JP3191936B2 - Color photographic recording material - Google Patents

Abstract

A color negative photographic recording material is described in which low emulsion coverage tabular grain silver halide emulsion imaging units are employed. The silver halide emulsion in at least one of the units comprises grains having a tabularity of between about 50 and 25,000. The imaging unit thickness is less than about 4.0 mu m, using a total of no more than 2.0 parts by weight of silver per part of coupler. The imaging unit yields a density of at least 2.0 when exposed and processed.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to negative working photographic recording materials that provide improved performance with reduced silver usage.

In the art relating to photosensitive multilayer color photographic films, the detrimental effects on image sharpness due to increased layer thickness are well known. This effect is due to light scattering by the silver halide grains. In particular, in multilayer color photographic materials, reducing the image sharpness of the emulsion layer closer to the support is of particular interest.

Previous attempts to improve the sharpness of multilayer color negative photographic materials by reducing the thickness of the image recording layer have had limited success. As the amount of silver halide in the image forming layer decreases, the granularity increases due to the smaller number of image forming centers. Other important photographic performance parameters, such as sensitivity, exposure latitude, and high contrast in separate (spectral color) exposures are also
It can be attenuated by reducing the amount of coated silver in the imaging layer.

As the sensitivity (speed) of multilayer color negative working photographic materials increases, the manufacture of such materials having low silver coverage, thin imaging layers without compromising other important photographic performance parameters becomes more difficult. Become. Higher sensitivity multi-layer color photographic materials have higher silver coverage but are often observed to suffer in color and image quality down to the lower speed counterpart. This observation,
It relates to a method of obtaining increased emulsion sensitivity by increasing the size of the silver halide grains to give a higher probability of grains absorbing more light.

This approach to obtaining increased light sensitivity is of limited utility due to the loss of light efficiency with relatively large size silver halide grains. This approach also requires that in an attempt to maintain the number of image centers and thereby minimize granularity, the amount of silver used must be increased. Partial grain development encountered in color negative development exacerbates this condition when most of the coated silver halide remains undeveloped,
And this ratio becomes larger as the particle volume increases.

A very useful approach to increasing the light trapping of particles is to change the particle morphology. US Patent 4,439,52
The use of high aspect ratio tabular silver halide emulsions, as described in US Pat. Nos. 4,672,027 and 4,693,954, provides significant advantages to color negative photographic recording materials. Succeeds. Such advantages include improved speed sensitivity-granularity relationships, increased photographic sensitivity, higher contrast for a given degree of particle size dispersion, higher separation of blue and minus blue speed sensitivity, processing time. And / or smaller image changes as a function of temperature change, the ability to optimize light transmission or reflection as a function of grain thickness, and background or airport X-ray emission with very high speed sensitive emulsions Includes reduced susceptibility to damage.

The silver halide coverage of the high speed sensitive recording material having the appropriate granularity, regardless of the morphology of the silver halide grains, reduces the sharpness of the underlying layer to an undesirable degree. The stringent requirement for reduced granularity in high speed speed films results in virtually complete use of the light incident on the photographic recording material. Thus, silver halide emulsion coverage is actually increased to the point where, as far as granularity is concerned, further changes do not produce any perceptible net benefit.

The sharpness loss occurs partially because the recording material structure thickness allows for geometric spread of light at high angles to the substantial parallel spacing. Large grain emulsions are often very hazy at the level of coverage required to provide acceptable granularity and image density. However, such difficulties can be minimized by using high aspect ratio emulsions. Light scattering by the overlying layers creates high angle light traveling at substantially parallel intervals within the multilayer photographic material, causing a reduction in the resolution of the material.

Other disadvantages result from both the high silver halide coverage and the resulting substantially diffuse light transmitted through the multilayer photographic material. Increasing the diffusion of incident light promotes its absorption by silver halide grains by increasing the optical path length or residence time in the layer. This increased interaction with silver halide is somewhat higher than the off-peak absorption (off-peak ab
sorption), but does not contribute usefully to photographic speed sensitivity. Undesirable non-maximal light absorption is enhanced to a uniform larger range as it results in color smearing.

Furthermore, the maximum light absorption by the overlying layers
Of on-peak light blocks the light that is desired to be absorbed by the underlying layer because the incident light is quantitatively limited. Thus, the spectral response of the underlying layer is substantially distorted from its desired normal state by these two processes. The broadened spectral response creates less accurate color reproduction and reduces the saturation of the rendered image.

Many of these interdependent problems of multilayer photographic materials will be ameliorated if thinner, less turbid silver halide emulsion layers are used. Although there is literature on reducing the level of silver or gelatin in color photographic silver halide recording materials, these documents disclose that reducing silver coverage can be achieved with speed sensitivity, density, exposure latitude contrast and / or granularity. It does not provide an element that does not sacrifice one or more of

Early attempts to reduce silver coverage involved using the silver image generated in the development step as a catalyst in the amplification step. Such a method is described in U.S. Pat.
No. 490, 3,748,138 and 3,822,129, which are referenced in the above-mentioned U.S. Pat. No. 4,439,520. The ultimate purpose of such materials and methods is
The aim was to reduce the amount of silver used in the photographic element. Such as granularity and colorsaturation,
No improvement in photographic performance parameters was obtained.

Attempts to obtain thin silver halide emulsions exhibiting sharpness with improved light sensitivity and reduced graininess are described in Meyer et al., European Patent Application No. 62202, published Oct. 13, 1982. . This application places a light-sensitive silver halide emulsion layer between color coupler layers that contain no light-sensitive silver halide or contain only low-sensitivity silver halide. However, no overall reduction in silver usage has been realized.

JP 63226651 aims at improved sharpness and reduced sensitivity to background radiation with reduced silver usage. However, at low silver coverage, density is sacrificed.

U.S. Pat. No. 4,818,667 describes the use of a photographic recording material having a total thickness of 18 .mu.m or less while maintaining image sharpness. However, this patent
It does not teach reducing silver usage while still maintaining the desired density value.

