JPH07111551B2 - Inverted photo elements - Google Patents

Abstract

Silver halide photographic elements are disclosed capable of producing reversal images including at least one emulsion layer comprised of a blend of tabular silver haloiodide grains and relatively fine grains consisting essentially of a silver salt more soluble than silver iodide.

Description

FIELD OF THE INVENTION This invention relates to improved photographic elements suitable for forming reversal images. The present invention is more particularly directed to a reversal silver halide photographic element containing tabular haloiodide grains in at least one emulsion layer.

[Conventional technology]

 The term "silver haloiodide" is recognized in the art.
It is used in the current usage, and iodide ion
Combined with at least one of Rabini chloride and bromide ion
Refers to silver halide grains containing silver ions
It The term "inverted photographic element" refers to a photographic image for observation.
To form, by imagewise exposure and development
Form a negative of the observed image, and then perform uniform exposure and
(Or) fog formation and treatment of residual silver halide
Photographs required to form a second visible image.
Refers to the element. As a typical example of an inverted photographic element,
Color slides, such as Kodachrome
And Ektachrome Made from
Can be raised. In overwhelmingly many applications,
The first image above is a negative and the second image is
It is J. U.S. Pat.No. 4,082,553 describes a Kabb et al.
Change by mixing a small amount of silver rogenide grains.
Conventional tabular grains containing characterized silver haloiodide grains.
Ip's inverted photographic element is disclosed. Furthermore, the country of Germany
The patent application publication gazette No. 3,402,840 is the above-mentioned US patent.
Same as No. 4,082,553, but from 0.3 μm
Is also expressed as being large and smaller than
Image-forming silver halide grains.
Also, in the case of such an application, fogged silver halide grains
Or low solubility in addition to those metals or metal sulfides
Additional organic compounds capable of forming silver salts
In need.

High aspect ratio tabular grain silver haloiodide emulsions bring about various photographic advantages, such as improvement in speed (speed) -graininess relationship, improvement in image sharpness, and reduction in blue sensitivity of the minus blue recording emulsion layer. It is recognized as a thing. The use of high aspect ratio tabular grain silver haloiodide emulsions in reflective photographic elements is described, for example, in Research Disclosure ,
Vol. 225, January 1983, Item 22534; and U.S. Pat. No. 4,43.
4,226, 4,439,520, 4,433,048, 4,4
00,463 and 4,435,501. The above Research Disclosure is a publication of the following publisher: Kenneth Mason Publication, Ltd., The Old.
Harbormaster ′s, 8 North Street, Emsworth, Hampshire
P010 7DD, England.

[Problems to be solved by the invention]

One object of the invention is to have a support and at least one image recording emulsion layer coated on the support,
The emulsion layer has a dispersion medium and a thickness of less than 0.5 μm and a minimum of 0.6.
having a diameter of μm and an average aspect ratio greater than 8: 1 and having a minimum total grain projected area of said emulsion layer
To provide a photographic element capable of forming a reversal image and exhibiting an increased reversal threshold speed, such as consisting of a blend of radiation-sensitive tabular silver haloiodide grains accounting for 35%. It is in. It is another object of the present invention to provide a reversal photographic element as described above, which exhibits reduced toe density and increased maximum density and contrast in the reversal image.

[Means for solving problems]

According to the present invention, the above-mentioned object is to mix relatively fine grains essentially consisting of a silver salt having a higher solubility than silver iodide with radiation-sensitive tabular silver haloiodide grains. And the fine particles are in a concentration sufficient to improve the reversal image formation.

When relatively fine grains consisting essentially of a silver salt that is more soluble than silver iodide are added to the layer containing the tabular silver haloiodide grains, the advantages of the reversal imaging process are combined. It was found that it could bring. The reversal threshold sensitivity of reversal photographic elements can be improved.
At the same time, it is possible to observe a decrease in the foot density of the inverted image and an increase in the maximum density and contrast.

The present invention thus relates to improvements in silver halide photographic elements useful in reversal imaging processes. These photographic elements consist of a support and one or more image recording silver halide emulsion layers coated on the support. At least one of the image recording emulsion layers is a dispersion medium,
It also contains radiation-sensitive tabular silver haloiodide grains mixed with relatively fine grains of a silver salt having a higher solubility than silver iodide.

A tabular grain is herein defined as a grain having two substantially parallel crystal faces, each of these crystal faces being distinctly longer than any of the other single crystal faces of the grain. Can be defined. The tabular grains used in the emulsion layers of the grain blends to form one or more layers of the reversal photographic element of the present invention are, according to the present invention, of a thickness of less than 0.5 .mu.m and a minimum of 0.6 .mu.m. The tabular grains having a diameter have an average aspect ratio greater than 8: 1 and can be selected in such a direction as to account for at least 35% of the total grain projected area of the emulsion layer of the grain blend in which they are present. it can.

It is convenient to blend (mix) a radiation sensitive high aspect ratio tabular grain emulsion with a relatively fine second group of grains to prepare a grain blended emulsion layer that meets the requirements sought in the present invention. There is one method. here,
The term “high aspect ratio tabular grain emulsion” is 0.3 μm.
And a tabular silver halide grain having a diameter of at least 0.6 μm has an average aspect ratio of greater than 8: 1 and such grain has a minimum of 50% of the total projected area of the grain present in the emulsion. Can be defined as what is essential to occupy. This term can therefore be defined consistent with the definition used in this term in the tabular grain emulsion patents cited above.

