 3). The tolerable line spreads according to (3) were determined by visual assessment Δb = 0.10 mm for yellow (G), purple (P) and blue-green (B).

realization exposure

• Papier: festliegend auf der Innenseite eines Halbzylinders
• Strahlmodulation: 8 bit Akusto-Optischer Modulator (AOM)
• Strahlmischung von Blau, Grün und Rot nach der jeweiligen Strahlmodulation
• Strahlfokussierung durch Linsen
• x-Ablenkung (Linienweise "Fast-Scan"): rotierendes Spiegel-polygon mit 2000 rpm
• y-Ablenkung (Slow-Scan): Lineare Verschiebung des Spiegel-Polygons entlang der Zylinderachse
• Auflösung 1016 dpi, Belichtungszeit je Pixel: 400 +/- 100 ns
• linearer Punkt-Überlapp ca. 30 %
• Der Belichter wird im leistungslinearen Modus bezüglich RGB (RGB = Rot, Grün, Blau), d.h. ohne eine materialspezifische Gerätekalibrierung ("Linearisierung") betrieben. Die maximale Belichtungsleistung für die drei Farbkanäle wird im Hinblick auf die unterschiedlichen Materialempfindlichkeiten für Gelb, Purpur und Blaugrün so reduziert, daß einerseits die Maximaldichte des Materials erreicht werden kann und andererseits beim Belichten eines identischen RGB-Tripels (z.B. RGB = (100, 100, 100)) ein zumindest näherungsweise neutrales Motiv entsteht (Blau: 6,5 µW, Grün: 10,4 µW, Rot: 680 µW).

A conventional laser exposure unit (Cymbolic Science, Vancouver (Canada) model CSI Light Jet 2080) with the following specification according to the manufacturer's instructions is used for exposure: colour Laser system wavelength Maximum Performance Beam diameter (FWHM) blue Argon ion 458 nm 150 µW 25µm green Helium neon 543 nm 80 µW 25 µm red Helium neon 633 nm 2600 µW 25 µm

• Paper: fixed on the inside of a half cylinder
• Beam modulation: 8 bit acoustic-optical modulator (AOM)
• Beam mixing of blue, green and red after the respective beam modulation
• Beam focusing through lenses
• x-deflection (line-wise "Fast-Scan"): rotating mirror polygon with 2000 rpm
• y-deflection (slow scan): linear displacement of the mirror polygon along the cylinder axis
• Resolution 1016 dpi, exposure time per pixel: 400 +/- 100 ns
• linear point overlap approx. 30%
• The imagesetter is operated in linear performance mode with respect to RGB (RGB = red, green, blue), ie without material-specific device calibration ("linearization"). The maximum exposure power for the three color channels is reduced in view of the different material sensitivities for yellow, purple and cyan, so that on the one hand the maximum density of the material can be achieved and on the other hand when exposing an identical RGB triple (e.g. RGB = (100, 100, 100)) creates an at least approximately neutral motif (blue: 6.5 µW, green: 10.4 µW, red: 680 µW).

In accordance with the condition 0 <Δb <b ₀ , b ₀ = 0.25 mm was chosen for the raster line test image. This corresponds to a spatial frequency of 2 line pairs / mm. The lines of the grid are written in the fast-scan direction, so that the effective blurring in terms of device technology corresponds to the beam diameter. Due to the resolution of 1016 dpi (= spatial frequency 20 / mm) used, this can be neglected compared to the material's own wash.

The test motif consists of a 29-step grid wedge and a full-surface wedge. The motif is created using a conventional program (for example Photoshop®), exposed with the scanning photoexposer on a photo paper and then processed in an AgfaColor process 94. Level 1 receives no exposure intensity (RGB = 255) and therefore realizes D _min , level 29 (RGB = 9) receives the maximum exposure intensity. Each pixel line was exposed in one pass (neglecting the line overlap). Analogous to the sketched neutral test motif, color separations for the colors yellow, purple and teal as well as for neutral were exposed by constantly setting the complementary RGB channels to 255 (without exposure). The size of a step field is 20.0 x 6.35 mm.

Fig. 1: Strichbreite b₀ und effektive Linienverbreiterung Δb durch Verwaschung

Fig. 2: Auswertung des Dichtezuwachses aufgrund von Linienverwaschung; Darstellung der Dichten gegen Stufe des Prüfmotivs (links) bzw. gegen Dichte des entsprechenden Vollfeldes (rechts)

• gemessene Dichte D_F Vollfeld

▪ gemessene Dichte D_R des Rasterfelds mit Verwaschung

o theoretische Dichte D_R* des idealen Rasterfelds ohne Verwaschung

Dichtezuwachs D_R-D_R* aufgrund Linienverwaschung

Fig. 3 Ermittlung der nutzbaren Maximaldichte D_F ^nutz aus der Linienverbreiterung Δb am Beispiel der Gelbdichte.

The pictures show:

Fig. 1: Line width b ₀ and effective line broadening Δb by blurring

Fig. 2: Evaluation of the increase in density due to line washout; Representation of the densities against the level of the test motif (left) or against the density of the corresponding full field (right)

• measured density D _F full field

▪ measured density D _{R of} the grid with blurring

o The theoretical density D _R * of the ideal grid without blurring

Density increase D _R -D _R * due to line washout

Fig. 3 Determination of the usable maximum density D _F ^payload from the line broadening .DELTA.b the example of the yellow density.

State of the art and task

It is known from EP 774 689 that to achieve a higher color density in the pixel-wise exposure with focused high intensity light (typically off Gas, diode lasers, LED or comparable devices) and very short exposure times per pixel (typically in the nano to microsecond range) Gradation of the light-sensitive layers of the color negative paper used in the exposure time range should be as steep as possible.

A common method of dividing the gradation of the photosensitive layers in color negative papers is the increase in the amount of silver halide or color coupler in the photosensitive layers. Disadvantages of this method are: increased Material costs and deterioration in processing stability (fluctuation Sensitometry depending on the processing process and depending on the process fluctuation within operation), especially with color development times of less than 45 seconds the high contrast is not such a material for an analog exposure suitable.

From US 5,759,762 it is known that in the presence of a water-soluble disulfide, for example glutaramidophenyl disulfide, doping with complexes of the type (Me ₂ NH ₂ ) _n (AgCl _n ) in AgCl emulsion grains can improve the stability of the material under laser exposure.

It is also known from EP 350 046 and US 5 500 329 that the gradation in Exposure range of seconds or milliseconds by doping the silver halides with metal ions from Group VIII metals or transition metals Group II of the Periodic Table of the Elements. It was but found that with shorter exposure times a µsec to nano-sec range Gradation flattened despite the doping and the sensitivity becomes lower.

The object of the invention was to provide a material for both digital exposure, especially to provide laser exposure as well as for integral exposure, which is characterized by a high color density with laser exposure and one with integral exposure contrast independent of the exposure times.

Surprisingly, this object is achieved when the one described at the beginning color photographic material contains at least one silver halide emulsion layer, which has solarization with integral exposure.

Solarization means that the color density increases with increasing exposure intensity with constant exposure time or with longer exposure time with constant Exposure intensity decreases (T.H. James, The Theory of the Photographie Process, pages 182-184; Macmillan Publishing C. Inc., Forth Edition).

The invention therefore relates to a negative developing color photographic silver halide material, at least 95 mol% of its silver halides from AgCl exist, the at least one blue sensitive, containing at least one yellow coupler Silver halide emulsion layer, at least one green sensitive, at least a silver halide emulsion layer containing purple coupler and at least a red sensitive silver halide emulsion layer containing at least one cyan coupler contains, characterized in that at least one Has silver halide emulsion layer with integral exposure solarization.

In a preferred embodiment, the at least one silver halide emulsion layer contains the solarization has at least 0.1 mmol AgI per mol AgCl.

The silver halide emulsion of the silver halide emulsion layer having solarization preferably contains silver halide grains of at least two differently felled zones.

This silver halide emulsion is preferably obtained by pre-precipitation and subsequent Precipitation of a silver halide is produced, the precipitation in particular by redissolving a very fine-grained silver halide emulsion (micrate emulsion) on the pre-precipitation.