European Patent Application No. 311104, published April 12, 1989, describes photographic recording materials having 3.0 to 9.0 g / m ² of silver. However, there is no indication that satisfactory density values, adequate contrast and reduced granularity values can be obtained with these materials.

There remains a need for color negative photographic recording materials having thin layers and low silver coverage and having improved photographic performance without sacrificing speed sensitivity.

[Disclosure of the Invention]

We have surprisingly found that when using certain silver halide emulsions, the coverage of silver halide in the imaging unit can be reduced without sacrificing image density, contrast and graininess, and It has been found that, without the need for a special amplification step, it can be substantially reduced than is generally used in color negative working silver halide photographic elements. This gives performance equal to or better than color negative working materials currently used at the same speed sensitivity, while at the same time reducing the amount of silver in the element, at higher speed sensitivity (ISO ≧ 100 2.) Enables the production of color negative photographic materials.

According to the present invention, there is provided a support and at least two silver halide emulsion image-forming units sensitive to different regions of the electromagnetic spectrum, each unit containing a dye-forming coupler and at least one The unit is a highly tabular, red-sensitive cyan dye-forming or green-sensitive magenta dye-forming unit, and (a) 0.2 to 2.0 g / m ^{2 based on} silver, 50% of the projected area of the grain
More than one consisting of a silver halide emulsion provided by tabular grains having a tabularity of between 50 and 25,000, (b) having a thickness (dry film thickness) of less than 4.0 μm, and (c) a coupler. Containing not more than 2.0 parts by weight of silver per part by weight, and (d) producing a maximum image dye density of at least 2.0 when the recording material is exposed and processed, and (e) a cyan or magenta dye-forming unit At least one of the layers has a flatness of 100-500 with more than 50% of the projected area
There is provided a negative working color photographic recording material comprising an emulsion provided by silver halide grains having zero tabular grains.

The color negative photographic recording materials to which the present invention relates typically have an exposure latitude of 2.0 or greater and a contrast (gamma) of 0.9 or less but with a positive sign. Exposure latitude and contrast
bel et al., Photographic Materials and Processe
s, pages 46-50, defined and measured as described in Focal Press, Boston, 1986.

Some color photographic materials intended for reversal processing can be described as containing silver levels and silver to coupler ratios within the above ranges. However, such reversal materials are not useful as color negative materials because they do not have the required exposure latitude and contrast.

The results observed in the present invention indicate that lower silver halide emulsion coverage and the formation of thinner layers would result in reduced image density in the type of high speed sensitive materials to which the present invention is directed. It is contrary. Using less silver and thinner layers leads to a number of advantages. The sharpness of the photographic image is substantially improved, the transmission of light to the underlying layers is improved, the negative blue to blue speed sensitivity separation is increased, and the sensitivity to higher energy background radiation or X-ray radiation Decrease.

Using less silver will result in using less gelatin and using less coupler, related solvents and / or dispersants. This further contributes to thinner layers and lowers raw material costs. Thinner photographic layers with low silver levels lead to increased transmission of incident light, as well as improvements in the distribution of absorbed light between the spectrally sensitized layers. In addition, thinner photographic layers with low silver levels reduce the consumption of processing chemicals, especially fixing agents, thereby reducing the cost of disposing of these chemicals.

Tabular grain silver halide emulsions useful in the present invention include:
It may be composed of silver bromide, silver chloride, silver iodide, silver chlorobromide, silver chloroiodide, silver bromoiodide, silver chlorobromoiodide, or a mixture thereof. These emulsions include (i) high aspect ratio tabular grain emulsions and (ii) thin medium aspect ratio tabular grain silver halide emulsions. High aspect ratio tabular grain emulsions are those that exhibit an average aspect ratio greater than 8: 1. Thin, medium aspect ratio emulsions
Tabular grains having an average thickness of less than 0.2 μm and an average aspect ratio in the range of 5: 1 to 8: 1. Such emulsions are described in Wilgus et al, U.S. Patent No. 4,434,226, Daube.
U.S. Pat.No. 4,414,310 to ndiek et al; U.S. Pat.No. 4,399,215 to Wey; U.S. Pat.No. 4,433,048 to Solberg et al.
No. 4,386,156 to Mignot, U.S. Pat.No. 4,504,570 to Evans et al, U.S. Pat.No. 4,400,463 to Maskasky
U.S. Patent No. 4,414,306 to Wey et al; U.S. Patent Nos. 4,435,501 and 4,643,966 to Maskasky; and Daub
endiek et al U.S. Pat.Nos. 4,672,027 and 4,693,9
No. 64 discloses it. Also, UK Patent No. 1,027,14
No. 6, U.S. Pat.No. 4,379,837, U.S. Pat.No. 4,444,877
No., U.S. Pat.No. 4,665,614, U.S. Pat.No. 4,636,461,
European Patent No. 264,954 and British Patent Application No. 891
6041.0 and 8916042.8 (both July 13, 1989)
Of the invention, such as those described in the title of the invention entitled "Method of Making Tabular Grain Silver Bromoiodide Emulsions and Emulsions Produced thereby")). Those silver bromoiodide grains having a high molar ratio are particularly contemplated. The silver halide emulsion may be monodisperse or polydisperse when precipitated. Emulsion grain size distribution is described in the art, for example, in US Pat. No. 4,865,964 (1989).
Different types and sizes of silver halide, including tabular grains, as described in the title of the invention, "Blend Emulsion Showing Improved Sensitivity-Granularity Relationship", issued September 12, 2012. It can be controlled by techniques for separating and blending the particles.

High aspect ratio tabular grain emulsions and thin medium aspect ratio tabular grain emulsions, and other emulsions useful in the present invention, are referred to as "tabularity" as related to aspect ratio (AR).
It can be characterized by a relationship called (T).
This relationship is given by the following equation: (Where, ecd is the average isometric circular diameter of the tabular grains, t
Is the average thickness of the tabular grains, the dimensions are measured in μm).