Tabular grains having a thickness of 0.3 .mu.m are generally useful. If the emulsion layer is intended to be used for recording blue light as opposed to green or red light, then the tabular grain thickness criterion is increased to less than 0.5 μm, instead of less than 0.3 μm. Is advantageous. Such an increase in tabular grain thickness is also recommended in applications where the inverted image is viewed without magnification and in cases where granularity is not critical. However, in the case of forming a reverse image, the above-mentioned uses and cases are relatively rare, and it is most common to project and observe the reverse image.
Tabular grain emulsions in which the tabular grains of those emulsions have a thickness of less than 0.5 .mu.m intended for blue light recording are described, for example, in U.S. Pat. No. 4,439,520, cited above.
Issue.

When tabular grains satisfying the criteria of 0.3 μm thickness and 0.6 μm diameter account for at least 50% of the total projected area of the grains in the high aspect ratio tabular grain emulsion, a second group of grains in such emulsion is used. It can be seen that when blended, the proportion of tabular grains in the total grain projected area is reduced. Tabular grain emulsions that can be considered for use to prepare emulsion layers of grain blends that meet the requirements of the invention are those that meet the criteria for thickness and diameter, and also in the emulsion layers of the grain blends. It should be possible to provide tabular grains which account for at least 35% of the total grain projected area. Therefore, the tabular grain emulsions used in the practice of this invention preferably provide a minimum of 50% of total grain projected area, which is not a requirement at least prior to blending the second grain group (total The above criteria of 35% of the projected area of the grain need only be met in the emulsion layer of the grain blend.) Therefore, high aspect ratio tabular grain emulsions are advantageous and highly preferred in the preparation of grain blend emulsions. In, the emulsion of the grain blend itself is a high aspect ratio tabular grain emulsion, but these are not necessary in all cases, and for certain applications, deviations may actually be taken advantage of. It is clear that However, for the sake of simplicity, the radiation-sensitive tabular grain emulsion will be examined below for the advantageous high aspect ratio tabular grain emulsion. In addition,
As will be appreciated, the teachings of the description generally apply to tabular grains as defined herein.

The advantageous high aspect ratio tabular grain silver haloiodide emulsions are:
At least 12 silver haloiodide grains having a thickness of less than 3 μm (optimally less than 0.2 μm) and a diameter of at least 0.6 μm:
1, optimally like having an average aspect ratio of at least 12: 1. These silver haloiodide emulsions satisfying the above-mentioned thickness and diameter criteria are, in a preferred embodiment of the present invention, at least 70% of the total projected area of silver halide grains.
%, Optimally at least 90%. In accordance with one highly preferred aspect of the present invention, the emulsions of grain blends sought according to the present invention can also meet the parameters set forth above, that is, those described for the advantageous high aspect ratio tabular grain emulsions.

Looking at tabular grains accounting for a given percentage of the projected area, it is observed that the thinner these grains, the higher the average aspect ratio of the emulsion. Generally, tabular grains have an average thickness of at least 0.03 µm, although in principle thinner tabular grains can be used.

High aspect ratio tabular grain emulsions useful in the practice of this invention can have very high average aspect ratios. The average aspect ratio of tabular grains can be increased by increasing the average grain size (grain diameter) of the grains. Increasing the average aspect ratio can provide advantages for sharpness, although usually the maximum average grain size is limited by the granularity requirements for particular photographic applications. The average aspect ratio of the tabular grains can also, or otherwise, be increased by reducing the average thickness of the grains. When the silver coverage is kept constant, the aspect ratio can generally be increased by reducing the thickness of the tabular grains, and the granularity can be improved as a direct function of increasing the aspect ratio. can do. For this reason, the maximum average aspect ratio of the tabular grain emulsions of this invention is a function of the maximum average grain size acceptable for the particular photographic use of the emulsion, and the minimum achievable tabular grain size that can be advantageously provided. It can be a function of particle thickness. It has been found that the maximum average aspect ratio can vary depending on the precipitation technique used and the composition of the tabular silver halide. High aspect ratio tabular grain silver haloiodide emulsions having average aspect ratios of 100: 1, 200: 1 or greater can be obtained, for example, by the double jet precipitation method.

The tabular silver haloiodide grains used in the practice of the present invention contain at least one of bromide and chloride in addition to iodide. Therefore, when referring to silver haloiodide, silver bromoiodide, silver chlorobromoiodide, and silver chloroiodide can be particularly considered. Silver bromoiodide emulsions can usually exhibit higher photographic speed and, for this reason, are the preferred and most commonly used emulsions for candid (snapshot) photography. it can.

Iodide must be present in a concentration sufficient to affect photographic performance when it is used in tabular silver haloiodide grains. Thus, it will be appreciated that at least about 0.5 mole percent iodide will be present in the tabular silver haloiodide grains. However, it is not necessary to use high concentrations of iodide to achieve the benefits of the present invention. Generally speaking, the tabular silver haloiodide grains contain iodide in amounts less than 8 mole percent. The concentration of iodide in the tabular silver haloiodide grains is preferably 1-7.
Mol%, optimally 2 to 6 mol%. All the above-mentioned mol% of iodide are based on the total amount of silver present in the tabular grains.