The pre-precipitation is preferably a homodisperse, cubic silver halide emulsion with at least 95 mol% AgCl and at most 4 mol% AgI. The micrate emulsion is preferably a homodisperse silver halide emulsion with at least 90 mol% AgCl and at most 8 mol% AgI (remainder is AgBr) and an average grain diameter (Diameter of the same volume ball) from 0.05 µm to 0.2 µm.

The finished silver halide emulsion is preferably homodisperse and cubic Silver halide grains with at least 95 mol% AgCl and an edge length the cube from 0.20 µm to 2 µm.

The molar ratio of the outer zone to the remaining silver of the grains is especially 1:24 to 6: 1.

At least one zone of said silver halide emulsion is preferred with at least one kind of ions or metal complexes of the metals of the groups VIII and IIB or the metals Re, Au, Pb or Tl doped.

When doping with more than one type of ion or metal complex from the Group VIII and IIB metals or the metals Re, Au, Pb or Tl can Ions or metal complexes in one zone or separately in several zones become.

Menge von Ir³⁺, Ir⁴⁺, Rh³⁺:

von 5 nmol/mol Ag bis 50 µmol/mol Ag, vorzugsweise von 10 nmol/mol Ag bis 500 nmol/mol Ag

Menge von Hg²⁺:

von 0,5 µmol/mol Ag bis 100 µmol/mol Ag, vorzugsweise von 1 µmol/mol Ag bis 30 µmol/mol Ag

Art der Zugabe von Ir³⁺, Ir⁴⁺, Rh³⁺ und Hg²⁺:

in NaCl-Einlauflösung

Preferred ions or metal complexes are: Ir ³⁺ , Ir ⁴⁺ , Rh ³⁺ and Hg ²⁺ .

Amount of Ir ³⁺ , Ir ⁴⁺ , Rh ³⁺ :

from 5 nmol / mol Ag to 50 µmol / mol Ag, preferably from 10 nmol / mol Ag to 500 nmol / mol Ag

Amount of Hg ²⁺ :

from 0.5 µmol / mol Ag to 100 µmol / mol Ag, preferably from 1 µmol / mol Ag to 30 µmol / mol Ag

Method of adding Ir ³⁺ , Ir ⁴⁺ , Rh ³⁺ and Hg ²⁺ :

in NaCl enema

An inner zone, in particular the core, is preferably doped with Hg ²⁺ and an outer zone, in particular the outermost zone, with Ir ³⁺ , Ir ⁴⁺ and / or Rh ³⁺ .

The preferred amount of AgI of the preferred embodiment is 0.01 to 20 mmol per mol AgCl, in particular 0.1 to 5 mmol AgI per mol AgCl.

The determination of the different doping of core and shell of a Silver halide emulsion, in which the halide composition of core and shell is the same or at least very similar. can be done as follows:

1. method

The silver halide grains are mixed with suitable silver halide solvents, e.g. a dilute aqueous thiosulfate solution, fractionally dissolved. In the Solutions is determined by means of ICP-MS type and amount of the doping metal, or the Doping metals determined.

2nd method

The direct methods without dissolving the silver halide grains are the Secondary Ion Mass Spectrometry (SIMS) and "Sputtered Neutral Mass Spectrometry" (SNMS) into consideration.

Combined methods are also conceivable.

The redissolution is carried out using NaCl solution or a bisthioether.

worin

R₁

einen Alkyl-, Alkenyl-, Cycloalkyl-, Aryl- oder Aralkylrest mit nicht mehr als 8 C-Atomen oder -C(R₆, R₇)-C(R₈, R₉)-(CH₂)_nNHCONHR₁₀,

R₂ bis R₉,

H oder Alkyl mit nicht mehr als 3 C-Atomen oder paarweise die Glieder eines Fünf- oder Sechsringes,

R₁₀

Wasserstoff oder einen Substituenten und

n

0 oder 1 bedeuten.

The bisthioethers correspond to the formula (I)

wherein

R ₁

an alkyl, alkenyl, cycloalkyl, aryl or aralkyl radical with not more than 8 carbon atoms or -C (R ₆ , R ₇ ) -C (R ₈ , R ₉ ) - (CH ₂ ) _n NHCONHR ₁₀ ,

R ₂ to R ₉ ,

H or alkyl with no more than 3 carbon atoms or in pairs the members of a five or six ring,

R ₁₀

Hydrogen or a substituent and

n

0 or 1 mean.

worin

R₁ bis R₉ und n

die vorstehend genannte Bedeutung besitzen und

R₁₁

H, eine Alkyl-, Alkenyl- oder Cycloalkylgruppe mit nicht mehr als 6 C-Atomen, eine Acyl-, Alkoxycarbonyl-, Carbamoyl- oder Sulfonylgruppe bedeutet.

Compounds of the formula (II) are preferred within the formula (I)

wherein

R ₁ to R ₉ and n

have the meaning given above and

R ₁₁

H, an alkyl, alkenyl or cycloalkyl group having no more than 6 carbon atoms, an acyl, alkoxycarbonyl, carbamoyl or sulfonyl group.

Suitable compounds of the formulas (I) or (II) are

I-21 C ₂ H ₅ -S-CH ₂ -CH ₂ -S-CH ₂ -CH ₂ -NHCO- (CH ₂ -) ₂ -COOH.

The color photographic material is preferably a copy material.

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

The color photographic copy materials indicate in the following Sequence on the carrier is usually a blue-sensitive, yellow-coupling one Silver halide emulsion layer, a green-sensitive, purple-coupling silver halide emulsion layer and a red sensitive, cyan-coupling silver halide emulsion layer on; the layers can be interchanged.

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 spectral sensitizers can be found in Research Disclosure 37254, Part 3 (1995), p. 286 and in Research Disclosure 37038, Part XV (1995), p. 89.

The precipitation can also take place in the presence of sensitizing dyes. Complexing agents and / or dyes can be used at any time render ineffective, e.g. by changing the pH or by an oxidative Treatment.

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. Die maximum absorption of that from the couplers and the color developer oxidation product Dyes formed are preferably in the following areas: yellow coupler 430 to 460 nm, magenta couplers 540 to 560 nm, cyan couplers 630 to 700 nm.

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 Binder solution (usually gelatin solution) emulsified and lie drying the layers as fine droplets (0.05 to 0.8 µm diameter) in before 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.

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

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, 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), 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 XIII (1995), P. 84 ff.

The layers of color photographic materials are usually hardened, i.e. that Binder used, preferably gelatin, is replaced by suitable chemical Process networked.

Immediate or rapid hardeners are preferably used, with instant or Fast hardeners are understood to be compounds that crosslink gelatin in such a way that immediately after casting, at the latest a few days after casting is far from complete that no further, due to the crosslinking reaction Change in the sensitometry and the swelling of the layer structure occurs. Under Swelling is the difference between wet film and dry film thickness at the understood aqueous processing of the material.

Suitable immediate and quick hardening substances can be found in Research Disclosure 37254, Part 9 (1995), p. 294 and in Research Disclosure 37038, Part XII (1995), Page 86.

After photographic exposure, color photographic materials become their character processed according to different processes. Procedural details 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. Together with exemplary materials. The color photographic material according to the invention is particularly suitable for a Short-term processing with development times from 10 to 30 seconds.

Halogen lamps or come in particular as the light sources for the exposure Laser imagesetter into consideration.

enthalten, worin

R₃₁, R₃₂, R₃₃ und R₃₄

unabhängig voneinander Wasserstoff, Alkyl, Aralkyl, Aryl, Aroxy, Alkylthio, Arylthio, Amino, Anilino, Acylamino, Cyano, Alkoxycarbonyl, Alkylcarbamoyl oder Alkylsulfamoyl, wobei diese Reste weiter substituiert sein können und wobei mindestens einer dieser Reste eine Ballastgruppe enthält, und

Y

einen von Wasserstoff verschiedenen, bei der chromogenen Kupplung abspaltbaren Rest (Fluchtgruppe) bedeuten.

R₃₁ und R₃₃

sind vorzugsweise tert.-Butyl; Y ist vorzugsweise Chlor.