Tabular grains have two substantially parallel crystal faces, each of which is substantially larger than all other single crystal faces of the grains. As used herein, the term “substantially parallel” is intended to include surfaces that appear parallel upon direct or indirect visual inspection at 10,000 magnification.

The grain characteristics described above for the silver halide emulsion of the present invention can be easily confirmed by methods well known to those skilled in the art. The isometric circular diameter of a grain is defined as the diameter of a circle having an area equal to the projected area of the grain when viewed in an optical micrograph or an electron micrograph of an emulsion sample. From the shaded electron micrographs of the emulsion samples, it is possible to determine the thickness and diameter of each grain, and the tabularity of the grains. From these measurements, the average thickness, average ecd, and flatness can be calculated.

The projected areas of the tabular silver halide grains meeting the tabularity criteria can be summed. The projected areas of the remaining silver halide grains in the optical micrograph can be summed separately. From the sum of the two,
The percent of total projected area of the silver halide grains provided by tabular grains meeting the tabularity criteria can be calculated.

When the tabular grain emulsion has a tabularity of 50 to 25,000,
Good results are obtained.

Elements wherein at least one emulsion has a tabularity of 100 to 5,000 are preferred, and elements using emulsions having a tabularity of 100 to 2,500 are particularly preferred.

As used herein, the term "unit" refers to all layers within an element that are intended to record radiation within a given region of the spectrum and form a corresponding dye image. It will be appreciated that each imaging unit may be comprised of one or more silver halide emulsion layers sensitive to the same region of the spectrum. This is usually with a high speed sensitive color negative material of the type to which the present invention relates, each unit consisting of two or three adjacent or non-adjacent layers. At least one layer in the unit comprises a silver halide emulsion, as described above, where more than 50% of the projected area is provided by silver halide grains having a tabularity of 50 to 25,000. Preferably, if the unit consists of more than one layer, the other layers or all layers
Although it may consist of an emulsion having a tabularity of 50 to 25,000, this emulsion is in the most light sensitive layer. Other layers (s) as long as the unit's projected area criterion is satisfied
The emulsion (s) used therein may be non-tabular emulsions or tabular emulsions that do not satisfy the tabularity criteria set forth above. If desired, other silver halide emulsions can be blended with the high tabularity emulsion as long as the projected area criteria are satisfied.

The silver halide in these other emulsions is, as in tabular emulsions, silver bromide, silver chloride, silver iodide, and silver bromoiodide, silver chlorobromide, and silver chlorobromoiodide. Or a mixture of various halides. A particularly preferred silver halide is silver bromoiodide for all emulsions of the element. Although the preferred ratio of iodide is 3 to 12 mole%, smaller or larger (up to the limit of iodide solubility in bromide) iodide ratios can be used. When mixed halides are used in the emulsion grains, the halide ratio can be uniform throughout the grains, or the ratio can be continuous across the grain diameter within the core-shell or multilayer grains. Or it can be changed discontinuously.

The amount of silver halide in the image-forming unit of the present invention is from 0.2 to 2.0 g / m ^{2 based} on silver. When the color photographic recording unit has two or more silver halide layers of different sensitivities to the same region of the visible spectrum,
A layer of larger sensitivity consists of about 0.10 to about 1.0 g / m ² of silver, a layer of smaller sensitivity (s), sufficient to meet the total unit imaging required amount as described above Made of silver. Preferably, the higher sensitivity layer is about
It can consist of 0.20 to about 0.6 g / m ² of silver.

One of the characteristics of the photographic recording materials of the present invention is the reduction made possible by the silver to coupler ratio. For example, conventional color negative-working photographic recording materials use a substantial excess of silver as compared to couplers, so that a ratio of about 3 parts silver per part coupler is common. Utilization of the present invention allows the use of at least less than one third of silver using the same amount of image coupler. Thus, the silver to coupler ratio is 2.0 to 1 or less by weight and can proceed as low as 0.5 to 1 or less. Preferably, this element uses a silver to coupler ratio in the range of 0.8: 1 to 1.5: 1. In determining the silver to coupler ratio, all compounds that bind to the oxidized developing agent in the unit are accounted for, whether or not they contribute to image density.

Gelatin is commonly used as a vehicle to suspend silver halide grains and prevent their formation. The reduction in the amount of silver and the use of lower silver to coupler ratios than before leads to the use of less binder or vehicle.

With the present invention, it is possible to reduce the gelatin usage by more than 50% from that normally used, while retaining the desired image properties and obtaining manufacturing and ecological advantages. For example, a typical cyan and magenta imaging unit in a color negative working photographic material is 2 to 3.3 g / m
Contains ² gelatins. With the present invention, it is also possible to reduce the level of gelatin usage to about 0.5-1.5 g / m ² .

The improvement made possible by using the tabular silver halide grains described above, in combination with a reduction in the amount of silver halide and gelatin used, results in a clearly thinner photosensitive recording unit. Thus, the color forming unit of the present invention has a thickness of 4.0 μm, and a unit as thin as 2.0 μm or less is possible. Preferred color forming units have a thickness in the range of 2.5-3.5 μm. When measuring unit thickness, only the dye-forming silver halide layer is included.

When typical of color negative working materials, the photographic elements of this invention preferably contain a development inhibitor releasing coupler, especially in the higher speed sensitive layers of a given unit. A typical DIR coupler is described in U.S. Pat.
No. 3,227,554, No. 3,617,291, No. 4,095,98
No. 4, No. 4,248,962, No. 4,409,323, No. 4,477,5
No. 63 and No. 4,782,012.

The advantage of the present invention is that, as the speed sensitivity of the material increases, the improvement in photographic performance becomes more difficult to achieve.
It is particularly applicable to higher sensitivity materials, ie, 100 ISO and higher. This advantage becomes particularly important for materials having a sensitivity of 400 to about 6400 ISO.