The radiation-sensitive tabular haloiodide grains necessary for the practice of the present invention are preferably the publications cited above: Research Disclosure , Vol. 225, January 1983, I.
tem 22534; and U.S. Pat.Nos. 4,434,226 and 4,439,5.
No. 20, No. 4,433,048, No. 4,400,463 and No. 4,43
It can be provided by selecting from among the various high aspect ratio tabular grain emulsions disclosed in 5,501;

The emulsions of grain blends necessary to carry out the present invention are conveniently tabular grain silver haloiodide emulsions as described above and a second group of grains (these grains being essentially iodide). Of a silver salt that is more soluble than silver). The silver salt should be sufficiently insoluble that it is capable of forming particles rather than being present in dissolved form. Useful silver salts can be selected from among those having a solubility product constant of 9.5 to less than 16. Preferred silver salts are those having a solubility product constant of 9.75 to 15.5, optimally 11 to 13. All solubility product constants shown are at a temperature of 20 ° C., unless otherwise specified. A review and listing of solubility product constants for typical silver salts can be found in, for example, James, Theory of the Photograph.
ic Process , 4th Ed., Macmillan, 1977, Chapter 1, Sectio
n F, G and H, pp. 5-10.

Advantageously, the silver salt forming the relatively fine grain is at least as soluble as most of the soluble silver salt present in the radiation sensitive tabular grains. For example, if the tabular grains consist essentially of silver chlorobromoiodide, the relatively finer grains preferably consist essentially of silver chloride or silver chlorobromide as opposed to silver bromide. You can When using radiation-sensitive tabular silver bromoiodide grains, the relatively fine grains can preferably consist essentially of silver bromide, silver thiocyanate or a combination of these silver salts. Advantages could be realized when using a combination of silver bromide and silver thiocyanate grains.

Although relatively fine grains are originally composed of silver salts having a higher solubility than silver iodide, it is possible that a less soluble silver salt can be present in a small amount that does not interfere with the effectiveness. Is recognized. For example, it is common to treat silver halide emulsions with solutions of soluble iodide salts in the context of spectral sensitization and to use compounds that form fairly insoluble silver salts as antifoggants and stabilizers. Is. Such conventional emulsion processing can result in the adsorption of small amounts of silver iodide or one or more other fairly insoluble silver salts to the surface of the relatively fine grains as a result of the processing. Nevertheless, it is usually compatible with the practice of the invention.

Grains consisting essentially of silver salts that are more soluble than silver iodide are finer when they are compared to tabular silver haloiodide grains. In general, for this second group of grains to be blended with radiation sensitive tabular grains, the acceptable size can be considered to be a direct function of the solubility of the silver salt forming the grains of that group. This second group of particles exhibits in all cases an average particle size of less than 0.5 μm and preferably an average particle size of less than 0.3 μm. Optimally, this second group of particles exhibits a mean particle size of less than 0.1 μm. Therefore, this second particle group is
Optimally, it can be provided by blending a conventional Lippmann emulsion with a radiation-sensitive tabular grain emulsion and thus preparing the emulsion of the grain blend necessary for the practice of this invention. The minimum mean diameter of this second group of particles is limited only by the convenience of synthesis, and is usually at least about 0.05.
μm.

The second group of grains can be used at any concentration which can enhance the photographic properties of the reversal photographic element. The minimum concentration of this second group of grains can be as low as about 0.5 mol% based on the total amount of silver in the emulsion layer of the grain blend, and
For maximum photographic advantage, concentrations above about 1 mol% are preferred and concentrations above about 5 mol% are optimal. To avoid inadequate use of silver salts, the maximum concentration of the second grain group is usually below that of the silver haloiodide which forms the radiation-sensitive tabular grains, ie, in the emulsion layer of the grain blend. Of less than 50 mol% based on the total amount of silver. The most effective utilization of silver can be achieved when the concentration of this second group of particles is less than about 40 mol%.

Generally, the emulsions necessary for the practice of this invention are prepared by blending a tabular silver haloiodide grain emulsion with a separately prepared emulsion containing a relatively fine second group of grains. It is most convenient to do this. The relatively fine grain emulsion can take the form of, for example, a relatively fine grain silver chloride, silver bromide or silver thiocyanate emulsion. The preparation of these fine grain emulsions is a technique well known to those skilled in the art, and therefore does not form a part of the present invention. As mentioned above, the relatively fine grain emulsions are optimally Lippmann emulsions. One or both of the emulsions containing tabular grains and the emulsions containing relatively finer grains may themselves be the product of conventional grain blends, so long as the grain requirements as described above are met. Can be

The reversal photographic elements of this invention can be in any convenient conventional form, apart from the particular characteristics of the grain-blended emulsions described above. These reversal photographic elements can take the form of either black or color reversal photographic elements.

In very simple form, a reversal photographic element according to the invention comprises a conventional photographic support, such as a transparent film support, and an emulsion layer of a grain blend as described above coated on the support. Can be Although commonly used overcoats and subbing layers are advantageous,
Only the emulsion layer of the grain blend is an essential element. After imagewise exposure, the silver halide is imagewise developed to form a first silver image (no visible need). If a silver reversal image or a silver intensifying dye reversal image is desired, the first silver image can be removed by bleaching prior to subsequent development. After that, in order to make it possible to develop the remaining silver halide uniformly,
Exposure or fog formation is performed. The development produces a reverse image. This reversal image can be a silver image, a silver enhancing dye image or a dye image only, depending on the choice of conventional processing technique used. Mason, Photographic Processing Chemis
try , 1966, Focal Press Ltd., pp. 160-161. If you are forming a dye-only image,
It is common to not bleach the silver until after the final dye image is formed.