Suitable purple couplers correspond to formulas III or IV

contain what

R ₃₁ , R ₃₂ , R ₃₃ and R ₃₄

independently of one another hydrogen, alkyl, aralkyl, aryl, aroxy, alkylthio, arylthio, amino, anilino, acylamino, cyano, alkoxycarbonyl, alkylcarbamoyl or alkylsulfamoyl, where these radicals can be further substituted and where at least one of these radicals contains a ballast group, and

Y

is a radical other than hydrogen which can be split off in the chromogenic coupling (escape group).

R ₃₁ and R ₃₃

are preferably tert-butyl; Y is preferably chlorine.

These couplers are due to the color brilliance of the purple dyes they produce particularly advantageous in itself.

sowie

Preferred couplers of the formula III are those of the following formula:

such as

sowie

Suitable couplers of the formula IV are couplers of the following formula:

such as

in welcher

R₅₁, R₅₂, R₅₃

unabhängig voneinander Alkyl bedeuten oder R₅₂ und R₅₃ gemeinsam einen drei- bis sechsgliedrigen Ring bilden;

R₅₄

Alkyl, Alkoxy oder Halogen,

R₅₅

Halogen, Alkyl, Alkoxy, Aryloxy, Alkoxycarbonyl, Alkylsulfonyl, Alkylcarbamoyl, Arylcarbamoyl, Alkylsulfamoyl, Arylsulfamoyl;

Z₁

-O-, -NR₅₆-;

Z₂

-NR₅₇- oder -C(R₅₈)R₅₉-;

R₅₆, R₅₇, R₅₈ und R₅₉

unabhängig voneinander Wasserstoff oder Alkyl bedeuten.

R₅₁, R₅₂ und R₅₃

sind vorzugsweise CH₃.

R₅₄

ist vorzugsweise Cl oder OCH₃.

R₅₅

ist vorzugsweise -COOR₆₀, -CONHR₆₀, -SO₂NHCOR₆₀, wobei R₆₀ C₁₀-C₁₈-Alkyl.

Suitable yellow couplers correspond to formula V

in which

R ₅₁ , R ₅₂ , R ₅₃

independently of one another are alkyl or R ₅₂ and R ₅₃ together form a three- to six-membered ring;

R ₅₄

Alkyl, alkoxy or halogen,

R ₅₅

Halogen, alkyl, alkoxy, aryloxy, alkoxycarbonyl, alkylsulfonyl, alkylcarbamoyl, arylcarbamoyl, alkylsulfamoyl, arylsulfamoyl;

Z ₁

-O-, -NR ₅₆ -;

Z ₂

-NR ₅₇ - or -C (R ₅₈ ) R ₅₉ -;

R ₅₆ , R ₅₇ , R ₅₈ and R ₅₉

are independently hydrogen or alkyl.

R ₅₁ , R ₅₂ and R ₅₃

are preferably CH ₃ .

R ₅₄

is preferably Cl or OCH ₃ .

R ₅₅

is preferably -COOR ₆₀ , -CONHR ₆₀ , -SO ₂ NHCOR ₆₀ , where R _{60 is} C ₁₀ -C ₁₈ alkyl.

Examples of yellow couplers of the formula (V) according to the invention are:

worin

R₆₁, R₆₂, R₆₃ und R₆₄

unabhängig voneinander Wasserstoff oder C₁-C₆-Alkyl bedeuten;

in der

R₇₁ und R₇₂

unabhängig voneinander für eine elektronenziehende Gruppe stehen,

X₇₁

für H oder eine bei der Reaktion mit Entwickleroxidationsprodukt abspaltbare Gruppe sieht,

Y₇₁

für eine Gruppe zur Vervollständigung eines stickstoffhaltigen Heterocyclus steht, mit der Maßgabe, daß eine durch R₇₂ dargestellte Gruppe an ein Kohlenstoffatom des Heterocyclus gebunden ist,

n

für 1 oder 2 steht;

in der

R₇₁, R₇₂ und X₇₁

die vorstehend genannte Bedeutung besitzen und

Z₇₁

für H oder einen Substituenten steht;

worin

R₈₁

Wasserstoff oder einen Substituenten,

X₈₁

ein Wasserstoffatom oder eine Abspaltgruppe und

Y₈₁

OR₈₂ oder

bedeuten, wobei

R₈₂

R₈₃

Alkyl,

R₈₄

Wasserstoff oder R₈₃,

R₈₅, R₈₆, R₈₈ und R₈₉

Wasserstoff oder einen Substituenten,

R₈₇

einen Substituenten und

Z₈₁

die restlichen nicht-metallischen Glieder eines 3- bis 8-gliedrigen Ringes bedeuten, wobei Z₈₁ weitersubstituiert sein kann.

R₆₁

ist bevorzugt CH₃ oder C₂H₅.

R₆₂

ist bevorzugt C₂-C₆-Alkyl,

R₆₃ und R₆₄

sind bevorzugt t-C₄H₉ oder t-C₅H₁₁.

Suitable cyan couplers correspond to formulas VI, VII, VIIa and VIII

wherein

R ₆₁ , R ₆₂ , R ₆₃ and R ₆₄

are independently hydrogen or C ₁ -C ₆ alkyl;

in the

R ₇₁ and R ₇₂

independently represent an electron-withdrawing group,

X ₇₁

for H or a group which can be split off in the reaction with developer oxidation product,

Y ₇₁

represents a group for completing a nitrogen-containing heterocycle, with the proviso that a group represented by R ₇₂ is bonded to a carbon atom of the heterocycle,

n

represents 1 or 2;

in the

R ₇₁ , R ₇₂ and X ₇₁

have the meaning given above and

Z ₇₁

represents H or a substituent;

wherein

R ₈₁

Hydrogen or a substituent,

X ₈₁

a hydrogen atom or a leaving group and

Y ₈₁

OR ₈₂ or

mean where

R ₈₂

R ₈₃

Alkyl,

R ₈₄

Hydrogen or R ₈₃ ,

R ₈₅ , R ₈₆ , R ₈₈ and R ₈₉

Hydrogen or a substituent,

R ₈₇

a substituent and

Z ₈₁

the remaining non-metallic members of a 3- to 8-membered ring mean, where Z ₈₁ can be further substituted.

R ₆₁

is preferably CH ₃ or C ₂ H ₅ .

R ₆₂

is preferably C ₂ -C ₆ alkyl,

R ₆₃ and R ₆₄

are preferably tC ₄ H ₉ or tC ₅ H ₁₁ .

VI-1 mit R₆₁ = C₂H₅, R₆₂ = n-C₄H₉, R₆₃ = R₆₄ = t-C₄H₉,

VI-2 mit R₆₁ = R₆₂ = C₂H₅, R₆₃ = R₆₄ = t-C₅H₁₁,

VI-3 mit R₆₁ = C₂H₅, R₆₂ = n-C₃H₇, R₆₃ = R₆₄ = t-C₅H₁₁,

VI-4 mit R₆₁ = CH₃, R₆₂ = C₂H₅, R₆₃ = R₆₄ = t-C₅H₁₁.

Examples of cyan couplers of formula VI are:

VI-1 with R ₆₁ = C ₂ H ₅ , R ₆₂ = nC ₄ H ₉ , R ₆₃ = R ₆₄ = tC ₄ H ₉ ,

VI-2 with R ₆₁ = R ₆₂ = C ₂ H ₅ , R ₆₃ = R ₆₄ = tC ₅ H ₁₁ ,

VI-3 with R ₆₁ = C ₂ H ₅ , R ₆₂ = nC ₃ H ₇ , R ₆₃ = R ₆₄ = tC ₅ H ₁₁ ,

VI-4 with R ₆₁ = CH ₃ , R ₆₂ = C ₂ H ₅ , R ₆₃ = R ₆₄ = tC ₅ H ₁₁ .

Examples of cyan couplers of formula VIIa are:

Suitable compounds of formula VIII are:

Preparation of the silver halide emulsions 0. Mikratemulsion (EmM1) (Doping-free Mikrate)

The following solutions are prepared with demineralized water: Solution 01 5500 g water 700 g gelatin 5 g n-decanol 20 g NaCl Solution 02 9300 g water 1800 g NaCl Solution 03 9000 g water 5000 g AgNO ₃

Solutions 02 and 03 are simultaneously added to solution 01 at 50 ° C over a period of 30 minutes with a constant feed rate at pAg 7.7 and pH 5.0 with vigorous stirring. During the precipitation, the pAg value by metering in a NaCl solution and the pH value by metering in H ₂ SO ₄ into the precipitation tank are kept constant. An AgCl emulsion with an average particle diameter of 0.09 μm is obtained. The gelatin / AgNO ₃ weight ratio is 0.14. The emulsion is ultrafiltered at 40 ° C., washed and redispersed with so much gelatin and water that the gelatin / AgNO ₃ weight ratio is 0.3 and the emulsion contains 200 g AgCl per kg. After redispersion, the grain size is 0.12 µm.