The photographic recording materials of the present invention are multicolor color elements containing dye image-forming units sensitive to different regions of the electromagnetic spectrum. Each unit may be comprised of a single silver halide emulsion layer or of multiple emulsion layers sensitive to a given region of the spectrum. The layers of the element, including the layers of the image-forming units, are described in the art, for example, in US Pat.
They can be arranged in various orders as known from 400,463 and 4,599,302.

Typically the element consists of image-forming units that produce cyan, magenta and yellow dye images, with the silver halide associated with each unit being exposed to a supplemental region of the electromagnetic spectrum. However, one or more silver halide layers may be incorrectly exposed to regions of the spectrum that are not complementary to the dyes produced by the couplers with which they are associated. For example, one, two, or three of the imageable units may be sensitive to different portions of the infrared region of the spectrum.

At least one image-forming unit of the element is an image-forming unit having the characteristics defined above. Since the visible information provided by each of the magenta and cyan dye-forming units is of greater significance than that provided by the yellow dye-forming unit, this unit is a magenta dye-forming unit or It is preferably a cyan dye-forming unit. In a preferred embodiment, both of these imageable units have the characteristics described above.

Typical multicolor photographic recording materials have at least one
Dye image-forming unit consisting of at least one red-sensitive silver halide emulsion layer having at least one magenta dye-forming coupler and at least one green-sensitive halide having at least one magenta dye-forming coupler A support having a magenta dye image-forming unit consisting of a silver emulsion layer and at least one blue dye-sensitive image forming unit consisting of at least one blue-sensitive silver halide emulsion layer having an associated at least one yellow dye-forming coupler Consists of In addition to couplers that form dyes that complement the associated silver halide emulsion sensitization, the layers may also contain one or more non-supplementary couplers to modify the perceived photographic performance. Good. The recording material is coated on a support and may include additional layers such as a filtering layer, an image modifying layer, an intermediate layer, a jacket layer, a subbing layer, and the like.

Processing the element in the manner sought to be used results in a maximum image density of at least 2.0. Image density refers to the density range between D _min and D _max of the exposed and processed element. This is one of the common color negative working processes used to develop color negative amateurs and motion picture films, such as the ECN-2 or C-41 processes. Typical processing is the 1988 Annual of the British Jou
rnal of Photography, pages 196-198, as follows.

(1) Potassium carbonate, anhydrous 34.30 g Potassium bicarbonate 2.32 g Sodium sulfite, anhydrous 0.38 g Sodium metabisulfite 2.78 g Potassium iodide 1.20 mg Sodium bromide 1.31 g Diethylenetriaminepentaacetic acid pentasodium salt (40
% Solution) 8.43 g hydroxylamine sulfate 2.41 g Kodak Color Developer CD-4 {2-[(4-amino-3-methylphenyl) ethylamino] ethanol sulfate} 4.52 g Water was added to add 1 liter pH (at 26 ° C) Develop in a solution consisting of 10.0 +/- 0.05 for 3 minutes 15 seconds at 37.8 ° C.

(2) Ammonium bromide 50.00 g 1,3-propanediaminetetraacetic acid 30.27 g ammonium hydroxide (28%) ammonia 35.20 g ferric nitrate nonahydrate 36.40 g glacial acetic acid 26.50 g 1,3-diamino-2-propanol Tetraacetic acid 1.00 g Ammonium ferric EDTA (1.56 M, pH 7.05, 44% by weight) (including a 10% molar excess of EDTA, 3.5% by weight) 149.00 g In a solution consisting of 1 liter with the addition of water, 37.8% Bleach for 4 minutes at a temperature of ° C.

(3) Wash with water at 35-36 ° C for 3 minutes.

(4) Ammonium thiosulfate (58% solution) (less than 1% ammonium sulfite) 214.00 g (Ethylenedinitrilo) tetraacetic acid disodium salt 2
Water salt 1.29 g Sodium metabisulfite 11.00 g Sodium hydroxide (50% solution) 4.70 g Add water and fix in 1 liter solution of pH 6.5 ± 0.15 at 37.8 ° C for 4 minutes.

(5) Wash with water at 35-36 ° C for 3 minutes. And (6) formaldehyde (37% solution, 12% methanol) 3.60 g polyalkoxylate dimethylpolysiloxane 0.83 g Add water and stabilize at 37.8 ° C. for 1 minute in a 1 liter solution.

In the following description of suitable materials for use in the recording material of the present invention, reference is made to the Kenneth Mason Publication.
s, Ltd., Dudley Annex, 12a North Street Emsworth, Hamp
shire P0107DQ, Research Disc published by ENGLAND
losure, December 1978, Item 17643, the disclosure of which is incorporated herein by reference. This publication will be referred to below as the term “Research Disclosure”.

Copper, thallium, lead, bismuth, cadmium, selenium,
Sensitizers such as iridium and other compounds of Group VIII noble metals may be present during precipitation of the silver halide emulsion.

Silver halide emulsions can be chemically sensitized. Noble metals (eg, gold), intermediate chalcogens (eg, sulfur, selenium, or tellurium), and reduction sensitizers, used individually or in combination, are specifically contemplated. A typical chemical sensitizer is described in Research Disclosure, Item 17643, Sec.
It is described in tion III. Chemical sensitization is described in U.S. Pat.
The reaction is carried out in the presence of a finishing modifier such as that described in US Pat.

Silver halide emulsions include cyanines, merocyanines,
Polymethine dyes, including complex cyanines and merocyanines (i.e., tri-, tetra-, and poly-nuclear cyanines and merocyanines), oxonols, hemioxonols, styryls, merostyrils, and streptocyanins Can be spectrally sensitized with dyes of various types including Representative spectral sensitizers are described in Research Disclosure, Item 17643, Section IV, cited above.