The reversal photographic element of the present invention, in a preferred form, is a color reversal photographic element capable of forming a multicolor image, i.e., an image that at least substantially reproduces the color of the subject. Specific examples of such color reversal photographic elements are described, for example, in U.S. Pat.
No. 0 and No. 4,082,553.
Such a color reversal photographic element has a simple structure. A support and at least three color-forming layer units (blue recording yellow image-forming layer unit and green recording unit) coated on the support are described. Magenta dye image forming layer unit,
And including the cyan dye image forming layer unit for red recording)
Can consist of Each color forming layer unit can have at least one radiation-sensitive silver halide emulsion layer. According to a preferred embodiment of the present invention, at least one of the radiation-sensitive emulsion layers contained in each color-forming layer unit has a grain blend emulsion as described above. The emulsion of grain blends in each color forming layer unit can be chemically and spectrally sensitized as taught, for example, in US Pat. No. 4,439,520. According to one preferred embodiment, the chemical and spectral sensitization of the tabular grain emulsion is completed prior to blending the second group of grains (thus the sensitizer remains substantially absent).
It is preferred to incorporate one or more dye image-forming materials, such as couplers, into each color-forming layer unit, although the alternative is to incorporate such materials into the element during processing of the photographic element. You can

Illustrative examples of color reversal photographic elements, particularly according to the present invention, are set forth below: I. Photographic Supports Typical advantageous photographic supports are cellulose acetate and poly (ethylene terephthalate) film supports and photographic paper supports. Bodies, in particular paper supports, such as partially acetylated or baryta and / or α-olefin polymers, in particular α having 2 to 10 carbon atoms.
Includes paper supports coated with polymers of olefins such as polyethylene, polypropylene and ethylene butene copolymers.

II. Subbing Layers It is advantageous to apply gelatin or other conventional subbing layers to facilitate the formation of coatings on photographic supports.

III. Red Recording Layer Unit At least one layer comprising a red sensitive, grain blended, high aspect ratio tabular grain silver haloiodide emulsion layer as described in detail above. In one emulsion layer or in a layer adjacent to it, there is included at least one conventional cyan dye image-forming coupler, such as some of the cyan dye image-forming couplers disclosed in the U.S. patents listed below. Have: 2,423,730; 2,706,684; 2,725,292,2,772,161; 2,772,162;
2,801,171; 2,895,826; 2,908,573; 2,920,961; 2,9767,14
6; 3,002,836; 3,034,892; 3,148,062,3,214,437; 3,227,55
4; 3,253,924; 3,311,476; 3,419,390; 3,458,315; and 3,47
6,563.

IV. INTERLAYER At least one hydrophilic colloid interlayer, preferably a gelatin interlayer, is provided containing a reducing agent such as an aminophenol or an alkyl-substituted hydroquinone to act as a scavenger for the oxidized developer.

V. Green Recording Layer Unit At least one layer consisting of a green sensitive, grain blended, high aspect ratio tabular grain silver haloiodide emulsion layer as described in detail above. In one emulsion layer or in a layer adjacent thereto, there is at least one conventional magenta dye image-forming coupler, such as one with the magenta dye image-forming couplers disclosed in the U.S. patents listed below. Has: 2,725,292; 2,772,161; 2,895,826; 2,90
8,573; 2,920,961; 2,933,391; 2,983,608; 3,005,712; 3,00
6,759; 3,062,653; 3,148,062; 3,152,896; 3,214,437; 3,22
7,554,3,253,924; 3,311,476; 3,419,391; 3,432,521; and
3,519,429.

VI. Yellow filter layer A yellow filter layer is provided for the purpose of absorbing blue light. The yellow filter layer may be in any convenient conventional form, such as a gelatin-yellow colloidal silver layer (ie, Carey Lea
It may take the form of a silver layer) or a yellow-containing gelatin layer. In addition to this, the filter layer was previously formed by the intermediate layer IV.
A reducing agent (acting as a scavenger for oxidized developer) as described in connection with can be included.

VII. Blue Recording Layer Unit At least one layer consisting of a blue sensitive, grain blended, high aspect ratio tabular grain silver haloiodide emulsion layer as described in detail above. In another possible form tabular grains can be thicker than high aspect ratio tabular grains. That is, the thickness criterion for such particles can be increased from 0.3 μm to less than 0.5 μm as described above. In this case, the particles as described above,
More natural blue sensitivity can be exhibited, which is preferably increased by the use of blue spectral sensitizers.
However, such blue sensitivity is not essential except for the highest achievable blue sensitivity. In one emulsion layer or in a layer adjacent thereto, there is included at least one conventional yellow image-forming coupler, such as one of the yellow image-forming couplers disclosed in the U.S. patents listed below. 2,875,057; 2,895,826; 2,908,573; 2,920,961;
3,148,062; 3,227,554; 3,253,924; 3,265,506; 3,277,155;
3,369,895; 3,384,657; 3,408,194; 3,415,652; and 3,447,
928.

VIII. Overcoat Layer At least one overcoat layer is provided. Such layers are generally transparent gelatin layers and are known additives for improving coating, handling and photographic properties, such as matting agents, surfactants, antistatic agents,
Contains UV absorbers, and similar additives.

