JPH01167751A - Color photographic negative copy material containing dir compound - Google Patents

Abstract

PURPOSE: To enable color reproduction improved in a wide exposure range by incorporating a comparatively large amount of a development inhibitor releasing(DIR) compound in at least one of plural silver halide emulsion layers having sensitivity in the same spectral region. CONSTITUTION: This photosensitive material has at least 2 fractional layers for recording at least one light image in red, green, and blue spectral wavelength regions and being different from each other in sensitivity. One of these fractional layers higher in sensitivity contains the DIR compound and this negative recording material is exposed to at least one of cyan and magenta and yellow colors and developed to obtain a color density of at least 0.4+0.2, preferably 0.4+0.25 after the white light color additive exposure process in an exposure (log I×t) capable of obtaining a color density of 0.4, thus permitting color reproduction performance to be made constant in a wide exposure range.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention describes the use of multilayer color photographs containing relatively large amounts of DIR compounds in at least one fast partial layer of several light-sensitive silver halide emulsion layers having the same spectral sensitivity. The present invention relates to a recording material which is a negative copying material, with which it is possible to obtain improved color reproduction over a wide exposure range.

Modern color photographic copying materials based on silver halide generally contain so-called 'DIR couplers (DIR-development inhibitor releasing) to improve color reproduction. When development takes place in a silver halide emulsion layer based on the suppressing effect of these DIR couplers, the gradations obtained in this layer combination after exposure to outgoing light are limited to only one color component of the light (e.g. red light only). , green light only or blue light only) than the tones obtained after exposure. This effect is referred to in the literature as the Interimage Effect (IIE).

This I I E (T. H. James, The Theory of the Photographic Process, 4th edition, Macmillan Company New York (T. H.

James, The Theory of the P
photographic Process.

4th Edition, McMillan Co.
, N, Y.), (1977) pp. 574 and 614)
is measured as the percentage increase in slope when the color tone obtained when exposed to light in a particular spectral region is compared to the color tone obtained when exposed to light output.

Other advantageous effects of DIR couplers consist in improved sharpness due to scattered color particles and high so-called edge effects (Reference: C, R.

Barr, J.R., Gistor, P.W., Pittam: “Development Inhibitor Releasing (D.I.R.
)・Coupler in Color 7 Otographie”,
Photography Science Engineering (C,R
, Barr, J., R., Thlstle, P.W.
, Vittum: ” Development
Inhibita Releasing (DIR)
Couplers in Co1our Photo
graphy”.

PhoLo, Sci, Eng, ), top 1174.2
14 (1969).

Modern color photographic copying materials generally contain not only one silver halide layer for each of the individual spectral regions, blue, green and red, but also several partial layers with different sensitivities. (For example, German patent no. 112147
No. 0). Such partial layers of the same spectral sensitivity can be duplicated adjacent to each other in a layer combination or form a multilayer packet. Other layer combinations are also known, in which the individual sublayers have other arrangements (separated from each other by separation layers or filter layers) (for example DE 195 8 709, DE 25
30645, 2622922).

In the case of photographic materials containing a number of light-sensitive sublayers of different sensitivities but sensitive to the same spectral region, DIR couplers are generally added only to the less sensitive sublayers, or at least They are distributed over the individual sublayers in such a way that they have the weakest suppressing effect in the sublayers with the highest photosensitivity.

Therefore, in modern color photographic negative copy materials, the difference between the color density curve obtained after exposure to the separated color components and the corresponding density curve obtained after exposure to Idemitsu is small in areas of low color density. much smaller than in areas of high color density (see curves 1 and 2a in FIG. 1). As a result of such variations in color density, the color reproduction of positive copies produced from such color negative recording materials will vary depending on whether the negative was underexposed, overexposed or overexposed. This is particularly disadvantageous for professional color negative films.

It is an object of the invention to provide a color photographic negative recording material in which the color reproduction is as constant as possible over a wide exposure range.

This problem is solved according to the invention by having at least one red-sensitive, at least one green-sensitive and at least one blue-sensitive silver halide emulsion layer, each of which has a complementary color to the spectral sensitivity. The photographic material has a color coupler associated with it to produce a colored image dye, and this photographic material has a color coupler that differs in sensitivity to record light from at least one of the red, green or blue spectral regions. Both contain two sublayers, the more sensitive layer of these sublayers containing a DIR compound, and the negative recording material contains a triplet of cyan,
For at least one of the magenta and yellow colors, the color density obtained after color separation exposure and development is 0.4 above the fog of the same color after additive exposure to Idemitsu. Exposure (logtxt
) at least 0.2, - preferably at least 0
．． The problem is solved by a color photographic negative recording material which is characterized by a large size.

The color density curve obtained after color separation exposure in the negative recording material according to the invention has a greater gradation in the low exposure areas than in the high exposure areas. The regions of underexposure and overexposure are defined by the exposure value (logl·E), which corresponds to a given color density value on the color density curve resulting from additive exposure to internal light. Thus, for example, according to the negative recording material according to the invention, exposures in which the color density of the same color obtained after additive white light exposure is between 0.1 and 0.5 above the fog, preferably between 0.2 and 0.4 The color gradation obtained after color separation exposure and development in the exposed area is as follows: Greater than the color gradation obtained.

The recording material according to the invention here differs from the conventional recording material in that the color gradation of the color density curve obtained after color separation exposure in the low exposure region defined above is smaller than in the high exposure range defined above. It is fundamentally different from

The invention will now be described with reference to the accompanying drawings.