Suitable vehicles for the emulsion layers and other layers of the element of the present invention are described in Research Disclosure, Item 17643, Section
IX and the publications cited therein.

Couplers useful in the present invention can be polymeric or non-polymeric. Typical cyan dye-forming couplers useful in the present invention are phenols and naphthols. Typical magenta dye-forming couplers are pyrazolones and pyrazoloazoles. Typical yellow dye-forming couplers are acetoacetanilides and benzoylacetanilides. Such dye image-forming couplers may be of the 1,2 or 4-equivalent type,
It can be coated in or adjacent to the silver halide emulsion layer, which is free to react with the oxidized developing agent to form the desired image. Small amounts of couplers that form images of different colors may be included in the dye-forming units of the present invention. For example, adding a small amount of cyan coupler to a magenta dye-forming layer changes the hue of the resulting magenta image. Further, the image-forming unit may contain an image-correcting coupler and a compound which releases a development inhibitor component, a development accelerator component, or a bleach acceleration component. These components are released from such compounds as a result of processing or from timing groups contained in such compounds.

The photographic recording material of the present invention includes a fluorescent whitening agent (Research D).
isclosure Section V), antifoggants and stabilizers (Res
earch Disclosure Section VI), stain inhibitor and image dye stabilizer (Research Disclosure Section VII, pa)
ragraph I and J), light absorption and scattering agent (Research Disclosu)
re Section VIII), Hardener (Research Disclosure Sec)
tion XI), plasticizers and lubricants (Research Disclosure Sec)
tion XII), matting agent (Research Disclosure Section)
XVI) and development modifier (Research Disclosure Section)
XXI) may be contained. The photographic material has a developing agent contained therein and may make it suitable for active processing as described in US Pat. No. 3,342,599.

The photographic materials can be coated on a variety of supports as described in Research Disclosure Section XVII and the literature described therein.

The photographic material is filtered to actinic radiation, typically in the visible region of the spectrum, to form a latent image as described in Research Disclosure Section XVIII, and then
It can be developed to form a visible dye image as described in Research Disclosure Section XIX. Processing to form a visible dye image includes the steps of contacting the element with a color developing agent, reducing developable silver halide, and oxidizing the color developing agent. The oxidized color developing agent then reacts with the coupler to form a dye.

 The following examples further illustrate the invention.

A series of color negative, coupler containing photographic materials were prepared by sequentially coating the following layers on a cellulose triacetate film support. The physical properties of the emulsion used, unit silver coverage, silver to coupler ratio, and unit thickness of the magenta unit are set forth in Tables I and II following the description of the preparation of photographic materials.

The first photographic recording material of the present invention comprises black colloidal silver 0.1.
Over 30 g / m ² and a cellulose triacetate film support having a layer of gelatin 2.44 g / m ^2, was prepared by coating the following layers in this order. This material is referred to as Element I.

Element I (Invention) layer 1 low sensitivity (Slow) cyan layer - red sensitized tabular silver bromoiodide grains (3.9 ^{mole% I -) 0.70gAg / m 2} , gelatin 1.61 g / m
² , cyan image-forming coupler A 0.54 g / m ² , DIR coupler B 0.0043 g / m ² , masking coupler C 0.068 g / m ² , and antifoggant 4-hydroxy-6-methyl-1,3,3a, 7−
Consists of 0.012 g / m ^{2 of} tetraazaindene.

Layer 2 sensitivity (Fast) Cyan Layer - higher-speed red-sensitized tabular silver bromoiodide grains (4.0 ^{mole% I -) 0.65gAg / m 2} , gelatin 1.15 g / m ^2, the cyan image-forming coupler D 0.29g /
m ^2, masking couplers C0.029g / m ^2, and antifoggant 4-hydroxy-6-methyl-1,3,3a, consists 7-tetraazaindene 0.011 g / m ^2.

Layer 3 intermediate layer - made of gelatin 0.65 g / m ² and oxidizing developer scavenger didodecylhydroquinone hydroquinone 0.054 g / m ^2.

Layer 4 Slow Magenta Layer - Green sensitized tabular silver bromoiodide grains (2.4 ^{mole% I -) 0.52gAg / m 2} , gelatin 1.16 g / m ^2, image-forming coupler E 0.30 g / m ² and F 0.13g / m ^2, DIR
Coupler B 0.027 g / m ² , Masking coupler G 0.069 g / m ² ,
And an antifoggant 4-hydroxy-6-methyl-1,3,3
It consists of 0.008 g / m ^{2 of} a, 7-tetraazaindene.

Layer 5 Fast Magenta Layer - Green sensitized for more sensitive tabular silver bromoiodide grains (4.0 ^{mole% I -) 0.39gAg / m 2} , gelatin
0.60 g / m ² , image-forming coupler E 0.075 g / m ² and F
0.032g / m ^2, DIR coupler H0.006g / m ^2, masking couplers G0.017g / m ^2, and antifoggant 4-hydroxy-6-
It consists of 0.006 g / m ^{2 of} methyl-1,3,3a, 7-tetraazaindene.

Layer 6 Yellow filter layer-gelatin 0.65 g / m ² , Care
yLea silver 0.022 g / m ^2, and consists of oxidized developing agent scavenger didodecyl hydroquinone 0.054 g / m ^2.

Layer 7 Slow Yellow Layer - blue sensitized tabular silver bromoiodide grains (4.2 ^{mole% I -) 0.32gAg / m 2} , gelatin 1.61 g / m ^2, image-forming coupler I 1.08g / m ^2, DIR Coupler J 0.065g / m
² , and antifoggant 4-hydroxy-6-methyl-1,
It consists of 0.003 g / m ^{2 of} 3,3a, 7-tetraazaindene.

Layer 8 Fast Yellow Layer - more sensitive blue-sensitized tabular silver bromoiodide grains (3.0 ^{mole% I -) 0.59gAg / m 2} , gelatin
1.20 g / m ² , image forming coupler I 0.43 g / m ² , DIR coupler J 0.032 g / m ² , and antifoggant 4-hydroxy-6
-Methyl-1,3,3a, 7-tetraazaindene 0.009 g / m ² .