High aspect ratio tabular grain emulsion layers, as disclosed in U.S. Pat.No. 4,439,520, use yellow filters to achieve green light or red light (yellow filter to achieve acceptable green or red exposure records). Substantially optimal sensitization (without requiring the use of layers) can show a sufficient difference in blue and green or red sensitivities. It will be appreciated that in the absence of the yellow filter layer, the color forming layer units can be coated on the support in any desired order. Only 1 for each record of blue, green and red exposure
Although only one single chromophoric layer unit is disclosed, it will be appreciated that two, three or more chromophoric layer units may record any one of blue, green and red. Further, any one or all of the blue, green and red color-developing layer units is a multilayer radiation-sensitive emulsion layer, and any, some, or all of such layers are the same as those of the grain blend of the present invention. It is possible to use those which meet the requirements of the emulsion.

Inverted photographic elements are, of course, other conventional feature elements known in the art, such as Research Discl.
What can be described with reference to Osure, Vol . 176, December 1978, Item 17643, can be included in addition to the characteristic components mentioned above. For example, silver halide emulsions other than the grain blend emulsions described can be selected from among those described in Research Disclosure paragraph I above and the silver halide emulsions can be chemically enhanced as described in paragraph III of the same book. And a silver halide emulsion can be spectrally sensitized as described in paragraph IV of the same, and any portion of the element can include a fluorescent whitening agent as described in paragraph V of the same. The emulsion layer may contain antifoggants and stabilizers as described in paragraph VI of the same, and the color forming layer unit may contain a color image forming substance as described in paragraph VII of the same. Yes, the element can include absorbing and scattering materials as described in paragraph VIII of the same, and the emulsion layer and other layers include a vehicle as described in paragraph IX of the same. The hydrophilic colloid layers and other layers of the element can include hardeners as described in paragraph X of the same, and the layers can include coating aids as described in paragraph XI of the same. And the layer can include plasticizers and lubricants as described in paragraph XII of the same book,
Ibid paragraph XVI on layers, especially those furthest from the support
Matting agents can be included, as described in (1), and the support can be selected from among those described in paragraph XVII of the same. It should be noted that the additives and features enumerated herein are not intended to limit or imply the absence of other conventional photographic features that are compatible with the practice of the invention. Absent.

The photographic element is, for example, Research Disclosure ,
Various forms of energy can optionally be used for image exposure, as disclosed in paragraph XVIII of Item 17643. In the case of forming a multicolor image, the photographic element can be exposed to visible light.

Multicolor reversal dye images are formed by first performing black and white development followed by color development in the case of photographic elements of the present invention having various spectrally sensitized silver halide emulsion layers. You can Examples of reversal processing are described below using conventional reversal processing compositions and methods.

〔Example〕

 The invention is then further described with particular reference to the examples below.
Will be explained in detail. In the examples, the covered amount in parentheses is g /
m²It is indicated by. In addition, the described elements are
, Unless otherwise specified, ratten 8 fill
With a 500W 2850 ° K light source through the center for 0.02 seconds.
Just exposed through the step tablet, and Koda
Click E-6 In the first development step for 3 minutes using the process
Reversed. Kodak E-6 The process is, for example,
British Journal of Photographic Annual, 1982, pp.201
-203.

Element 1 (Inventive Example) The following layers were coated on a film support in the order listed.

Layer 1 Gelatin (1.08) Layer 2 Very sensitive green-sensitive high aspect ratio tabular grain silver bromoiodide emulsion comprising (a) average aspect ratio 18: 1, average tabular grain thickness 0.1 μm and bromide. / High aspect ratio tabular bromoiodide grains having a molar ratio of 97: 3 (1.08);
(B) 0.08 μm silver bromide grains (0.86) provided by blending the Lippmann emulsion with the high aspect ratio tabular grain silver bromoiodide emulsion giving the grains of (a) above;
(C) gelatin (2.16); and (d) magenta dye-forming coupler, 1- (2,4,6-trichlorophenyl)-
3- {3- [α- (2,4-di-tert.-amylphenoxy) acetamido] benzamide} -5-pyrazolone (0.86).

Layer 3 Gelatin (1.08), and 1.75 wt% bis (vinylsulfonyl), based on the total amount of gelatin in all layers.
Methane hardener.

Element 2 (Comparative Example) This element 2 is the same as the element 1 described above. However, in this element the Lippmann emulsion was not blended to form Layer 2.

Element 3 (Comparative Example) This element 3 is the same as the element 1 described above. However, for this element, the Lippmann emulsion was not blended into layer 2 and instead the Lippmann emulsion was halved and blended into layers 1 and 3, respectively.

FIG. 2 shows the characteristic curves of the elements 1, 2 and 3 described above as curves E1, C2 and C3, respectively. By reference to this figure, the photographic behavior of the described color reversal photographic elements can be compared. Curve E1 to curve C2
And C3, it can be seen that a higher maximum density and contrast is realized, and a lower density is realized at the foot of curve E1. Surprisingly, when the silver bromide Lippmann emulsion was evenly divided into overcoat and undercoat layers, a reduction in photographic behavior was caused, and thus compared to the absence of the Lippmann emulsion at all. Lower maximum densities and contrasts and higher minimum densities are observed. Moreover, very surprisingly, when splitting a Lippmann emulsion, results are obtained which are exactly the opposite of those obtained by blending a Lippmann emulsion with a high aspect ratio tabular grain silver bromoiodide emulsion.