Production of Mikratemulsion EmM2:

as EmM1, but with the difference that an additional 570 µg K ₂ IrCl _{6 is added} to solution 02. The emulsion contains 20 nmol Ir ⁴⁺ per mol AgCl.

Production of Mikratemulsion EmM3:

Like EmM2, but the amount of K ₂ IrCl ₆ in solution 02 is increased to 28.5 mg. The emulsion contains 1 mmol Ir ⁴⁺ per mol AgCl.

Production of Mikratemulsion EmM4:

like EmM1, but with the difference that an additional 1140 µg K ₂ IrCl _{6 are added} to solution 02.

Production of Mikratemulsion EmM5:

as EmM1, but with the difference that an additional 20.4 g of KI is added to solution 02 are given.

Production of Mikratemulsion EmM6:

as EmM1, but with the difference that an additional 1140 µg K ₂ IrCl ₆ and 20.4 g KI are added to solution 02.

1. Blue-sensitive emulsions EmB1-EmB10 EmB1

The following solutions are prepared with demineralized water: Solution 11 1100 g water 136 g gelatin 1 g n-decanol 4 g NaCl 65 g EmM1 Solution 12 1860 g water 360 g NaCl 57 µg K ₂ IrCl ₆ Solution 13 1800 g water 1000 g AgNO ₃

Solutions 12 and 13 are added at 50 ° C. over a period of 150 minutes at a pAg of 7.7, with vigorous stirring, to the solution 11 presented in the precipitation kettle. The pAg and pH are checked in the same way as for the precipitation of the emulsion (EmM1). The feed is controlled in such a way that the feed rate of solution 13 increases linearly from 2 ml / min to 18 ml / min in the first 100 minutes and the rate of feed in the remaining 50 minutes is constant at 20 ml / min. An AgCl emulsion with an average particle diameter of 0.71 μm is obtained. The emulsion contains 10 nmol Ir ⁴⁺ per mol AgCl. The gelatin / AgNO ₃ - (the amount of AgCl in the emulsion is subsequently converted to AgNO ₃ ) weight ratio is 0.14. The emulsion is ultrafiltered, washed and redispersed with so much gelatin and water that the gelatin / AgNO ₃ weight ratio is 0.56 and the emulsion contains 200 g AgNO ₃ per kg.

The emulsion is ripened at a pH of 0.53 with an optimal amount of gold (III) chloride and Na ₂ S ₂ O ₃ at a temperature of 50 ° C. for 2 hours. After chemical ripening, the emulsion is spectrally sensitized at 40 ° C. with 30 mmol of the compound (Sens B), stabilized with 0.4 mmol of the compound (rod 1) and then mixed with 0.006 mol KBr.

EmB2

Precipitation, desalination, redispersion, chemical ripening, spectral sensitization and stabilization are the same as for EmB1, but with the difference that before the Start of the precipitation 100 mg of the bisthioether I-9 are added to solution 11.

EmB3

1. Vor dem Start der Fällung enthält die in dem Fällungskessel vorgelegte Lösung 11 keine Verbindung I-9 und die Lösung 12 kein K₂IrCl₆.

2. Die Zugabe von 100 mg der Verbindung I-9 in den Fällungskessel und die Zugabe von 57 µg K₂IrCl₆ in die Lösung 12 erfolgen erst 10 Minuten nachdem 50 % der Lösung 13 zudosiert worden sind.

Like EmB2 but with the differences:

1. Before the start of the precipitation, the solution 11 presented in the precipitation kettle contains no compound I-9 and the solution 12 contains no K ₂ IrCl ₆ .

2. The addition of 100 mg of compound I-9 in the precipitation kettle and the addition of 57 μg of K ₂ IrCl ₆ in solution 12 take place only 10 minutes after 50% of solution 13 have been metered in.

Desalination and redispersion are the same as for EmB1. The grain size after redispersion is 0.72 µm. The outermost zone differs from the inner zones in that it contains 20 nmol Ir ⁴⁺ per mol AgCl and that reduction nuclei are produced by the compound I-9. Chemical maturation, spectral sensitization and stabilization take place as with EmB1.

EmB4

The emulsion is produced by redissolving the EmM2 micrate emulsion for a preliminary EmV1.

Production of the Precipitation EmV1: (Doping- Free Precipitation)

1. Lösung 12 enthält kein K₂IrCl₆

2. Verdoppelung der Menge der Zusätze in Lösung 11

3. Die Zulaufgeschwindigkeit der Lösung 13 steigt linear von 4 ml/min bis 36 ml/min an, so daß die Fällung innerhalb 100 Minuten abgeschlossen ist. Es wird eine AgCl-Emulsion mit dem mittleren Teilchendurchmesser von 0,56 µm erhalten. Das Gelatine/AgNO₃-Gewichtsverhältnis beträgt 0,144. Die Emulsion wird ultrafiltriert, gewaschen und mit so viel Gelatine redispergiert, daß das Gelatine/AgNO₃-Gewichtsverhältnis 0,56 beträgt.

like EmB1 but with the differences:

1. Solution 12 does not contain K ₂ IrCl ₆

2. Doubling the amount of additives in solution 11

3. The feed rate of solution 13 increases linearly from 4 ml / min to 36 ml / min, so that the precipitation is completed within 100 minutes. An AgCl emulsion with an average particle diameter of 0.56 μm is obtained. The gelatin / AgNO ₃ weight ratio is 0.144. The emulsion is ultrafiltered, washed and redispersed with enough gelatin that the gelatin / AgNO ₃ weight ratio is 0.56.

Production of EmB4:

2.5 kg of the pre-precipitation EmV1 (corresponds to 500 g AgNO ₃ ) are placed in a precipitation kettle and melted at 40 ° C. 2.5 kg of EmM2 (corresponds to 500 g of AgNO ₃ ) are placed in an inlet vessel provided with a stirrer and melted at 40 ° C. With vigorous stirring of the precipitation EmV1, 100 mg of the compound 1-9 are added. After 5 minutes, the micro emulsion EmM2 is metered in at a constant rate within 50 minutes. After 10 minutes, the emulsion is redispersed with enough gelatin that the gelating / AgNO ₃ weight ratio is 0.56. An AgCl emulsion with an average particle diameter of 0.72 μm is obtained. Chemical maturation, spectral sensitization and stabilization take place as with EmB1.

EmB5

The emulsion is prepared as for the EmB4, but before the Redissolution of the micro emulsion EmM2 to the pre-precipitation EmV1 instead of compound I-9 100 ml of 20 wt .-% aqueous NaCl solution added. It becomes an AgCl emulsion obtained with the mean particle diameter of 0.70 µm. Chemical Maturation, spectral sensitization and stabilization take place as with EmB1.

EmB6

1. Die Vorfällung EmV1 enthält 114 mg K₂IrCl₆ (= 20 nmol K₂IrCl₆ pro mol Ag).

2. Als Mikratemulsion für die Umlösung wird EmM1 statt EmM2 genommen.

The emulsion is produced as for the EmB4, but with the following differences:

1. The pre-precipitation EmV1 contains 114 mg K ₂ IrCl ₆ (= 20 nmol K ₂ IrCl ₆ per mol Ag).

2. EmM1 instead of EmM2 is used as the micrate emulsion for the redissolution.

The emulsion contains 20 nmol Ir ⁴⁺ . Compound I-9 produces reduction nuclei in the core and in the shell.

EmB7

Precipitation, desalination, redispersion, chemical ripening, spectral sensitization and stabilization are the same as for EmB1, but with the difference that additional 1.02 g of KI are added to solution 12. The grain size is 0.72 µm.