FIG. 1 diagrammatically compares the color density curve with a conventional recording material obtained from color separation exposure (curve 2a) with that obtained with the material according to the invention (curve 2b); shows the corresponding color density curves of the same color (identical for both recording materials) obtained from white light exposure;
FIG. 2 shows the color density curve bgXs p obtained from a color separation exposure of a conventional recording material (Example 1, Sample IA).
p' and gb' (solid curves) and the corresponding color density curves (dashed curves) of the same color obtained from additive white light exposure; Figures 3 and 4 show two different recording materials according to the invention (
Example 11 Color density curve bg' obtained from color separation exposure of samples IB and Ic), pp tree, gb book (solid curve) and corresponding color density curve of the same color obtained from additive white light exposure (dashed curve) shows.

Thus, the negative recording material according to the invention shows that the color density curve obtained from the color separation exposure (FIG. 1, curve 2b) is different from the curve obtained from the conventional material (FIG. 1, curve 2a); two color density curves that rise steeply at the low color densities of the negative and then run almost parallel to the corresponding color density curves with internal light exposure over a wide exposure range, thereby creating two color density curves over as wide an exposure range as possible. An almost constant density difference between (color separation exposure and internal light exposure) is obtained.

The difference between the color density curve obtained from an additive white light exposure (curve 1) and that obtained from a color separation exposure (curves 2a and 2b) as exemplified in FIG. This is explained by the mutual image effect that occurs between layers with different values. In other words, the negative recording material according to the invention has a special interaction depending on the exposure and which can be seen diagrammatically in the comparison of curves 2bC (according to the invention) and 2a (commonly used recording material) in FIG. Characterized by image effects. Whereas in conventional recording materials the interimage effect is, to a first approximation, proportional to the exposure (logl-t) or the color density over a wide range of exposures;
In the negative recording material according to the invention it is essentially constant over a wide range of exposures, especially in the range of overexposures, and is therefore largely independent of the exposure actually carried out.

Such color density dependent IIE curves (according to the invention) also improve detail recording at high color saturations (especially in overexposed areas of negative recording materials). The measures described herein are therefore described in German Patent Application No. 362 176
It is particularly advantageous to combine it with the measures for improving detail recording at high color saturation as described in No. 4.

The exposure-dependent IIE curve according to the present invention can be expressed, for example, by the following means (the present invention is not limited to these means):
This can be achieved by: a) DIR compounds, especially those in which the inhibitor has a high diffusivity Df (>0.4), exclusively or It is added at least in an amount that provides stronger suppression in the color density region of the most sensitive sublayer than in other sublayer regions. The reduction in tone due to internal light exposure resulting from development inhibition in the most sensitive layer can advantageously be compensated by the application of higher amounts of silver halide and/or coupler.

b) The IIE curve according to the invention is constructed by a) in which the most sensitive sublayers containing the appropriate loading of DIR compounds are arranged alternately (always separated by a separating layer and/or a filter layer) and combined to Particular advantage is obtained if a sensitive layer packet is formed, while the less sensitive sublayers are accommodated as single, double or multilayer packets and form a layer unit of lower sensitivity from time to time. .

C) Also for the recording material according to the invention, the DIR coupler used in the less sensitive partial layer has a low diffusivity (≦
It is advantageous if it contains a suppressor of 0.4) (as opposed to the most sensitive partial layer). In this case, it is also possible to omit adding the DIR compound into all of the less sensitive partial layers, unless prohibited by the desired color grain size. this is,
This is possible, for example, when T-particles with a particle size of

d) In a particular embodiment of the invention, so-called smearing couplers are additionally used in the most sensitive partial layer. These are normally resistant to diffusion, but when processed result in smeared color particles due to the limited diffusivity of the dye produced (UK Patent No. 2083640, European Patent No. 00
96873, German Patent Application Publication No. 3324533, European Patent No. 0109831). The otherwise occurring increase in color grain size can then be eliminated, for example by increasing the coupler/silver halide ratio in these fast partial layers.

e) It is also advantageous to use DAR or FAR couplers in the most sensitive sublayers to increase the sensitivity.

f) Combination with the measures described in German Patent Application No. 3,621,764 to improve detail reproduction in high color saturation.

g) German Patent Application No. 363 for increasing sensitivity
3713 is combined with a fully colorimetric, black coupling layer.

Recording materials having the properties according to the invention can be obtained by incorporating DIR compounds from conventional recording materials into the l or more most sensitive sublayers present or when these sublayers already contain DIR compounds. This can be obtained by increasing the amount so that the resulting suppression is greater in the most sensitive sublayer than in the corresponding less sensitive sublayer. DI in the most sensitive sublayer
Instead of or in addition to increasing the amount of R compounds, it is also possible to reduce the amount of DIR compounds in the less sensitive sublayers. Mixtures of two or more DIR compounds can be used in both the most sensitive and less sensitive sublayers.

The most sensitive sublayer is highly diffusive (Df > 0, 4)
In addition to containing DIR compounds that release inhibitors of
DIR compounds releasing inhibitors of low diffusivity (D[≦0,4) can also be included in small amounts, for example in amounts up to 30 mol %, based on the total amount of DIR compounds in these layers. On the other hand, the less sensitive partial layer can also contain a DIR compound that releases a highly diffusible inhibitor; It should have a smaller effect than the DIR compound and should therefore be present in the layer in small amounts, for example up to 30 mole % based on the total amount of DIR compound in the slow layer. Maintaining the effectiveness of claim 1 consists in adjusting the amount of DIR compound that releases too high or too low a diffusivity inhibitor. The amount of DIR compound required can be determined from a series of tests, which does not present any difficulty to the person skilled in the art. The following method can be used: exposing the combination layer to be tested behind a gray stage wedge as follows: a) one sample to red light (through a red filter), b)
C) another sample to green light (through a green filter); C) another sample to blue light (through a blue filter); d) another sample to additively sequential red, green, and blue light.