Element 4 (Comparative Example) An element identical to Element 1 above was prepared except for the following points.
That is, for this element, instead of blending a high aspect ratio tabular grain emulsion with a silver bromide Lippmann emulsion, (a) a non-tabular grain having an average diameter of 0.54 μm and a bromide / iodide molar ratio of 96.5: 3.4. A single jet process ammonia-ripened silver bromoiodide emulsion containing grains is used in place of the high aspect ratio tabular grain silver bromoiodide emulsion, and (b) the coating coverage of silver bromide grains is It decreased to 0.43 g / m ² .

Element 5 (Comparative Example) This element 5 is the same as the element 4 described above. However, for this element Lippman emulsion was not blended to form Layer 2.

Element 6 (Comparative Example) This element 6 is the same as the element 4 described above. However, in the case of this element, the coating amount of Lippmann emulsion was increased to 0.86 g / m ² ,
Also, this emulsion was not blended into Layer 2, but halves were blended into Layer 1 and Layer 3, respectively.

The photographic behavior of these color reversal photographic elements is described in Section III.
Comparison can be made by reference to the figures, ie the characteristic curves of the elements 4, 5 and 6 illustrated as curves C4, C5 and C6 respectively. Comparing the behavior of these elements, blending Lippmann silver bromide grains in a non-tabular silver bromoiodide emulsion is represented by element 1 represented by dotted curve E1 or curves C5 and C6, respectively. It can be seen that when compared with elements 5 and 6, it has the effect of significantly reducing the sensitivity of element 4. When a Lippmann silver bromide emulsion was present in Layer 2 of Element 4, an increase in maximum density and a slight increase in contrast as compared to Element 5 resulted, but due to the significant loss of sensitivity. It can be seen that this prevents the achievement of reduced toe density. Furthermore, it can be particularly noted that the relationship between curves C5 and C6 is opposite to that expected from the relationship between curves C2 and C3.

Element 7 (Comparative Example) This element 7 is the same as the element 4 described above. However, in the case of this element, the bromide / iodide molar ratio of 93.7: 6.3 and the average particle size of 0.
A single jet ammonia ripened silver bromoiodide emulsion having a thickness of 70 μm was used.

Element 8 (Comparative) This element 8 is the same as element 7 above except that no Lippmann emulsion was blended to form layer 2.

Element 9 (Comparative) This element 9 increased the coverage of the Lippmann emulsion to 0.86 g / m ² and did not blend it into layer 2 but instead bisected it into layers 1 each. And element 7 above except that it was blended into layer 3.

The behaviors of the elements 7, 8 and 9 are respectively the curves C7 and C8 of FIG.
And C9. A comparison of the curves in FIGS. 3 and 4 reveals that the relative behavior of elements 7.8 and 9 is similar to that of elements 4,5 and 6, respectively.

Element 10 (Comparative) The following layers were coated in the order listed on a transparent film support.

Layer 1 A very sensitive green-sensitive high aspect ratio tabular grain silver bromoiodide emulsion having (a) an average aspect ratio of 18: 1, an average tabular grain thickness of 0.1 μm and a bromide / iodide molar ratio of 97. High aspect ratio tabular bromoiodide grains with: 3 (1.08);
(B) gelatin (2.16); and (c) cyan dye-forming coupler, 3- [α- (2,4-di-tert.-amylphenoxy) hexanamide] -2-pentafluorobutyramide phenol (0.97). Consisting of.

Layer 2 Gelatin (0.97), and 1.75 wt% bis (vinylsulfonyl) methane hardener based on the total amount of gelatin in both layers.

Element 11 (Inventive Example) This element is the same as that of Element 11 except that 0.08 μm silver bromide grains in the form of a Lippmann emulsion, 0.054 g / m ^2, were blended with high aspect ratio tabular grain silver bromoiodide emulsions. Same as 10.

Element 12 (Inventive Example) This element 12 was prepared by multiplying the coated amount of silver bromide grains by about 2 times.
Same as Element 11 above except 0.11 g / m ² .

Element 13 (Inventive Example) This element 13 has a coating amount of silver bromide grains doubled to 0.22.
Same as element 12 except g / m ² .

The behavior of element 10 represented by curve C10 and the behavior of element 13 represented by curve E13 are compared in FIG.
It is clear that curve E13 demonstrates higher maximum density, threshold sensitivity and contrast and lower toe density. Elements 11 and 12 exhibited some behavior in the intermediate range between elements 10 and 13 except element 11 exhibited a lower maximum density than element 10 and no higher contrast. However, when the obtained characteristic curve is considered by superimposing it at the time of the minimum exposure (the left end of the plot), the threshold value sensitivity and the contrast gradually increase as functions of the Lippmann emulsion mixture, and the factor 10 is It was found that element 13 exhibits the lowest threshold sensitivity and contrast and element 13 exhibits the highest threshold sensitivity and contrast.

Element 14 to Element 17 The above comparison was repeated with reference to Element 10 to Element 13.
However, in the case of these elements, instead of silver bromide grains,
0.4 μm silver thiocyanate particles were used. The concentration of silver thiocyanate is as shown in Table I below. Curve C1
The results for element 14 represented by 4 and element 17 represented by curve E17 are as illustrated in Figure 6 of the accompanying drawings. Elements 15 and 16 exhibited intermediate behavior. Element 14 did not meet the requirements of the invention, while elements 15-17 met the requirements of the invention.

Table I element curve ^{AgSCN (g / m 2) 14} C14 No 15 --- 0.055 16 --- 0.11 17 E17 0.22 element 18 (Comparative Example) transparent film support on the order according to the layer below Was applied to.