EmB8

Like EmB7, but with the difference that 57 µg K ₂ IrCl ₆ , 1.02 g KI and 100 mg of compound I-9 are only added after 75% of solution 13 has been metered in. The grain size after redispersion is 0.72 µm.

EmB9

Like EmB8, but solutions 12 and 13 are divided as follows: Solution 22 1395 g water 270 g NaCl 1.02 g AI 57 µg K ₂ IrCl ₆ Solution 23 1350 g water 750 g AgNO ₃ Solution 24 465 g water 90 g NaCl Solution 25 450 g water 250 g AgNO ₃

The first run-in takes place with solutions 22 and 23. The second run-in takes place with solutions 24 and 25. The feed rate is the same as for EmB1. 10th Minutes before the start of the second enema, 100 mg of compound I-9 dem Precipitation kettle added. The grain size after redispersion is 0.72 µm.

EmB10

like EmB8 but with the difference that no K ₂ IrCl _{6 is} added to solution 12. The grain size after redispersion is 0.71 µm.

Preparation of the blue sensitive emulsions EmB11-EmB18

The emulsions are prepared by redissolving the micrate emulsions a precondition.

Production of the precursors EmV2-EmV6 1.1 EmV2

1) Lösung 12 enthält keine K₂IrCl₆-Verbindung

2) Die Menge der Zusätze in Lösung 11 wird um 35 % erhöht

3) Die Zulaufgeschwindigkeit der Lösung 13 steigt linear von 4 ml/min bis 36 ml/min an, so daß die Fällung innerhalb 100 Minuten abgeschlossen ist. Es wird eine AgCl-Emulsion mit dem mittleren Teilchendurchmesser von 0,64 µm erhalten. Das Gelatine/AgNO₃-Gewichtsverhältnis beträgt 0,144. Die Emulsion wird ultrafiltriert, gewaschen und mit so viel Gelatine redispergiert, daß das Gelatine/AgNO₃-Gewichtsverhältnis 0,56 beträgt.

like EmB1 but with the differences:

1) Solution 12 contains no K ₂ IrCl ₆ compound

2) The amount of additives in solution 11 is increased by 35%

3) The feed rate of solution 13 increases linearly from 4 ml / min to 36 ml / min, so that the precipitation is completed within 100 minutes. An AgCl emulsion with an average particle diameter of 0.64 μm is obtained. The gelatin / AgNO ₃ weight ratio is 0.144. The emulsion is ultrafiltered, washed and redispersed with enough gelatin that the gelatin / AgNO ₃ weight ratio is 0.56.

1.2 EmV3

as EmV2, but adding 1.36 g of KI to solution 12.

1.3 EmV4

like EmV2, but adding 76 µg K ₂ IrCl ₆ to solution 12.

1.4 EmV5

as EmV2, but adding 76 µg K ₂ IrCl ₆ and 1.36 g KI to solution 12.

1.5 EmV6

Like EmV2, but adding 760 Mg K ₂ IrCl ₆ and 13.6 g KI to solution 12.

Preparation of the blue-sensitive emulsion EmB11-B18 Manufacturing EmB11

900 g of the pre-precipitation EmV2 (corresponds to 180 g AgNO ₃ ) are placed in a precipitation kettle and melted at 40 ° C. 300 g of micro emulsion EmM1 (corresponds to 60 g of AgNO ₃ ) are placed in an inlet kettle installed with a stirrer and melted at 40 ° C. 95 mg of the compound I-9 are added with vigorous stirring of the precipitation EmV2. After a 5 minute break, the micro emulsion EmM1 is metered in at a constant speed within 20 minutes. After a 10 minute break, the emulsion is redispersed with enough gelatin that the gelatin / AgNO ₃ weight ratio is 0.56. An AgCl emulsion with an average particle diameter of 0.73 μm is obtained. Chemical maturation, spectral sensitization and stabilization take place as with EmB1.

Manufacturing EmB12

like EmB11, but with EmV3 prefix instead of EmV2.

Manufacturing EmB13

like EmB11, but with EmV5 instead of EmV2.

Manufacturing EmB14

like EmB11, but with micro emulsion EmM5 instead of EmM1.

Manufacturing EmB15

like EmB15, but with EmV4 instead of EmV2.

Manufacturing EmB16

like EmB11, but with micro emulsion EmM6 instead of EmM1.

Manufacturing EmB17

like EmB17, but with EmV4 instead of EmV2.

Manufacturing EmB18

like EmB17, but with EmV6 prefix instead of EmV2.

The blue-sensitive emulsions B1 and B7 to B19 are shown below in terms of grain structure and doping. emulsion Zones Made from Ir ⁴⁺ doping (nmol / mol Ag) AgI doping (mmol / mol Ag) Share of zones in the total grain B 1 1 EmM1 0 0 1.3% 2 Double inlet 10 0 98.7% B 7 1 EmM1 0 0 1.3% 2 Double inlet 10 1 98.7% B 8 1 EmM1 0 0 1.3% 2 Double inlet 0 0 74% 3rd Double inlet 40 4th 24.7% B 9 1 EmM1 0 0 1.3% 2 Double inlet 13.3 1.33 74% 3rd Double inlet 0 0 24.7% B 10 1 EmM1 0 0 1.3% 2 Double inlet 0 0 74% 3rd Double inlet 0 4th 24.7% B 11 1 EmM1 0 0 0.975% 2 Double inlet 0 0 74.025% 3rd Redeployment 0 0 25% B 12 1 EmM1 0 0 0.975% 2 Double inlet 0 1.33 74.025% 3rd Redeployment 0 0 25% B 13 1 EmM1 0 0 0.975% 2 Double inlet 13.3 1.33 74.025% 3rd Redeployment 0 0 25% B 14 1 EmM5 0 0 0.975% 2 Double inlet 0 0 74.025% 3rd Redeployment 0 4th 25% B 15 1 EmM5 0 0 0.975% 2 Double inlet 13.3 0 74.025% 3rd Redeployment 0 4th 25% B 16 1 EmM6 0 0 0.975% 2 Double inlet 0 0 74.025% 3rd Redeployment 40 4th 25% B 17 1 EmM6 0 0 0.975% 2 Double inlet 13.3 0 74.025% 3rd Redeployment 40 4th 25% B 18 1 EmM6 0 0 0.975% 2 Double inlet 133 13.3 74.025% 3rd Redeployment 40 4th 25%

2. Green sensitive emulsions EmG1 - EmG2 EmG1

The following solutions are prepared with demineralized water: Solution 21 1100 g water 136 g gelatin 1 g n-decanol 4 g NaCl 186 g EmM1 Solution 22 1860 g water 3600 g NaCl 57 µg K ₂ IrCl ₆ Solution 23 1800 g water 1000 g AgNO ₃ 4.8 mg HgCl ₂

Solutions 22 and 23 are added at 40 ° C. over the course of 75 minutes at a pAg of 7.7 to the solution 21 presented in the precipitation kettle, with vigorous stirring. The pAg and pH are checked in the same way as for the precipitation of the EmM1 emulsion. The feed is controlled in such a way that the feed rate of solution 23 increases linearly from 4 ml / min to 36 ml / min in the first 50 minutes and the rate of feed in the remaining 25 minutes is constant at 40 ml / min. An AgCl emulsion with an average particle diameter of 0.50 μm is obtained. The emulsion contains 10 nmol Ir ⁴⁺ and 3 µmol HgCl ₂ per mol AgCl. The gelatin / AgNO ₃ weight ratio is 0.14. The emulsion is ultrafiltered, washed and redispersed with so much gelatin and water that the gelatin / AgNO ₃ weight ratio is 0.56 and the emulsion contains 200 g AgNO ₃ per kg.

2.5 kg of the emulsion (corresponds to 500 g AgNO ₃ ) is ripened at a pH of 0.53 with an optimal amount of gold (III) chloride and Na ₂ S ₂ O ₃ at a temperature of 60 ° C. for 2 hours. After chemical ripening, per mole of AgCl in the emulsion is spectrally sensitized at 50 ° C with 40 mmol of the compound (Sens G), with 0.4 mmol of the compound (Rod 1) and 0.4 mmol of the compound (Rod 2) and 0, 4 mmol of the compound (rod 3) stabilized and then mixed with 0.01 mol KBr.