Layer 9 Protective jacket and UV filter layer-gelatin 1.22 g /
m ^2, silver bromide Lippmann emulsion 0.11g / m ^2, UV absorbers 0.23g / m ^2,
And bis (vinylsulfonyl) methane; 2.0% of total gelatin weight.

Element II (Invention) A second photographic recording material of the invention, designated Element II, was prepared in the same manner as Element I. The following modifications were made to the magenta dye-forming unit.

Reduced layer 4 Slow Magenta layer -DIR couplers B to 0.019 g / m ^2.

Layer 5 High Sensitivity Magenta Layer--Increase the coverage of more sensitive green sensitized tabular silver bromoiodide grains to 0.65 g Ag / m ² , increase gelatin to 0.97 g / m ² , and add DIR coupler H 0.011g / m ²
Increased.

A third color photographic recording material of the present invention for color negative tone development, Element III, was prepared by applying the following layers in a predetermined order to a transparent support of cellulose triacetate. All silver halide emulsions were stabilized with 2 g of 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene per mole of silver.

Element III (invention) Layer 1 (antihalation layer) silver 0.236 g / m ² and gelatin
Black colloidal silver sol containing 2.44 g / m ² .

Layer 2 Slow Cyan Layer - red sensitized silver iodobromide emulsion (4 ^{mol% I -) 0.194g / m 2} , a red sensitized silver iodobromide emulsion (4 mol% I ^-) 0.280g / m ² , Cyan dye-forming image coupler D0.46
3g / m ^2, DIR compound B0.032g / m ^2, BAR compound N0.020g / m ^2,
It consists of 1.053 g / m ^{2 of} gelatin.

Layer 3 Highly sensitive cyan layer-Red sensitized silver iodobromide emulsion (4.1
^{Mole% I -) 0.495g / m 2} , the cyan dye-forming image coupler D
0.183g / m ^2, DIR compound B0.019g / m ^2, BAR compound N0.016g / m
² , consisting of 0.720 g / m ^{2 of} gelatin.

Layer 4 (Interlayer) Oxidized developer agent scavenger didodecyl hydroquinone 0.054 g / m ^2, the dye ^{MD-1; 0.107g / m 2} , the dye YD-1; 0.150 g
/ m ² , consisting of 0.645 g / m ^{2 of} gelatin.

Layer 5 Low-sensitivity magenta layer-Green sensitized silver iodobromide emulsion (2.
6 ^{mole% I -) 0.204g / m 2} , a green sensitized silver iodobromide emulsion (3 ^{mol% I -) 0.065g / m 2} , the magenta dye-forming image coupler E
0.151 g / m ² , magenta dye-forming image coupler F 0.194 g / m
² , DIR compound B consisting of 0.012 g / m ² and gelatin 0.613 g / m ² .

Layer 6 High-sensitivity magenta layer-Green sensitized silver iodobromide emulsion (4
^{Mole% I -) 0.430g / m 2} , the magenta dye-forming image coupler E 0.0425g / m ^2, the magenta dye-forming image coupler F
0.043 g / m ² , DIR compound H 0.0097 g / m ² , gelatin 0.527 g / m ²
Consists of

Layer 7 (Interlayer) Oxidized developer agent scavenger didodecyl hydroquinone 0.54 g / m ^2, yellow colloidal silver 0.022 g / m ^2, consisting of gelatin 0.645 g / m ^2.

Layer 8 Low-sensitivity yellow layer-Blue sensitized silver iodobromide emulsion (4
^{Mole% I -) 0.322g / m 2} , yellow dye-forming image coupler I 0.613g / m ^2, DIR compound J0.0194g / m ^2, 2- propargyl amino - benzoxazole 0.043 g / m ^2, gelatin
Consists of 0.914 g / m ² .

Layer 9 High-sensitivity yellow layer-Blue sensitized silver iodobromide emulsion (3
^{Mole% I -) 0.409g / m 2} , yellow dye-forming image coupler I 0.226g / m ^2, DIR compound J0.0097g / m ^2, 2- propargyl amino - benzoxazole 0.043 g / m ^2, gelatin
Consisting of 0.645g / m ^2.

Layer 10 (protective layer 1) gelatin 0.967 g / m ² , dye UV-1; 0.108
g / m ^2, Dye UV-2; consisting of 0.118 g / m ^2.

Layer 11 (Protective Layer 2) Unsensitized silver bromide Lippmann emulsion 0.108 g
/ m ² , anti-mat polymethyl methacrylate beads 0.025 g /
m ^2, gelatin 0.54 g / m ^2, consisting of hardener H-1 of 2 wt% relative to the total gelatin.

A control color negative photographic recording material, known as Element IV, to produce an ISO 400 speed sensitivity, was coated in a similar manner on a cellulose triacetate support having an antihalation layer in the layer sequence described. .

Layer 1 Slow Cyan layer -3 or red sensitized silver bromoiodide grains, a medium size tabular grain emulsion (6.0 mole% I ^-) 0.91 g
Ag / m ² , smaller tabular grain emulsion (3.0 mol% I ⁻ ) 0.28
gAg / m ² , and non-tabular grain emulsion (4.4 mol% I ⁻ ) 0.97 gAg
/ m ² blend, gelatin 2.59 g / m ² , cyan image-forming coupler A 0.72 g / m ² , DIR coupler K 0.044 g / m ² , masking coupler C 0.054 g / m ² , bleach accelerator releasing coupler N0 .0
75 g / m ^2, and antifoggant 4-hydroxy-6-methyl-1,3,3a, consists 7-tetraazaindene 0.071 g / m ^2.