Layer 1 A very sensitive green-sensitive high aspect ratio tabular grain silver bromoiodide emulsion having (a) an average aspect ratio of 18: 1, an average tabular grain thickness of 0.1 μm and a bromide / iodide molar ratio of 97. High aspect ratio tabular bromoiodide grains with: 3 (1.08);
(B) gelatin (2.16); and (c) cyan dye-forming coupler, 3- [α- (2,4-di-tert.-amylphenoxy) hexanamide] -2-heptafluorobutyramide phenol (0.97). Consisting of.

Layer 2 UV absorber, 3- (di-n-hexylamino) arylidene malonitrile (0.11) and n-propyl-α-cyano-p-methoxycinnamate (0.11), 0.08 μm silver bromide particles (0.12) , Gelatin (1.36), and 1.75% by weight of hardener, based on the total amount of gelatin in all layers,
Bis (vinylsulfonyl) methane.

Elements 19 and 20 (Inventive Example) Elements 19 and 20 were the same as Element 18. However, in the case of these elements, the green-sensitive high aspect ratio tabular grain emulsion from which Layer 1 is formed is further 0.11 g / m ² and 0.22, respectively.
It contained 0.08 μm silver bromide grains (introduced by a blend of Lippmann emulsions) at g / m ² . The development time was 4 minutes and 30 seconds.

FIG. 7 is a comparison of the behaviors of the element 18 represented by the inversion characteristic curve C18 and the element 20 represented by the inversion characteristic curve E20. For element 20, a very significant increase in maximum density, threshold sensitivity and contrast and a very significant decrease in toe density are observed. The behavior of element 19 was intermediate to that of elements 18 and 20, but closer to that of element 20.

Element 21 and Element 22 (Inventive Example) Elements 21 and 22 were the same as Element 18. However, in the case of these elements, the green-sensitive high aspect ratio tabular grain emulsion forming Layer 1 was further added with 0.054 g / m ² and 0.1 respectively.
It contained 1 g / m ² of 0.2-0.4 μm average diameter silver thiocyanate particles.

The reversal characteristic curve E21 of the element 21 and the reversal characteristic curve C18 of the element 18 are compared in FIG. From this figure, it can be seen that the maximum density and contrast are greater for element 21 than for element 18. Element 21 had a much lower density at the foot of the curve compared to Element 18.

Element 22, which had approximately twice as much silver thiocyanate coating coverage, was qualitatively similar to element 21.
And the difference was shown. However, the difference from this element 18 is
Element 22 was larger.

Element 23 (Inventive Example) This element 23 further comprises 0.11 g / m ² of 0.2 to 0.4 μm of the green-sensitive high aspect ratio tabular grain emulsion forming layer 1.
Same as Element 18 except that it contained average diameter silver thiocyanate grains and 0.22 g / m ² of 0.08 μm silver bromide grains.

The inversion characteristic curve E23 obtained for the element 23 is plotted in FIG. From this figure, elements 18 and 21 respectively
It can be seen that higher maximum densities and contrasts are embodied compared to the corresponding curves C18 and E21 representing Also, a lower foot density is realized.

Element 24 (Comparative) An element similar to Element 14 above was prepared, exposed and processed. However, for Element 24, additional silver iodide grains (0.11) with an average diameter of less than 0.1 μm were included in the emulsion layer as a result of blending in the Lippmann silver iodide emulsion.

Characteristic curve for element 14, that of curve C14 and element 24,
FIG. 9 shows a comparison with the curve C24. From this FIG. 9 it is clear that an increase in density can be achieved at any exposure level when fine silver iodide grains are added. No reduction in toe density was observed, contrast increase was minimal, and minimum density was increased. Therefore, it was not possible to realize the advantages of the present invention by substituting silver iodide grains.

Element 25 (Comparative) A control element is coated with a high sensitivity red spectrally sensitized high aspect ratio tabular grain silver bromoiodide emulsion chemically sensitized with sulfur and gold on a gelatin (4.89) subbing film support. It was prepared by The tabular silver bromoiodide grains have an average diameter of 1.
It was 6 μm and the average thickness was 0.11 μm. The silver coverage was 1.46 g / m ² and the emulsion layer gelatin coverage was 2.15 g / m ² . The emulsion layer was overcoated with gelatin (0.98), and 1.57 based on total gelatin.
The element was hardened with wt% bis (vinylsulfonyl) methane. The film support was provided with an antihalation layer (containing process removable carbon) of the type disclosed in the Simmons U.S. Patent.

Element 26 (Inventive Example) An element similar to element 25 above was prepared. However, this element 26
In the case of, the silver coverage was increased to 5% by weight by blending in a Lippmann emulsion with silver bromide grains with an average diameter of 0.08 μm in the silver bromoiodide emulsion before coating.

Element 27 (Inventive Example) An element similar to element 25 above was prepared. However, this element 27
In the case of, the silver coverage was increased to 10% by weight by blending in a Lippmann emulsion with silver bromide grains with an average diameter of 0.08 μm into the silver bromoiodide emulsion before coating.

Element 28 (Inventive Example) An element similar to element 25 above was prepared. However, this element 28
In the case of, the silver coverage was increased to 20% by weight by blending in a Lippmann emulsion with silver bromide grains with an average diameter of 0.08 μm in the silver bromoiodide emulsion before coating.