EmG2

2.5 kg of the emulsion EmG1 (corresponds to 500 g AgNO ₃ ) are placed in a precipitation kettle and melted at 40 ° C. 250 g EmM3 (corresponds to 50 g AgNO ₃ ) are placed in an inlet vessel equipped with a stirrer and melted at 40 ° C. With intensive stirring of the EmG1 emulsion, EmM3 is metered in at a constant rate within 5 minutes. After 10 minutes, the emulsion is redispersed with enough gelatin that the gelatin / AgNO ₃ weight ratio is 0.56. An AgCl emulsion with an average particle diameter of 0.52 μm is obtained. Chemical ripening, spectral sensitization and stabilization take place as with EmG1.

Red-sensitive emulsion EmR1

Precipitation, desalination and redispersion are the same as for the green-sensitive EmG1 emulsion. After chemical ripening with an optimal amount of gold (III) chloride and Na ₂ S ₂ O ₃ at a temperature of 60 ° C, the emulsion is spectrally sensitized at 40 ° C with 50 µmol of the compound (Sens R) and with 954 µmol (rod 4) and 2.24 mmol (rod 2) per mol of AgNO ₃ stabilized. Then 0.003 mol KBr are added.

The type and amount of doping of the silver halide emulsions follows from Table 1. The zones are numbered from the inside out. emulsion Number of zones Endowment Part of the zone in the grain B-1 1 10 nmol Ir ⁴⁺ / mol AgCl 100% B-2 1 10 nmol Ir ⁴⁺ / mol AgCl 100% B-3 2 Zone 1 - 50% Zone 2: 20 nmol Ir ⁴⁺ / mol AgCl 50% B-4 2 Zone 1 - 50% Zone 2: 20 nmol Ir ⁴⁺ / mol AgCl 50% B-5 2 Zone 1 - 50% Zone 2: 20 nmol Ir ⁴⁺ / mol AgCl 50% B-6 2 Zone 1: 20 nmol Ir ⁴⁺ / mol AgCl 50% Zone 2 - 50% G 1 1 10 nmol Ir ⁴⁺ and 3 µmol Hg ²⁺ / mol AgCl 100% G 2 2 Zone 1: 10 nmol Ir ⁴⁺ and 3 µmol Hg ²⁺ / mol AgCl 90.9% Zone 2: 1000 nmol Ir ⁴⁺ / mol AgCl 9.1% R 1 1 10 nmol Ir ⁴⁺ and 3 µmol Hg ²⁺ / mol AgCl 100%

Layer structures

A color photographic recording material was produced by applying the following layers in the order given to a support made of paper coated on both sides with polyethylene. The quantities given relate to 1 m ² . The corresponding amounts of AgNO ₃ are given for the silver halide application.

Layer structure 1

1st layer (substrate layer):
0.3 g gelatin

EmB1 aus 0,40 g AgNO₃

0,635 g Gelatine

0,55 g Gelbkuppler V-1

0,38 g Trikresylphosphat (TKP)

2nd layer (blue-sensitive layer):

EmB1 from 0.40 g AgNO ₃

0.635 g gelatin

0.55 g yellow coupler V-1

0.38 g tricresyl phosphate (CPM)

1,1 g Gelatine

0,08 g Scavenger SC

0,02 g Weißkuppler WK

0,1 g TKP

3rd layer (intermediate layer):

1.1 g gelatin

0.08 g Scavenger SC

0.02 g white coupler WK

0.1 g CPM

EmG1 aus 0,23 g AgNO₃

1,2 g Gelatine

0,23 g Purpurkuppler III-1

0,23 g Farbstabilisator ST-3

0,17 g Farbstabilisator ST-4

0,23 g TKP

4th layer (green-sensitive layer):

EmG1 from 0.23 g AgNO ₃

1.2 g gelatin

0.23 g purple coupler III-1

0.23 g color stabilizer ST-3

0.17 g color stabilizer ST-4

0.23 g CPM

1,1 g Gelatine

0,08 g SC

0,02 g WK

0,6 g UV-Absorber UV

0,1 g TKP

5th layer (UV protective layer):

1.1 g gelatin

0.08 g SC

0.02 g WK

0.6 g UV absorber UV

0.1 g CPM

EmR-1 aus 0,26 g AgNO₃ mit

0,75 g Gelatine

0,40 g Blaugrünkuppler VI-2

0,36 g TKP

6th layer (red-sensitive layer):

EmR-1 from 0.26 g AgNO ₃ with

0.75 g gelatin

0.40 g of cyan coupler VI-2

0.36 g CPM

0,35 g Gelatine

0,15 g UV

0,075 g TKP

7th layer (UV protective layer):

0.35 g gelatin

0.15 g UV

0.075 g CPM

0,9 g Gelatine

0,3 g Härtungsmittel HM

8th layer (UV protective layer):

0.9 g gelatin

0.3 g HM hardening agent

Layer structure 2:

like layer structure 1, but the blue-sensitive emulsion in the second layer is EmB2 with 0.4 g AgNO ₃ / m ² .

Layer structure 3:

like layer structure 1, but the blue-sensitive emulsion in the second layer is EmB3 with 0.4 g AgNO ₃ / m ² .

Layer structure 4:

like layer structure 1, but the blue-sensitive emulsion in the second layer is EmB4 with 0.4 g AgNO ₃ / m ² .

Layer structure 5:

like layer structure 1, but the blue-sensitive emulsion in the second layer is EmB5 with 0.4 g AgNO ₃ / m ² .

Layer structure 6:

like layer structure 1, but the blue-sensitive emulsion in the second layer is EmB6 with 0.4 g AgNO ₃ / m ² .

Layer structure 7:

like layer structure 1, but the green-sensitive emulsion in the fourth layer is EmG2 with 0.23 g AgNO ₃ / m ² .

Layer structure 8:

Like layer structure 1, but with 0.15 g yellow coupler V-54 and 0.40 g yellow coupler V-52 instead of 0.55 g yellow coupler V-1; and with 0.23 g purple coupler III-2 instead of 0.23 g purple coupler III-1.

Layer structure 9:

like layer structure 8, but the blue-sensitive emulsion in the second layer is EmB7 with 0.4 g AgNO ₃ / m ² .

Layer structure 10:

like layer structure 8, but the blue-sensitive emulsion in the second layer is EmB8 with 0.4 g AgNO ₃ / m ² .

Layer structure 11:

like layer structure 8, but the blue-sensitive emulsion in the second layer is EmB9 with 0.4 g AgNO ₃ / m ² .

Layer structure 12:

like layer structure 8, but the blue-sensitive emulsion in the second layer is EmB10 with 0.4 g AgNO ₃ / m ² .

Layer structure 13:

like layer structure 8, but the blue-sensitive emulsion in the second layer is EmB11 with 0.4 g AgNO ₃ / m ² .

Layer structure 14:

like layer structure 8, but the blue-sensitive emulsion in the second layer is EmB12 with 0.40 g AgNO ₃ / m ² .

Layer structure 15:

like layer structure 8, but the blue-sensitive emulsion in the second layer is EmB13 with 0.40 g AgNO ₃ / m ² .

Layer structure 16:

like layer structure 8, but the blue-sensitive emulsion in the second layer is EmB14 with 0.40 g AgNO ₃ / m ² .

Layer structure 17:

like layer structure 8, but the blue-sensitive emulsion in the second layer is EmB15 with 0.40 g AgNO ₃ / m ² .

Layer structure 18:

like layer structure 8, but the blue-sensitive emulsion in the second layer is EmB16 with 0.40 g AgNO ₃ / m ² .

Layer structure 19:

like layer structure 8, but the blue-sensitive emulsion in the second layer is EmB17 with 0.40 g AgNO ₃ / m ² .

Layer structure 20:

like layer structure 8, but the blue-sensitive emulsion in the second layer is EmB18 with 0.40 g AgNO ₃ / m ² .