The intensities of red, green and blue light should be adjusted so that additive exposure (-d) gives the same photosensitivity curve as internal light exposure to standard sunlight.

Color density D of 0.4 (above fog) due to additive exposure
(density of the same color) light intensity (logl-t)
in which the color density obtained in the spectrally sensitive layer for a given color when exposed to light of a given color component is at least 0.2 (preferably at least 0.25) greater than 0.4. If found, this is an indication that the amount of DIR compound in the most sensitive layer is sufficient to achieve the objectives of the invention.

In other words, at an exposure (lOgl-1) where the additive exposure gives a density of 0.4 above the fog, the color density obtained from exposure to the separate color components is at least 0.4.
6, preferably 0.65 (above fog).

DIR compounds are primarily coupling compounds, ie compounds that can enter into a coupling reaction with the oxidation products of the color developer used.

The term "DIR compound" does not mean that the present invention is limited to the use of DIR couplers which produce colored products as a result of the coupling reaction, but which, upon reaction with color developer oxidation products, release inhibitors. It is possible,
It was chosen to indicate that it also includes compounds that do not at the same time contribute significantly to the production of color images. Nevertheless, the use of DIR couplers is preferred.

Color couplers can be of the type that provide cyan, magenta or yellow dyes when color developed. Cyan DIR couplers are generally phenolic or
It has a tall-type structure.

Magenta DIR couplers are generally derived from 5-pyrazolones. Yellow DIR couplers can be derived from α-acyl-anilides such as pivaloyl-acetanilide, benzoyl acetanilide or malonic dianilide.

Couplers that give primarily colorless products and at the same time provide development inhibitors are described, for example, in U.S. Pat.
No. 88491.

The inhibitor is introduced into the coupling position of the coupler via a TIME group, a group which can release the inhibitor during a secondary reaction after being released from the coupling position of the coupler when reacting with the oxidation products of the silver halide developer. can be combined. The group TIME is also referred to as a timing group because in the presence of such a group there is often some delay before the inhibitor attached to it is released and becomes active. Known time control groups include, for example, the group 2〇-CH (where the 0 atom is attached to the coupling position of the coupler and the C is attached to the Nl of the inhibitor) (for example, the German patent application no. No. 27031
No. 45); a group which, after separation from the coupler, is subjected to an intramolecular nucleophilic rearrangement reaction and at the same time releases the inhibitor (eg DE 2855697): after separation from the coupler, electron transfer occurs along the conjugated system; a group from which the inhibitor is released (e.g. German Patent Application No. 3105026); or a group in which X (e.g. and R is, for example, aryl (e.g., EP 012
No. 7063) is included.

The group TIME can occur once or twice in the same or different structures or it can be absent at all.

The inhibitor released from the DIR compound upon development can be a heterocyclic mercapto compound or a heterocyclic compound containing nitrogen or without a mercapto group, such as a triazole or benzotriazole derivative. D.I.R.
Many inhibitors of this type are known as components of compounds and are described, for example, in U.S. Pat. No. 3,227,554;
No. 7291, German Patent Application No. 2414006,
Same No. 2655781, Same No. 2842063, Same No. 3
No. 209486, No. 3427235 and No. 371
No. 1418. The inhibitors released from the DIR compounds, especially those in the sensitive partial layer, have a high diffusivity Df (degree of diffusion), which is advantageously greater than 0.4. For the definition of diffusivity Df and its assay method, see European Patent No. 0115302.

For the purposes of the present invention, the degree of diffusivity Df is calibrated and defined by the following method: Multilayer test materials A and B are prepared as follows: Test material A on a transparent layer support of cellulose triacetate. Apply the following layers in the order listed.

The amount stated is based on 1 m''. The applied amount of silver halide is the equivalent of the corresponding AgN0.Silver halide emulsion 1i AgNOs l 00 0.5 per II: 4 of j
- Stabilized with hydroxy-6-methyl-1,3,3a,7-thitraazaindene.

Silver halide emulsion = Silver iodobromide emulsion containing 7 mol% silver iodide, cubic crystals with an average grain size of 0.5 μm and one rounded corner.

Layer 1: Red sensitized silver halide emulsion of the above type from AgNOx 4-57f/, cyan coupler KO,751 dissolved and dispersed in dibutyl phthalate 0.62, gelatin 0.603. ? .

Layer 2: AgNOs 2-63j? , white coupler 0.382 and gelatin 1.17. ? An unsensitized silver halide emulsion.

Layer 3: Protective layer containing 1.339 gelatin.

Layer 4: Gelatin 0.82. ? and carbamoylpyridinium salt (CAS registration number 6541 l-60-1) 0.
A hardened layer containing 541.

Cyan Coupler K H3 ■ Test Material B Test material B was prepared in the same manner as test material A except that layer 2 consisted of 0.3461 i of white coupler and 0.90 i of gelatin.

Test materials A and B were exposed to interstitial illumination of a 100 watt incandescent lamp in a dark room at a distance of 1.5 m and an exposure time of 15 minutes.

Developed using “The Journal of Photography” (
”The Journal of Photography
hy") 1974, pp. 597-598, except that the developer was diluted to 20% by volume.

The modified developer solution containing the development inhibitor to be tested was a methanol/water (8:2) mixture (pH adjusted if necessary for dissolution).
(can contain up to 9 NaOH) medium suppressant 0.0
It was prepared by adding a 2 molar solution to the developer solution and then adding water until a 20% diluted developer solution by volume was obtained.

Each of test materials A and B is developed in an inhibitor-free developer and then processed in successive operating steps.