Elements 25, 26, 27 and 28 were similarly exposed and processed. Dry
After drying the element 0.61 neutral density filter and Daylight V
Filter Plus Ratten 23A Dew through the filter
Light (1/50 seconds, 500W / 2850 ° K). Antihalation layer
After removing the element, the element is replaced by Battaglini et al. U.S. Pat.
No. 263, 8 in a black and white developer of the type disclosed in Example 1.
Treat for 0 seconds, wash, and evenly expose to red light
And Schwan et al., US Pat. No. 2,959,970, Example 1.
A cyan coupler-containing color-developing method
Processed in image solution.

The characteristic curves obtained for elements 25 and 28 are
Figure 10 is plotted as C25 and E28. From this figure it can be seen that curve E28 has a higher maximum density and contrast than curve C25 and exhibits reduced density at the foot of the characteristic curve. The characteristic curves of elements 26 and 27, not shown here, are in the middle of characteristic curves C25 and E28, but
It was located closer to E28.

〔The invention's effect〕

To make the advantages of the invention demonstrated in the above examples more specific and clear, a photographic element according to the invention,
A conventional reversal photographic element consisting essentially of a silver salt having a greater solubility than silver iodide, the only difference being the absence of relatively fine grains. The relative reversal imaging behavior of the is plotted in FIG. In the figure,
Curve 1 is the reversal characteristic curve provided by the emulsion layer of a conventional reversal photographic element in which radiation-sensitive tabular silver haloiodide grains are present, but in the absence of the finer grains. Curve 2 is the reversal characteristic curve given by the same emulsion layer as above with the only difference being the inclusion of relatively fine grains. It should be understood here that the exposure and processing used to form these curves is the same. It can be seen that in the foot 2a of the characteristic curve 2, the density of this part is lower than that of the corresponding foot 1a of the characteristic curve 1. Therefore, the inverted photographic elements of this invention can form images with brighter highlights. Comparing the middle parts 1b and 2b of the characteristic curve, it can be seen that the characteristic curve of a photographic element according to the invention can exhibit a significantly higher contrast. Characteristic curve shoulders 1c and 2c
It can be seen by comparing the above that the invention is satisfied, that is, the shoulder 2c of the characteristic curve of the reversal photographic element of the invention has a much higher density. In the comparison of the shoulders 1c and 2c of the characteristic curve, curve 2 shows a decrease in density from the maximum density at the lowest exposure level shown, while in the case of curve 1 the decrease in threshold value from the maximum density of the curve. It can be acknowledged that occurs well within the concentration scale. Therefore, it can be considered that the inversion threshold sensitivity shown by the curve 2 is higher than that of the curve 1. The reversal threshold value sensitivity can be defined as an exposure level corresponding to a decrease in the threshold value (which can be detected first) from the maximum density of the reversal characteristic curve. If you describe it as the photographer's word as the final user, not the word of the photo scientist,
The invention is capable of imparting speed and "snap" to reversal photographic elements using radiation-sensitive tabular grain emulsions.

The features of the inverted photographic element according to the invention disclosed herein can be emphasized in the following cases. That is,
Very similar reversal photographic elements having one or more of the essential features of this invention as a difference are qualitative when the relatively fine grain silver salt is incorporated into those reversal photographic elements. This is the case when it is clear that no similar behavioral behavior can be expected. In particular, when relatively fine silver salt grains are present in the layer adjacent to it rather than in the radiation-sensitive tabular grain emulsion layer, the result is a loss of maximum density, loss of contrast, and foot and minimum density. The increase of If conventional non-tabular silver haloiodide emulsions are used in place of tabular grain emulsion layers, the result is significant reversal desensitization and, therefore, necessarily comparable exposure levels. At that time, an increase in foot density is caused. If relatively fine silver iodide grains are used in place of the relatively fine grains exhibiting high levels of solubility, no improvement in the shape of the characteristic curve can be observed. Furthermore, the advantage of the reversal characteristic curve can only be obtained if the radiation-sensitive tabular grains are in contrast to tabular silver halide grains which are silver haloiodide grains and lack iodide as a constituent. It was possible to implement such changes.

[Brief description of drawings]

FIG. 1 shows the reversal characteristic curve 2 of a reversal photographic element according to the present invention.
Is a graph prepared for the purpose of qualitatively comparing with the reversal characteristic curve 1 of the reversal photographic element having the difference only in the lack of the second grain group, and FIGS. Is the symbol E before the element number, respectively.
5 is a graph showing the comparison of the elements of the present invention shown by the symbols and the elements of the comparative example shown by adding the symbol C before the element numbers with respect to the inversion characteristic curve.

Continuation of the front page (56) Reference JP 58-113926 (JP, A) JP 58-111934 (JP, A) JP 58-111936 (JP, A) JP 60-12540 (JP , A) JP 58-160948 (JP, A)

Claims (1)

[Claims] 1. Having at least one image-recording emulsion layer in which the emulsion layer has a thickness of less than 0.5 μm and a minimum of 0.6.
A radiation-sensitive tabular silver haloiodide grain having a diameter of .mu.m and an average aspect ratio greater than 8: 1 is a photographic element occupying at least 35% of the total grain projected area of the emulsion layer. Grains having an average particle size of 0.05 μm or more and less than 0.5 μm, which consist essentially of a silver salt having a higher solubility than silver halide, are 0.5% or more based on the total amount of silver in the emulsion layer after grain blending 50
A photographic element capable of forming a reversal image, characterized in that it is mixed with said radiation-sensitive tabular silver haloiodide grains in a concentration of less than mol%.