Connections used for the first time in layer structure 1 to 20:

Processing : Conventional (integral) exposure:

a) Farbentwickler - 45 s - 35°C Triethanolamin 9,0 g N,N-Diethylhydroxylamin 4,0 g Diethylenglykol 0,05 g 3-Methyl-4-amino-N-ethyl-N-methansulfonamidoethyl-anilin-sulfat 5,0 g Kaliumsulfit 0,2 g Triethylenglykol 0,05 g Kaliumcarbonat 22 g Kaliumhydroxid 0,4 g Ethylendiamintetraessigsäure-di-Na-Salz 2,2 g Kaliumchlorid 2,5 g 1,2-Dihydroxybenzol-3,4,6-trisulfonsäuretrinatriumsalz 0,3 g auffüllen mit Wasser auf 1 000 ml; pH 10,0

b) Bleichfixierbad - 45 s - 35°C Ammoniumthiosulfat 75 g Natriumhydrogensulfit 13,5 g Ammoniumacetat 2,0 g Ethylendiamintetraessigsäure (Eisen-Ammonium-Salz) 57 g Ammoniak 25 %ig 9,5 g auffüllen mit Essigsäure auf 1 000 ml; pH 5,5

c) Wässern - 2 min - 33°C

d) Trocknen

The samples were exposed behind a graduated gray wedge with a density gradation of 0.1 / step 5 ms, 40 ms, 5 s and 40 s with a constant amount of light and processed in process AP 94 as follows:

a) Color developer - 45 s - 35 ° C Triethanolamine 9.0 g N, N-diethylhydroxylamine 4.0 g Diethylene glycol 0.05 g 3-methyl-4-amino-N-ethyl-N-methanesulfonamidoethyl aniline sulfate 5.0 g Potassium sulfite 0.2 g Triethylene glycol 0.05 g Potassium carbonate 22 g Potassium hydroxide 0.4 g Ethylenediaminetetraacetic acid di-Na salt 2.2 g Potassium chloride 2.5 g 1,2-Dihydroxybenzene-3,4,6-trisulfonic acid trisodium salt 0.3 g make up to 1,000 ml with water; pH 10.0

b) bleach-fix bath - 45 s - 35 ° C Ammonium thiosulfate 75 g Sodium bisulfite 13.5 g Ammonium acetate 2.0 g Ethylenediaminetetraacetic acid (iron ammonium salt) 57 g 25% ammonia 9.5 g make up to 1,000 ml with acetic acid; pH 5.5

c) Soak - 2 min - 33 ° C

d) drying

Dmin:

Dichte im Bereich der Farbdichtekurve im nicht belichteten Bereich

Empfindlichkeit E:

Abszisse zur Dichte = 0,6 Als Abszissenwert wird die Dichte des Vorlagekeils angegeben (relativer Empfindlichkeitswert)

Gamma-Wert G1:

Schwellengradation: ist die Steigung der Sekante zwischen dem Empfindlichkeitspunkt mit der Dichte D = Dmin + 0,10 und dem Kurvenpunkt mit der Dichte D = Dmin+ 0,85.

Gamma-Wert G2:

Schultergradation: ist die Steigung der Sekante zwischen dem Empfindlichkeitspunkt mit der Dichte D = Dmin + 0,85 und dem Kurvenpunkt mit der Dichte D = Dmin+ 1,60.

Dmax:

Dichte im Bereich des horizontalen Verlaufs der Farbdichtekurve bei Überbelichtung.

The results of the analog exposure are shown in the form of the following parameters:

Dmin:

Density in the area of the color density curve in the unexposed area

Sensitivity E:

Abscissa to density = 0.6 The abscissa value is the density of the template wedge (relative sensitivity value)

Gamma value G1:

Threshold gradation: is the slope of the secant between the sensitivity point with the density D = Dmin + 0.10 and the curve point with the density D = Dmin + 0.85.

Gamma value G2:

Shoulder gradation: is the slope of the secant between the sensitivity point with the density D = Dmin + 0.85 and the curve point with the density D = Dmin + 1.60.

Dmax:

Density in the area of the horizontal course of the color density curve in the event of overexposure.

Laser exposure:

The samples were exposed in the laser exposure unit mentioned at the beginning with the raster step wedge and the full step wedge: Red: minimal: 0.7 nW maximum: 25 µW Green: minimal: 1 nW maximum: 2 µW Blue: minimal: 1 nW maximum: 5 µW

Processing is the same as for analog exposure.

D_F (rot):

Die nutzbare Blaugrün-Maximaldichte bei einer tolerierbaren Linienverbreitung gemäß Abbildung (3) und Gleichung (3)

D_F (grün):

wie D_F (rot) aber für Purpur-Farbdichte

D_F (blau):

wie D_F (rot) aber für Gelb-Farbdichte

The results of the laser exposures are shown in the form of the following parameters:

D _F (red):

The usable teal maximum density with a tolerable line spread according to figure (3) and equation (3)

D _F (green):

like D _F (red) but for purple color density

D _F (blue):

like D _F (red) but for yellow color density

Solarization :

Execution: The unprocessed samples from the layer structures 1 to 7 were exposed to sunlight (daylight saving time Europe) 0.0h, 0.5h, 1h, 2h, 16h and 48h. The exposed samples were processed in process AP 94. Then were the yellow, purple and teal color densities measured using X-Rite (Status A).

The results are shown in Tables 2a, 2b, 3a, 3b, 4a, 4b, 5a and 5b.

Results:

Layer structure sensitive layer Solarization Exploitable DF with laser exposure comment (0.5 h-0.0 h) (1h-0.0h) (2h-0.0h) (16h-0.0h) (48h-0.0h) D _F (blue) 1 yellow -0.00 -0.01 -0.01 -0.00 -0.03 1.90 comparison 2nd yellow -0.00 -0.00 -0.00 -0.01 -0.02 1.95 comparison 3rd yellow -0.00 -0.18 -0.25 -0.51 -0.02 2.05 invention 4th yellow -0.00 -0.30 -0.45 -0.72 -0.05 2.10 invention 5 yellow -0.00 -0.23 -0.34 -0.60 -0.03 2.13 invention 6 yellow -0.00 -0.26 -0.38 -0.64 -0.02 2.12 invention Layer structure sensitive layer Solarization Exploitable DF with laser exposure comment (0.5 h-0.0 h) (1h-0.0h) (2h-0.0h) (16h-0.0h) (48h-0.0h) D _F (green) 1 purple -0.00 -0.00 -0.00 -0.01 +0.01 2.28 comparison 7 purple -0.00 -0.05 -0.10 -0.18 -0.02 2.37 invention

It becomes clear that materials with solarization properties achieve a higher usable color density with laser exposure. Layer structure sensitive layer Gamma 1 at exposure time Gamma 2 at exposure time comment 5 msec 40 msec 5 sec 5 msec 40 msec 5 sec 1 yellow 1.65 1.80 1.78 2.62 3.00 2.98 comparison 2 yellow 1.63 1.75 1.76 2.57 2.80 2.82 comparison 3rd yellow 1.73 1.76 1.76 2.75 2.85 2.85 invention 4th yellow 1.74 1.76 1.76 2.87 2.90 2.90 invention 5 yellow 1.75 1.77 1.77 2.90 2.95 2.95 invention 6 yellow 1.72 1.76 1.77 2.83 2.89 2.88 invention Layer structure sensitive layer Gamma 1 at exposure time Gamma 2 at exposure time comment 5 msec 40 msec 5 sec 5 msec 40 msec 5 sec 1 purple 1.75 1.82 1.78 2.90 3.20 3.05 comparison 7 purple 1.81 1.84 1.82 3.18 3.22 3.17 invention