The resulting cyan density is measured with an optical densitometer.

The diffusivity width is determined according to the following formula: where D is the color density of test materials A and B after development in the developer described above without added inhibitor, and DA, DB is the color density of test materials A and B after development in the developer described above containing an inhibitor at a concentration meeting the formula:

Examples of a number of inhibitors and their diffusivity Df are shown below: D.

D.

D.

Since it is desirable for the sweetly released inhibitor to enter the development process as soon as possible, it is highly desirable to use highly reactive DIR compounds, i.e. those with high reaction rates in reaction with developer oxidation products. It's advantageous.

A method for assaying coupling reactivity is described in German Patent Application No. 2704797.

Preferred DIR compounds for the present invention have reactivity K greater than 5.000 tomol"1 sec-1. Examples of suitable IR compounds are shown below:
lo loco
B
[B] Zeng
Flash 〇-ri Rolo
Lolo
Q Lolo
Lo Lolo
Lo Lolo
Lolo
8%
(% J Rollo DIR to the most sensitive partial layer of the negative recording material of the present invention
Addition of compounds or increasing the amount of DIR compounds in these layers generally results in a reduction in the gray scale obtained when exposing these layers to internal light. This fundamentally undesirable effect can be compensated by increasing the amount of silver halide and/or also the amount of color coupler in these layers.

If the most sensitive sublayers with different spectral sensitivities (
These may optionally be separated only by a separation layer or a filter layer) are combined to form one layer packet (which is generally placed above a less sensitive sublayer differing in spectral sensitivity). It is particularly advantageous, especially for obtaining high mutual image effects. On the other hand, these less sensitive partial layers can also be combined to form a layer packet of single, double or multilayers of different spectral sensitivities. In this embodiment of the negative recording material according to the invention, it is possible to insert not only non-light-sensitive layers but also sub-layers of different spectrally sensitive nature between the same spectrally sensitive sub-layers (US Pat. No. 3,663,228). (see German Patent Application No. 2530645). In this embodiment, therefore, since the most sensitive sublayers of different spectral sensitivities are arranged relatively close together in the combined layer, they are capable of particularly close interaction and the resulting mutual interaction. The image effect is mainly due to relatively low exposure
The result is a portion of the color density curve corresponding to og I·t, which is desirable for the purposes of the present invention.

For the materials according to the invention, a higher than usual coupler/silver halide ratio (i.e. coupler approximately 0-1 jJ:
the ratio of AgNOs l l) in the most sensitive sublayer, and the aforementioned so-called smearing where it takes part in the color coupling reaction to produce a dye with little or limited mobility. It is advantageous to keep the color granularity in these partial layers sufficiently low by using couplers.

By "slight or limited mobility" is meant such mobility that the peripheries of the individual color spots produced in color primary development sink into each other at the edges, creating a smearing effect. This degree of mobility is to be distinguished from complete immobility in conventional photographic layers, which is a desirable property of color couplers and resulting dyes to produce sharp images in conventional photographic recording materials. and is also to be distinguished from the complete mobility of the dye, which is required, for example, in dye diffusion methods. The last-mentioned dyes almost always contain at least one group which makes them soluble in alkaline media. The degree of slight mobility required by the invention can be adjusted by varying the substituents, e.g. to adjust the solubility of the oil former in organic media or the affinity for the binder matrix as desired. be able to.

The use of DAR or FAR couplers to increase the sensitivity in knee fast partial layers, i.e. development accelerators or the use of a coupler releasing a fogging agent; - the generation of a light external sensitivity in one of the green-sensitive layer and the blue-sensitive layer; this light external sensitivity is 8 to 25 DIN lower than the main sensitivity; as described in German Patent Application No. 3,621,764; and - the additional use of a panchromatically sensitized silver halide emulsion layer, which produces gray (black and white) images and is the most sensitive color-producing layer. German Patent Application No. 1547707 and German Patent Application No. 363, which have a higher photosensitivity than German Patent Application No.
Described in No. 3713.

The color photographic negative recording material according to the invention contains a series of several silver halide emulsion layers, each of which has a color coupler spatially and spectrally associated with it;
an optional non-photosensitive binder layer is disposed between the silver halide emulsion layers, and at least one spectral region,
It comprises at least two partial layers of different sensitivity for recording red, green or blue, the more sensitive layer containing a relatively large amount of DIR compounds.

The halide in the light-sensitive silver halide emulsion used in the light-sensitive layer can be chloride, bromide, iodide or mixtures thereof. For example, the halide content of at least one layer can consist of 0-12 mol% iodide, 0-50 mol% chloride, and 50-100 mol% bromide.

In embodiments, the halide is primarily in a tight crystalline form, such as cubic or octahedral;
can be a transitional form. They may be characterized by the fact that their thickness is primarily greater than 0.2 μm. The average diameter to thickness ratio is preferably less than 8:1, where the particle diameter is defined as the diameter of a circle with an area equal to the projected area of the particle. In other embodiments, all or some of the emulsions may contain primarily tabular silver halide crystals, the diameter to thickness ratio of which is greater than 8:1. The emulsion can be a heterodisperse or a monodisperse emulsion, which preferably has an average grain size of 0.3 μm=1.2 μm. Silver halide grains can also be used, for example in German Patent Application No. 3,404,854.
It can also have a layered particle structure as described in the above issue.

The emulsions can be chemically and/or spectrally sensitized by conventional methods and they can also be stabilized with suitable additives. Suitable chemical sensitizers, spectral sensitizers and stabilizers are described, for example, in Research Disclosure.
1 7643, especially chapters ■, ■, and ■.