Layer 2 Fast Cyan Layer - more sensitive red-sensitized tabular silver bromoiodide grains (6.0 ^{mole% I -) 1.29gAg / m 2} , gelatin 1.7
3 g / m ^2, the cyan image forming coupler D 0.23g / m ^2, DIR coupler K0.043g / m ^2, masking couplers C0.043g / m ^2, and antifoggant 4-hydroxy-6-methyl-1,3 , 3a, 7
It consists of 0.043 g / m ^{2 of} tetraazaindene;

Layer 3 Middle layer-gelatin 1.29 g / m ² and dye DY-1; 0.031 g
consisting of / m ^2.

Layer 4 Slow Magenta Layer - green sensitized silver bromoiodide grains, tabular silver bromoiodide grains (3.0 ^{mole% I -) 0.38gAg / m 2} , the non-tabular silver bromoiodide grains (4.8 mole% I ^-) a blend of 0.81 g / m ^2, gelatin 2.15 g / m ^2, the image forming coupler F 0.59 g /
m ^2, DIR coupler H0.011g / m ^2, masking coupler G0.05
9 g / m ^2, and antifoggant 4-hydroxy-6-methyl-1,3,3a, consists 7-tetraazaindene 0.019 g / m ^2.

Layer 5 Fast Magenta Layer - more sensitive green-sensitized tabular silver bromoiodide grains (6.0 ^{mole% I -) 1.23gAg / m 2} , gelatin
1.80 g / m ² , image-forming coupler F 0.17 g / m ² , DIR coupler H 0.011 g / m ² , masking coupler G 0.028 g / m ² , and antifoggant 4-hydroxy-6-methyl-1,3 , 3a, 7−
It consists of 0.015 g / m ^{2 of} tetraazaindene.

Layer 6 Yellow filter layer-gelatin 1.29 g / m ² , and
It consists of 0.022 g / m ^{2 of} Cary Lea silver.

Layer 7 Slow Yellow Layer - blue sensitized tabular silver bromoiodide grains (6.0 ^{mole% I -) 0.75gAg / m 2} , gelatin 2.27 g / m ^2, the image forming coupler L 1.58g / m ^2, DIR Coupler M0.083g / m
² , and antifoggant 4-hydroxy-6-methyl-1,
It consists of 0.013 g / m ^{2 of} 3,3a, 7-tetraazaindene.

Layer 8 Fast Yellow Layer - more sensitive blue-sensitized low aspect ratio silver bromoiodide grains (9.0 ^{mole% I -) 0.74g / m 2} , gelatin 1.60 g / m ^2, image-forming coupler L 0.23 g / m ^2, and antifoggant 4-hydroxy-6-methyl-1,3,3a, 7
- consisting tetraazaindene 0.012 g / m ^2.

Layer 9 Protective jacket and UV filter layer-gelatin 1.15 g /
m ^2, silver bromide Lippmann emulsion 0.22gAg / m ^2, and bis (vinylsulfonyl) methane; consisting of 2.0% addition of the total gelatin weight.

The above photographic elements were evaluated to determine photographic properties as described in Table III. In one evaluation, each element was filtered by a Daylight Va filter at 5500
A 600 W, 3000 K tungsten light source filtered to に K was exposed for 1/100 second through a 0-4.0 density step tablet graded to determine minimum density and gamma. In another evaluation, each element was exposed as described above except that the exposure time was 0.2 seconds to determine the maximum density. In other evaluations, each element was exposed for 0.2 seconds, and a green wratte was used to evaluate the separation exposure gamma and maximum density.
n 99 filter was added. To determine rms granularity, HC Schmitt, Jr. and JHAltman, Applied Optics 9,
According to the method described on pages 871-874, April 1970, 0.6
Each element was exposed as in the first evaluation, except that the filter pack containing the neutral density and 0-4.0 density step tablets was replaced by a 0-3.0 density step tablet and a matt glass diffuser.

Sharpness measurement is based on the Journal of Applied Phtographic Eng
ineering, 6 (1): 1-8, by determining the modulation transfer function (MTF) by the method described in 1980. The modulation transfer function for red light is 70B and 20C
Obtained by exposing each element for 1/15 second with 60% modulation using a KODAK color correction filter and a 0.2 neutral density filter.

The exposed sample was developed for 3.25 minutes in the 6-step development described on pages 15-17. The processed film pieces were then evaluated for sensitivity, contrast, net maximum density (D _max minus D _min ) for both white and green light exposure, and granularity for the magenta color forming unit.
35mm system cascade modulation transmission (System Cascaded Mo
dulation Transfer) (AMT) acutance rates are listed in Table III for the cyan color forming units.
The results are shown in Table III.

The construction of a thin color magenta color-forming unit containing a tabular grain silver halide emulsion of the preferred grain tabularity according to this invention provides light density, contrast, maximum density and granularity at substantial exposure latitude, reduced silver. Indicated to provide improved sharpness to the underlying emulsion layer while improving or maintaining coverage.

Construction To further demonstrate the performance of high tabularity emulsions coated with thin layers and low silver / coupler ratio, at least 2.0
A series of 20 two-color containing coupler photographic coatings were prepared to produce a maximum image dye density of This series consists of five different silver bromoiodide (4.0 mol% I) emulsions (approximately within the scope of the invention) of altered physical properties having approximately the same surface area per grain to obtain equal spectrally sensitized sensitivity. 3 and 2 out of the scope of the present invention). Each of the five emulsions was coated in four separate types of elements with varying amounts of material in the magenta unit. Three provide elements with unit silver, silver / coupler ratio, and thickness values of the invention, and the fourth serves as a control. The following layers were prepared by sequentially coating on a cellulose triacetate film support having an antihalation layer on the opposite side.