It becomes clear that materials with solarization properties have better Schwarzschild behavior with regard to Gamma 1 and Gamma 2. Layer structure Blue sensitive layer Solarization Exploitable DF with laser exposure comment (0.5 h-0.0 h) (1 h-0.0 h) (2 h-0.0 h) (16 h-0.0 h) (48 h-0.0 h) D _F (red) D _F (green) D _F (blue) 8th EmB 1 -0.00 -0.01 -0.01 -0.00 -0.04 2.47 2.38 1.95 comparison 9 EmB 7 -0.00 -0.00 -0.00 -0.01 -0.03 2.46 2.39 2.00 comparison 10 EmB 8 -0.00 -0.16 -0.25 -0.40 -0.02 2.48 2.41 2.25 invention 11 EmB 9 -0.00 -0.15 -0.20 -0.32 -0.05 2.47 2.42 2.20 invention 12th EmB 10 -0.00 -0.22 -0.38 -0.40 -0.03 2.46 2.44 2.15 invention Layer structure Blue sensitive layer Solarization Exploitable DF with laser exposure comment (0.5 h-0.0 h) (1 h-0.0 h) (2 h-0.0 h) (16 h-0.0 h) (48 h-0.0 h) D _F (red) D _F (green) D _F (blue) 13 EmB 11 -0.00 -0.01 -0.01 -0.00 -0.03 2.44 2.38 1.90 comparison 14 EmB 12 -0.00 -0.00 -0.25 -0.51 -0.02 2.43 2.40 2.00 invention 15 EmB 13 -0.00 -0.30 -0.35 -0.62 -0.05 2.47 2.42 2.05 invention 16 EmB 14 -0.00 -0.13 -0.24 -0.50 -0.03 2.46 2.43 2.08 invention 17th EmB 15 -0.00 -0.12 -0.34 -0.60 -0.03 2.44 2.44 2.15 invention 18th EmB 16 -0.00 -0.15 -0.37 -0.60 -0.02 2.43 2.47 2.20 invention 19th EmB 17 -0.00 -0.18 -0.25 -0.51 -0.02 2.45 2.50 2.28 invention 20th EmB 18 -0.00 -0.30 -0.45 -0.72 -0.05 2.47 2.46 2.20 invention

It becomes clear that materials with solarization properties achieve a higher usable color density with laser exposure. Layer structure Blue sensitive emulsion Gamma 1 at exposure time Gamma 2 at exposure time comment 5 msec 40 msec 5 sec 5 msec 40 msec 5 sec 8th EmB1 1.65 1.80 1.76 2.63 3.01 2.98 comparison 9 EmB7 1.62 1.75 1.76 2.82 3.05 3.05 comparison 10 EmB8 1.79 1.81 1.80 3.20 3.30 3.30 invention 11 EmB9 1.76 1.78 1.76 3.22 3.25 3.25 invention 12th EmB10 1.74 1.75 1.77 3.10 3.15 3.15 invention Layer structure Blue sensitive layer Gamma 1 at exposure time Gamma 2 at exposure time comment 5 msec 40 msec 5 sec 5 msec 40 msec 5 sec 13 EmB11 1.65 1.80 1.78 2.62 3.00 2.95 comparison 14 EmB12 1.73 1.78 1.80 3.12 3.15 3.20 invention 15 EmB13 1.74 1.76 1.78 3.10 3.12 3.14 invention 16 EmB14 1.78 1.80 1.78 3.15 3.15 3.19 invention 17th EmB15 1.75 1.75 1.78 3.17 3.18 3.20 invention 18th EmB16 1.81 1.81 1.80 3.29 3.28 3.27 invention 19th EmB17 1.85 1.83 1.82 3.45 3.40 3.40 invention 20th EmB18 1.81 1.82 1.80 3.25 3.25 3.25 invention

It becomes clear that materials with solarization properties have better Schwarzschild behavior in terms of gamma 1 and gamma 2.

Claims (14)

1. Negatively developing colour photographic silver halide material having a support and at least one blue-sensitive silver halide emulsion layer containing at least one yellow coupler, at least one green-sensitive silver halide emulsion layer containing at least one magenta coupler and at least one red-sensitive silver halide emulsion layer containing at least one cyan coupler, at least 95 mol% of the silver halides of which consist of AgCl, characterised in that at least one silver halide emulsion layer exhibits solarisation on analogue exposure.
2. Colour photographic silver halide material according to claim 1, characterised in that at least one silver halide emulsion layer contains a silver halide emulsion, the grains of which consist of at least two differently precipitated zones and the silver ratio of the outer zone to the remaining silver of the grains is 1/24 to 6/1.
3. Colour photographic silver halide material according to claim 2, characterised in that the outermost zone is produced by recrystallising a micrate emulsion onto the previously produced preliminary precipitate.
4. Colour photographic silver halide material according to claim 2, characterised in that at least one zone of the stated silver halide emulsion is doped with at least one metal from group VIII or IIB of the periodic system of elements or with Re, Au, Pb or T1.
5. Colour photographic silver halide material according to claim 3, characterised in that the recrystallisation solvent used for recrystallisation of the micrate emulsion is a bisthioether and/or an NaCI solution.
6. Colour photographic silver halide material according to claim 5, characterised in that the bisthioether is of the formula I

   

   in which

   R₁

   means an alkyl, alkenyl, cycloalkyl, aryl or aralkyl radical having no more than 8 C atoms or -C(R₆, R₇)-C(R₈, R₉)-(CH₂)_nNHCONHR₁₀,

   R₂ to R₉

   mean H or alkyl having no more than 3 C atoms or, in pairs, the members of a five- or six-membered ring,

   R₁₀

   means hydrogen or a substituent and

   n

   means 0 or 1.

7. Colour photographic silver halide material according to claim 1, characterised in that the magenta coupler is of the formulae III or IV

   

   in which

   R₃₁, R₃₂, R₃₃ and R₃₄

   mutually independently mean hydrogen, alkyl, aralkyl, aryl, aroxy, alkylthio, arylthio, amino, anilino, acylamino, cyano, alkoxycarbonyl, alkylcarbamoyl or alkylsulphamoyl, where these radicals may be further substituted and where at least one of these radicals contains a ballast group, and

   Y

   means a radical seperable during chromogenic coupling (fugitive group) other than hydrogen.

8. Colour photographic silver halide material according to claim 1, characterised in that the yellow coupler is of the formula V

   

   in which

   R₅₁, R₅₂, R₅₃

   mutually independently mean alkyl or R₅₂ and R₅₃ together form a three- to six-membered ring;

   R₅₄

   means alkyl, alkoxy or halogen,

   R₅₅

   means halogen, alkyl, alkoxy, aryloxy, alkoxycarbonyl, alkylsulphonyl, alkylcarbamoyl, arylcarbamoyl, alkylsulphamoyl, arylsulphamoyl;

   Z₁

   means -O-, -NR₅₆-;

   Z₂

   means -NR₅₇- or -C(R₅₈)R₅₉-;

   R₅₆, R₅₇, R₅₈ and R₅₉

   mutually independently mean hydrogen or alkyl.

9. Colour photographic silver halide material according to claim 1, characterised in that the cyan coupler is of the formula VI, VII and VIII

   

   in which

   R₆₁, R₆₂, R₆₃ and R₆₄

   mutually independently mean hydrogen or C₁-C₆ alkyl;

   

   in which

   R₇₁ and R₇₂

   mutually independently mean an electron withdrawing group,

   X₇₁

   means H or a group detachable during the reaction with developer oxidation product,

   Y₇₁

   means a group for the completion of a nitrogen-containing heterocycle with the proviso that a group represented by R₇₂ is linked to a carbon atom of said heterocycle, and

   n

   means a number 1 or 2;

   

   in which

   R₈₁

   means hydrogen or a substituent,

   X₈₁

   means a hydrogen atom or a detachable group, and

   Y₈₁

   means OR₈₂ or

   

   where

   R₈₂

   means

   

   or alkyl,

   R₈₃

   means alkyl,

   R₈₄

   means hydrogen or R₈₃,

   R₈₅, R₈₆, R₈₈ and R₈₉

   means hydrogen or a substituent,

   R₈₇

   means a substituent and

   Z₈₁

   means the remaining non-metallic members of a 3- to 8-membered ring, it being possible for Z₈₁ to be further substituted.

10. Colour photographic silver halide material according to claim 4, characterised in that iridium, rhodium or mercury is used as the doping metal.
11. Colour photographic silver halide material according to claim 4, characterised in that an inner zone of the silver halide emulsion is doped with Hg²⁺ and an outer zone with Ir³⁺, Ir⁴⁺ and/or Rh³⁺.
12. Colour photographic silver halide material according to claim 1, characterised in that at least one silver halide emulsion layer contains at least 0.01 mmol AgI/mol AgCl.
13. Colour photographic silver halide material according to claim 4, characterised in that the zone being doped with at least one metal from group VIII or IIB of the periodic system of elements contains simultaneously AgI.
14. Colour photographic silver halide material according to claim 12, characterised in that the amount of AgI is 0.1 to 20 mmol/mol AgCl.

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