"Spatial association" refers to the spatial relationship of the color couplers with respect to the silver halide emulsion layer, i.e., their interaction with the silver image produced by development and the color coupler. This means that the spatial positional relationship is such that an image match can be obtained between the color image and the color image that is displayed. This is generally achieved by incorporating the color coupler directly into the silver halide emulsion layer or into an optionally non-light sensitive binder layer adjacent thereto.

“Spectral association” means that the spectral sensitivities of each of the light-sensitive silver halide emulsions and the colors of the partial color images produced from the color couplers spatially associated therewith have a certain relationship to each other. , meaning that each of the spectral sensitivities (red, green, blue) is associated with a different color of the corresponding partial color image (generally in the order of the colors cyan, magenta and yellow, for example).

Each of the silver halide emulsion layers can be associated with one or more color couplers. When a number of silver halide emulsion layers of the same spectrally sensitive nature are present, each of these layers can contain color couplers and the various color couplers need not necessarily be identical, provided that they are color developable. When used, at least approximately the same color is produced, usually a color that is complementary to the color of the light to which these silver halide emulsion layers are primarily sensitive.

The radiation-sensitive silver halide emulsion layer most often has associated with it a non-adhesive color coupler, usually a phenolic or a-7 thol-based coupler, to produce a cyan partial color image: green The light-sensitive silver halide emulsion layer has associated therewith at least one non-diffusive color coupler, generally a yagenta coupler of the 5-pyrazolone, indashilon or pyrazoloazole series, for producing a magenta partial color image. and the blue-sensitive silver halide emulsion layer has associated therewith at least one non-diffusive color coupler, generally a color coupler containing an open chain ketomethylene group, for producing a yellow portion color image.

Color couplers of this type are known in large numbers and are described in many patent specifications. Reference may be made, for example, to the following publications: “Mitteiungen Aus den Verschungslaboratorienkushide J Reagfa, Lebenorekusen/Munich” (“Mittei
Lungen atls den Forschung
sIaboratorien der Agfa, L
everkusen/M(inchen”)s Volume 1
11 pages (1961), W. Peltz (W.

PELZ) by “FarbKglar” (“FarbK”)
ul)I)ler”) and “The Chemistry of Synthetic Dice”, Academic Press (
“The Chemistry of 5ynthet
ic Dyes'', Academic Press),
4, 341-387 (1971) Publication by Nio (K, vENKATARAMAN).

Color couplers are conventional 4-equivalent couplers or 2-equivalent couplers, which generally require less silver halide for color production.
Any equivalent coupler may be used.

2-equivalent couplers are those which are virtually colorless and those which themselves have a strong color which is lost during the color coupling reaction and replaced by the color of the image dye formed;
It includes both. The latter coupler can additionally be present to serve as a masking coupler to offset undesirable lateral density of image dye. White couplers can also be recognized as 2-equivalent couplers, although they do not provide dye on reaction with developer oxidation products. Examples of such 2-equivalent couplers also include DIR couplers and DAR and FAR couplers used in accordance with the present invention.

The usual layer supports are suitable for the recording material according to the invention, for example supports of cellulose esters such as cellulose acetate or supports of polyester. Pure supports are also suitable, which can be coated, for example, with polyolefins, especially polyethylene or polypropylene. For example, see Research Disclosure 17643, Chapter X■, mentioned above.

Common hydrophilic film formers, such as proteins, as protective colloids or binders for the layers of the recording material.
In particular gelatin can be used. Casting aids and plasticizers can also be used. Regarding this, see Research Disclosure 17643, ■, ■, and ■.
See chapter.

The layers of the photographic material can be hardened in conventional manner, for example using hardeners containing at least two reactive oxirane, aziridine or acryloyl groups. The layer can also be hardened by the method described in DE-A-2218009.

Additionally, the photographic layers or photographic multilayer materials can be hardened with hardeners based on diazine, triazine or 1,2-dihydroquinoline, or hardeners of the vinyl sulfone type.

Other suitable curing agents include German Patent Application No. 2439
No. 551, No. 2225230, No. 2217672
No. and Research Disclosure 17643. It is described in Chapter X.

Other suitable additives are listed in Research Disclosure 17643 and the “Product Licensing Index”.
ndex”), December 1971, pp. 107-110.

Suitable color developer materials for the materials according to the invention include, in particular, materials based on p-phenylenediamine, such as 4-
Amino-N,N-diethyl-aniline hydrochloride, 4-amino-3-methyl-N-dithyl-N-β-(methanesulfonamido)-dithylaniline sulfate hydrate, 4-amino-3-methyl-N -ethyl-N-β-hydroxyethylaniline sulfate, 4-amino-N-ethyl-N-(2-
methoxyethyl)-m-toluidine-di-p-toluenesulfonic acid and N-ethyl-N-β-hydroxyethyl-p-phenylenediamine. Other suitable color developers are described, for example, in the Journal of the American Chemical Society.
Chen+, Soc, ) 73.3100 (1951)
and G. Heist, Modern Photographic Grossing, 1979, John Riley &
Sands, New York (G, Haist, Moder
n Photographic Processing
.

1979, John Wiley and 5ons,
New York) from page 545 onwards.

After color development, the material is usually bleached and fixed. Bleaching and fixing can be carried out separately or together. Compounds common as bleaching agents, such as Fe3+ salts and Fe”
Complex salts such as ferricyanide, dichromate, water-soluble cobalt complex salts, etc. can be used. Iron-■ complex salts of aminopolycarboxylic acids are particularly preferred, particularly complex salts of, for example, ethylenediaminotetraacetic acid, nitrilotriacetic acid, iminodiacetic acid, N-hydroxyethyl-ethylenediaminotriacetic acid and alkyliminodicarboxylic acids and the corresponding phosphonic acids. Persulfates are also suitable bleaching agents.