Element A (invention) layer 1 cyan layer -3 or red sensitized silver bromoiodide grains, a medium size tabular grain emulsion (6.0 ^{mole% I -) 0.91gAg / m 2} ,
Smaller tabular grain emulsion (3.0 mole% I ^-) 0.28gAg /
m ² , and non-tabular grain emulsion (4.8 mol% I ⁻ ) 0.97 gAg / m ²
Blend, gelatin 2.59 g / m ² , cyan image-forming coupler A 0.72 g / m ² , DIR coupler K 0.044 g / m ² , masking coupler C 0.054 g / m ² , bleach accelerator releasing coupler N 0.075 g / m
m ² , and an antifoggant 4-hydroxy-6-methyl-1,
It consists of 0.071 g / m ^{2 of} 3,3a, 7-tetraazaindene.

Layer 2 Middle layer-consisting of 1.29 g / m ^{2 of} gelatin.

Layer 3 Magenta Layer - Five green sensitized silver bromoiodide emulsion described in Table I (4.0 mole% I ^-) One 0.49gAg / m ^2, gelatin 1.30 g / m ^2, and the image-forming coupler E Consists of 0.49 g / m ² .

Layer 4 Protective jacket layer-consisting of 1.08 g / m ^{2 of} gelatin with 2.0% by weight of hardener H-1 based on total gelatin.

Element B (Invention) A second photographic recording material, designated Element B, was prepared in the same manner as Element A, with the following modifications to the magenta dye-forming unit.

Layer 3 Magenta layer-0.72 g Ag / g of green sensitized silver bromoiodide emulsion
It was increased to m ^2. The gelatin was increased to 1.86 g / m ² and the image-forming coupler E was increased to 0.72 g / m ² .

Element C (Invention) A third photographic recording material, designated Element C, was prepared in the same manner as Element A, with the following modifications to the magenta dye-forming unit.

Layer 3 Magenta layer-green sensitized silver bromoiodide emulsion at 1.00 g Ag /
It was increased to m ^2. Increased gelatin 1.95 g / m ^2.

Element D (Control) A fourth photographic recording material, designated Element D, was prepared in a manner similar to Element A, with the following modifications to the magenta dye-forming unit.

Layer 3 Magenta layer-green sensitized silver bromoiodide emulsion at 1.73 gAg /
It was increased to m ^2. Increased gelatin 2.91 g / m ^2.

600W, 300 photographic element filtered with Daylight Va filter to 5500 ゜ K and Green Wratten 99 filter
Exposure to a 0 ° K tungsten light source for 1/10 seconds through a graded 0-4.0 density step tablet, and these were processed for 3.25 minutes under the conditions described above. The film pieces were then evaluated for net maximum density ( _{Dmax- Dmin} ).

The data in Table VI indicate that it is necessary to use higher levels of silver and silver to coupler ratio, resulting in thicker coatings, to obtain useful maximum density in low tabularity emulsions .

Although the present invention has been described in detail with reference to preferred embodiments thereof, it will be understood that variations and modifications can be effected within the spirit and scope of the invention.

 The following describes additional embodiments of the present invention.

2. The recording material according to claim 1, wherein the tabular grains have a tabularity of between 100 and 5,000.

3. Recording material according to claim 1, wherein the tabular grains have a tabularity of between 100 and 2,500.

4. The recording material of claim 1 wherein said high flatness unit comprises at least two silver halide emulsion layers having different sensitivities in the same region of the spectrum.

5. The recording material according to the above item 4, wherein the photosensitive layer further comprises 0.10 to 1.0 g / m ² of silver.

6. The recording material according to item 4, wherein the photosensitive layer further comprises 0.20 to 0.6 g / m ² of silver.

7. The recording material according to claim 1, wherein 0.8 to 1.5 parts of silver is present per part of the coupler in the high flatness unit.

8. The recording material according to claim 1, wherein 0.5 to 1 part of silver is present per part of the coupler in the high flatness unit.

9. The recording material according to claim 1, wherein the unit thickness of the high flatness unit is 2.5 to 3.5 μm.

10. A recording material according to claim 1, comprising at least three silver halide image-forming units sensitive to different regions of the spectrum.

11. The recording material according to claim 1, wherein the tabular grains comprise at least one kind of silver bromide or silver bromoiodide.

12. The recording material according to claim 1, wherein the high flatness unit is a cyan dye-forming unit or a magenta dye-forming unit.

13. The recording material according to claim 1, wherein at least one unit contains a development inhibitor releasing coupler.

14. The recording material according to claim 1, wherein the high flatness unit contains a development inhibitor releasing coupler.

────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Blast, Thomas Bronnell, United States of America, 14559, Spencerport, Cottage Street 13 (72) Inventor Cofflon, James Thomas, United States of America, New York 14616, Rochester, Elmer Drive 123 (72) Inventor House, Gary Lawrence United States, New York 14564 Victor, Oak Ridge Road 1037 (56) References JP-A-2-33 (JP, A) JP-A-62-266538 (JP, A) (58) Int.Cl. ⁷ , DB name) G03C 1/74 G03C 1/035

Claims (2)

(57) [Claims] 1. A support comprising at least two silver halide emulsion image-forming units sensitive to different regions of the electromagnetic spectrum, each unit containing a dye-forming coupler and at least one unit. Are high tabular, red-sensitive cyan dye-forming or green-sensitive magenta dye-forming units, and (a) 0.2 to 2.0 g / m ^{2 based on} silver, 50% of the projected area of the grains
More than one consisting of a silver halide emulsion provided by tabular grains having a tabularity of between 50 and 25,000, (b) having a thickness (dry film thickness) of less than 4.0 μm, and (c) a coupler. Containing not more than 2.0 parts by weight of silver per part by weight, and (d) producing a maximum image dye density of at least 2.0 when the recording material is exposed and processed, and (e) a cyan or magenta dye-forming unit At least one of the layers has a flatness of 100-500 with more than 50% of the projected area
A negative working color photographic recording material comprising an emulsion provided by silver halide grains having 0 tabular grains. 2. The method according to claim 1, wherein said at least one unit has a silver content of 0.5.
2. The color photographic recording material according to claim 1, wherein the amount is ² to 0.6 g / m2.