Example 1 A color photographic recording material for color negative development was prepared by applying the following layers to a transparent layer support of cellulose triacetate in the order given.

The quantities relate in each case to 1 m2. The amount of silver halide applied is the corresponding equivalent of AgNO3. All silver halide emulsions were AgN0. lOOj? Hit 0.52
4-hydroxy-6-methy” l * 3 + 3
a.

It was stabilized with 7-tetraazaindene.

Layer l (antihalation layer) Black colloidal silver sol containing 0.22 Ag, 1.29 gelatin, 0.11 UV absorber UV-1° 0.22 UV absorber UV-2, 0,021 Tricresyl phosphate (TCP) of 0.031, and dibutyl phthalate (DBP) of 0.031; Layer 2 (Miclad interlayer) 0.25. ? Silver iodobromide microclad emulsion (0.5 mol % iodide; average grain size 0 .07 μm); Layer 3 (first red sensitized layer) 3.0.9 AgN0. and 2.52 gelatin, 0.75jl cyan coupler C-1° 0.041 red mask MR-1° 0.042 DIR coupler DC-1° 0.5.9 T
Red sensitized silver iodobromide emulsion obtained from DBP of CP and 0.12j) (3 mol% iodide;
Average particle size 0.3 μm) + Layer 4 (middle layer) 0.82 gelatin, 01.0052 2,5-di-t-pentadecylhydroquinone, 0.05j TKP and 0.0! M's DBP.

Layer 5 (first green sensitizing layer) 2.62 AgNO3 and 2.02 gelatin, 0.69 magenta coupler M-1° 0.092 yellow mask MY-11 0.02 jl DIR coupler DC- 2,0,04j?
DIR coupler DC-3,0.49 TCP and 0.39 DBP.

Green-sensitized silver iodobromide emulsion (4.5 mol % iodide; average grain size 0.3 μm) obtained from Layer 6 (yellow filter layer) Yellow colloidal silver containing 0.02jJ of Ag passivated with g/I Ag), 0.82 gelatin, 0.15. ? of 2,5-di-t-pentadecylhydroquinone and 0.22 of TCP; Layer 7 (first blue sensitive layer) 0.9 jl of AgN (h and 1.752 of gelatin, 0.85 jl of yellow coupler Y) -1° DIR coupler D-3 of 0.22 and TCP of 0.9I.

Silver iodobromide emulsion obtained from (4.5 mol % iodide; average grain size 0.3 μm); Layer 8 (intermediate layer same as layer 4) Layer 9 (second red sensitized layer) 3. 0. ? of AgNO3 and 2, OI of gelatin, cyan coupler C-2 of 0.201, red mask MR-1 of 0.021°, TCP of 0.152 and DBP of 0.102.

Red sensitized silver iodobromide emulsion obtained from (6 mol% iodide,
Average particle size 0.8μn+) + Layer 10 (intermediate layer same as layer 4) Layer 11 (second green sensitized layer) AgN0. of 2.32. and 1.6jl gelatin, 0.149 magenta coupler M-2, 0,039 yellow mask MY-1 and 0.159 TCP.

Green sensitized silver iodobromide emulsion (6 mol% iodide,
Average particle size: 0.7 μm); Layer 12 (yellow filter layer, same as layer 6); Layer 13 (second blue-sensitive layer): 0.95. ? AgN0. and 0.72 gelatin, 0.18 jl yellow coupler Y-1 and 0.22 TCP.

Silver iodobromide emulsion obtained from 0.59 AgN0. and gelatin of 1.21, hardener H-1 of 0.41, compound F-1 of 1.02, DBP of 0.089.

Silver iodobromide micrad emulsion (0.5 mol % iodide, average particle size 0.07 μm).

Sample IB (according to the invention) AgNO, dosage: in layer 3, decreased from 3.02 to 2.2:J, in layer 5, 2.
62 to 2. Decrease to OI, in layer 7, from 0.92 to 0.8
Decrease to 2.

Coupler coverage: In layer 9: 0.401 of cyan coupler C-2 instead of 0.201; in layer 11: magenta coupler M-2 of 0.30 JP instead of 0.141; in layer 13: 0. Yellow coupler Y-1° DIR coupler coverage of 0.25 & instead of 189: In layer 3: 0.25 & instead of 0.041. Olj DIR coupler DC-1° in layer 5: 0.0H DIR coupler D instead of 0.02
C-2 and no DIR coupler DC-3, in layer 7: 0.059 DIR coupler DC-3 instead of 0.02,9, in layer 9: 0.041 DIR coupler DC-4, layer 11
Middle: 0.02j DIR coupler DC-4 and 0.03
DIR coupler DC-3 at 0.102° in layer 13: DIR coupler DC-3 at 0.102° Sample 1c (according to the invention) Same as sample 1B with the following changes: Layer 9 is replaced by cyan coupler C-2 Contains 0.322 cyan coupler C-3 (smearing coupler).

Layer 11 contains 0.261 magenta coupler M-3 (smearing coupler) instead of magenta coupler M-2.

The following compounds were used:
9 Yo.

Each of samples IA, IB and Ic was exposed to white, red, green or blue light behind a gray step wedge (exposures to one light were done additively with sequential exposures of red, green and blue light). ).

The sample was then “The British Journal of
Photography” (“The Br1tish Jo
Urnalof Photography”) 1974
．． It was processed by the color negative processing method described on pages 597-598.

FIG. 2 shows the color density curve obtained with layer combination IA. The three color density curves (yellow, magenta and cyan) obtained after (additive) light exposure are shown in dashed lines in FIG.

The solid curves are the color density curves obtained after exposure to the separated color components, i.e. the cyan curve after red exposure (bg''), the magenta curve after green exposure (pp lines) and the yellow curve after blue exposure (gb*). ).

From Figure 2, it can be seen that the density of the corresponding color density curve obtained by exposure to color separation components and (additively) 1
The density difference between those obtained by exposure to light is seen to increase as usual with increasing exposure. This has the undesirable result that the color reproduction of the positive will be different depending on whether the negative was underexposed, normally exposed or overexposed.

The corresponding color density curves of samples according to the invention are shown in Figure 3 (
Layer combination IB) and FIG. 4 (layer combination IG).

In this case, the density difference between the curve with internal light exposure and the corresponding curve with separate color component exposure is virtually constant over a wide exposure range, and therefore underexposure of the negative within this exposure range, Approximately constant color reproduction over exposure and overexposure is obtained in the positive.

The increased loading of coupler in the fast partial layers (9, 11 and 13) of layer combination IB (compared to CIA) increases the color granularity. Table 1 shows that the disadvantages due to this high coupler/silver halide ratio can be largely eliminated by using so-called smearing couplers, which cause color particles to bleed due to limited dye diffusion during processing. can.

Table 1 Color granularity (RMS) layer combination at color density 1.0 Cyan Magenta IA
I3.2 14.71B 29
．． 0 31.9Ic 14.4
15.0 Example 2 For comparison, sample 2A was prepared containing the following layers: Support, layer 1 (antihalation layer) and layer 2 (microclad interlayer) as in example 1.

Layer 3 (low sensitivity red sensitive layer) 1.22 AgN0. and i, oo, p gelatin, 0.2. ? cyan coupler C-11 0,252 cyan coupler C-4, 0,02,? Red mask MR-1゜0.025. ? DIR coupler DC-1゜0.309
TCP of.

Red sensitized silver bromide iodide emulsion obtained from 0.1/DBP1 (4 mol% iodide;
Core/shell type; uniform dispersion; average particle size 0.22 μm); Layer 4 (medium sensitivity red sensitive layer) 1.61 AgNO3 and 1.209 gelatin, 0.121 cyan coupler C-1°0. 201 cyan coupler C-4, 0,02:I red mask MR-1° 0.0309 DIR coupler DC-1° 0.017.
f? DIR coupler DC-3,0,22 TCP.

DBP of 0.152.

Red sensitized silver bromide iodide emulsion obtained from (3 mol% iodide;
Core/shell type; uniform dispersion; average particle size 0.6 μm); Layer 5 (intermediate layer same as layer 4 of Example 1): Layer 6 (low sensitivity green sensitive layer) 1, OI AgNO3 and 0.60 ．． ? gelatin of 0.429, magenta coupler M-4 of 0.082, yellow mask MY-1° of 0.021, DIR coupler DC-2 of 0.021 TCP of 0.05j'.

Green sensitized silver bromide iodide emulsion obtained from (4.5 mol % iodide; core/shell type: uniformly dispersed; average grain size 0.5 μm): Layer 7 (medium sensitivity green sensitive layer) 1, 52 AgNO3 and 0.91 gelatin, 0.481 magenta coupler M-4, 0,049 yellow mask MY-1° 0.025. ? DIR coupler DC-2,0,016
jl DIR Coupler DC-3,0,60&TCP.

Green sensitized silver bromide iodide emulsion obtained from (4.5 mol % iodide: core/shell type: uniformly dispersed; average grain size 0.5 μm); Layer 8 (same as layer 6 of Example 1) yellow filter layer): layer 9 (
Low sensitivity blue sensitive layer) 0.652 AgN0. and 1.60j? gelatin, 0.9M yellow coupler Y-2, 0,239 DIR coupler DC-3, 1,09 TC
P.

Enhanced sensitized silver bromide iodide emulsion (4.5 mol % iodide; uniformly dispersed; average grain size 0.3 μm) obtained from red photosensitive layer) 2.02 AgN0. and 1.70jJ gelatin, 0.18jJ cyan coupler C-5, 0,029 red mask MR-1°0.16# DBP.

Red sensitized silver bromide iodide emulsion (8 mol % iodide; average grain size 0.9 μm) obtained from Layer 12 (intermediate layer same as layer 5) Layer 13 (highly sensitive green sensitive layer) 1.81 AgNO3 and 1.50.9 gelatin, o, t s, p magenta coupler M-5,0,05,
9 yellow mask MY-1° TCP of 0.172.

Green sensitized silver bromide iodide emulsion obtained from (6 mol% iodide;
Average particle size 0.9 μm); Layer 14 (yellow filter layer same as layer 8) Layer 15 (high sensitivity blue sensitive layer) 1.09 AgNO3, 0.809 gelatin, 0.242 yellow coupler Y-3 , 0,2(H polybutyl acrylate, 0.205' TCP.

Blue sensitized silver bromide iodide emulsion obtained from (10 mol % iodide; average grain size 1.2 μm); Layer 16 (protective layer) 0.42 AgN01 and 1.02 gelatin, 0.32 Same UV absorber mixture as in layer l, DBP of 0.12.

Silver bromide iodide microrad emulsion (0.5 mol % iodide) obtained from Layer 17 (hardened layer) 0.51 gelatin, 0.42 hardener (CAS registration number 65411-60-
1) Polymethacrylate particles of 0.25mm (average particle size 1.5
μm).

Sample 2B (according to the invention) was prepared with layers 1-17 as in Sample 2A, but with the following changes.

Coupler dosage: In layer 3, 0.121 cyan coupler C-L instead of 0.209 0.152 cyan coupler C-4 instead of 0.25I
, in layer 4, 0.12. ? 0.0761 cyan coupler C-1 instead of 0.13jl cyan coupler C-4 instead of 0.21
, 116, magenta coupler M-4 of 0.25 & instead of 0.429; in layer 7, magenta coupler M-4 of 0.29:j instead of 0.481; in layer 9, 0.92 of Yellow coupler Y- instead of 0.65&
2. In layer 11, cyan coupler C-5 at 0.382 instead of 0.189; in layer 13, magenta coupler M5 at 0.369 instead of 0.189; in layer 15, instead of 0.241. 0.45: I yellow coupler Y-3° DIR coupler dosage: In layer 3, no DIR coupler; in layer 4, DIR coupler DC-1° of 0.0152 instead of 0.031; instead of 0.0179 DIR coupler D of 0.0087 to
C-3, no DIR coupler in layer 6, 0.012. in layer 7 instead of 0.0251. ? DIR of
Coupler DC-2, DIR coupler D of 0°0072 instead of 0,0169
C-3, no DIR coupler in layer 9, 0.06ff DIR coupler in layer 11 DC-layer 13
Medium, 0.059 DIR coupler DC-4, layer 15, 0.02j? The following color couplers were additionally used in Example 2:
Size CJ L)
The following DIR couplers were additionally used in Example 2: Samples 2A and 2B were exposed and processed as in Example 1.

The obtained color density curve was calculated in the same manner as in Example 1, Figure 5 for sample 2A (comparison); Sample 2B (according to the invention) is shown in FIG.

The characteristics of the obtained color density curve are listed in Table 3.

:1 The main features and aspects of the invention are as follows.

1. Contains at least one red-sensitive, at least one green-sensitive, and at least one blue-sensitive silver halide emulsion layer, each of which emulsions provide a complementary color image for their respective sensitivity spectra. The recording of light from at least one of the red, green and blue spectral regions, having a color coupler associated to form a dye, consists of at least two sublayers differing in their photosensitivity. In photographic negative recording materials in which the higher partial layer of is carried out by one containing a DIR compound, for at least one color of the triad of cyan, magenta and yellow, additive white light exposure is applied to that color. The color density obtained after color separation exposure and development at an exposure (log I·t) that produces a color density of 0.4 above fog is at least 0.2 greater than the density obtained from an additive white light exposure. Recording material characterized by.

2. Recording material according to item 1 above, in which the inhibitor released from the DIR metallurgy in one of the most sensitive partial layers has a diffusivity D greater than 0.4.

3. Clause 1 or 2 above, wherein the inhibitor released from the DIR compound in one of the less sensitive sublayers has a diffusivity less than or at most equal to 0.4. Recording materials listed.

4. The DIR coupler in the most sensitive partial layer is 5.
4. The recording material according to any one of items 1 to 3 above, which has a coupling reactivity of 000J2X molar IX seconds-1 or more.

5. at least one relatively sensitive silver halide emulsion sublayer containing a DIR compound for recording light from each of the spectral regions red, green and blue and at least one less sensitive halogen; The more sensitive silver halide emulsion sublayers, which may optionally be separated only by non-photoforming layers, are combined to form a more sensitive silver halide emulsion layer. 5. The recording material according to any one of items 1 to 4 above, which forms a unit.

6. at least one more sensitive silver halide emulsion sublayer containing a DIR compound contains a coupler that yields a dye with limited mobility upon color development;
The recording material according to any one of items 1 to 5 above.

7. The method according to items 1 to 6 above, wherein a highly sensitive silver halide emulsion layer which is sensitized in a panchromatic manner and which produces black and white images is disposed on the layer which produces color images. Recording materials listed in any of the above.

[Brief explanation of the drawing]

FIG. 1 shows the color density curves obtained by color separation exposure (curve 2a with conventional recording material, curve 2b with recording material of the invention) and the corresponding color density curves obtained by additive white light exposure (curve 2a with conventional recording material, curve 2b with recording material of the invention). 1) is shown. Figure 2 shows the color density curves obtained from a conventional recording material (Example 11 Sample IA), and Figures 3 and 4 show the color density curves of two recording materials according to the invention (Example 1, Samples IB and Ic). Figure 5 shows the recording material of the comparative example (Example 2, Sample 2A), and Figure 6 shows the recording material of the present invention (Example 2, Sample 2B).
is the color density curve obtained from . In Figures 2 to 6, the solid line bg tree, pp tree, and gb tree are color density curves obtained by color separation exposure, and the dashed line bg,
pp and gb indicate those obtained by additive white exposure. Patent Applicant Age7 Agewelt AktiO□ 〇 -Too〇-1111

Claims (1)

[Scope of Claims] 1. Contains at least one red-sensitive, at least one green-sensitive, and at least one blue-sensitive silver halide emulsion layer, each emulsion layer having a respective sensitivity spectrum. The recording of light from at least one of the spectral regions of red, green and blue has at least two portions having different light sensitivities, with a color coupler associated to produce a color image dye of a complementary color to In photographic negative recording materials consisting of layers, the more sensitive sublayers of which contain DIR compounds, for at least one color of the triad of cyan, magenta and yellow colors: The color density obtained after color separation exposure and development at an exposure (logI·t) where an additive white light exposure yields a color density of 0.4 above the fog for that color is less than that obtained from an additive white light exposure. Recording material characterized in that it is at least 0.2 larger. 2. Recording material according to claim 1, wherein the inhibitor released from the DIR compound in one of the most sensitive sublayers has a diffusivity D_f greater than 0.4. 3. Disposed on the color image forming layer is a panchromatically sensitized high frequency silver halide emulsion layer forming black and white images. Section and 2nd
Recording materials described in any of the paragraphs.