JPH09127636A - Color silver halide photographic element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve color balance of a reversal color silver halide photographic element. SOLUTION: This photographic element is the multilayer and multicolor silver halide photographic element and at least one of dye forming units is spectrally sensitized in the same region of the visible spectra and has >=2 emulsion layers different in photographic sensitivity and each emulsion layer contains an image dye producing coupler and at least one (not all) of the emulsion layers in the above units contains a benzoazolium compound represented by formula I in a hydrolyzed or nonhydrolyzed form. In formula I, Z is an S, Se, or Te atom; R<1> is a substituted 1-4C anionic alkyl group; R<2> is an alkyl or aryl group or an H atom; each of R<3> and R<4> is, independently, an H or halogen atom or a nitro group or the like.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to "push processing".
To a color silver halide photographic element having at least one emulsion layer with certain benzoazolium compounds in a multilayer format, making it suitable for processing known in the art as. More specifically,
This invention relates to color silver halide reversal photographic elements.

[0002]

BACKGROUND OF THE INVENTION Push processing is a technique often used in the photographic industry to correct for intentional or unintentional underexposure. In essence, a photographer who has underexposed the photographic element (e.g., a fast-moving participant or a sports event to photograph an object, who has exposed a slower film at a faster than appropriate speed). ) Is a relatively small amount of silver formed underexposed,
It can be corrected (for example, the lost speed is regained by prolonging the development of the film in the black and white primary developer).

However, since an increase in the speed of one color record does not match the speed of the other color records in the element,
Push processing often results in poor color balance. It would be desirable to provide a method of independently and selectively (for specific color records and specific densities) color imbalance correction during push processing. These methods consist of mechanisms of development inhibition and development acceleration with an extended first development time. U.S. Pat. No. 5,460,932 describes a photographic element containing a compound that releases a development accelerator and a development inhibitor.

US Pat. No. 5,354,650 describes photographic elements containing compounds which release development inhibitors after extended development times. Thus, in the areas of the photographic element where the inhibitor is located, the inhibitor primarily affects the properties of the photographic element after the initial development stage. This affects color balance by slowing the development of one silver halide emulsion layer during the push stage, while at the same time continuing to develop other silver halide emulsion layers uninhibited.

Development accelerators are described in US Pat. No. 3,535,4
No. 87; No. 5,041,367; No. 5,460,93
No. 2 each specification; and Research Disclosure, 1989
December 08, Item 08119, Section XXI BD. Development accelerators include, for example, competitors of oxidizable developing agents as described in U.S. Pat. No. 4,923,787; U.S. Pat. Nos. 4,656,122 and 4,4.
082,553, 2,996,382, 3,1
78,282, 3,397,987 and 4,6
Also included are fine grain silver halide crystals (eg, Lippmann) or fine grain silver (eg, Carey Lea silver), as exemplified by No. 26,498, or surface or internally fogged silver halide grains. . These development accelerators, when mixed in a silver halide emulsion layer, shift the emulsion characteristic curve towards lower doses (faster speeds) at each density level (often above the final sensitometric curve). With a greater effect on the lower scale than on the scale). Development accelerators typically achieve their effect by affecting silver development or dye formation. Also, typically,
The development accelerator increases fog in the first development and causes a decrease in Dmax of the final sensitometric curve of the reversal system during push processing (even in normal processing in some cases).

[0006]

SUMMARY OF THE INVENTION The present invention provides a specific emulsion layer (exposure amount / density region) without a decrease in Dmax (due to an increase in first development fog) under both normal processing conditions and push processing conditions. Provide push promotion. The present inventors have discovered that the addition of certain benzoazolium compounds to specific layers of multilayer film elements (particularly reversal film elements) enhances the speed of certain parts of the color record during push processing (such an increase is desired). If it is)
I have found that I can.

Benzoazolium salts are used for a variety of purposes in photographic elements. US Pat. No. 3,326,26
681 describes the use of benzothiazolium salts having carboxyalkyl or sulfoalkyl substituents which are useful as antifoggants in diffusion transfer systems. U.S. Pat. No. 4,578,348 describes the speed / fog relationship of certain benzothiazolium salts. US Pat. No. 5,149,6
No. 19 describes the use of methoxybenzothiazolium salts in silver chlorobromide infrared sensitive emulsions to increase speed. US Pat. No. 5,320,93
No. 8 describes the use of benzothiazolium salts as incubation stabilizers added after sensitization of high chloride tabular grain emulsions. However, nowhere in these documents is the use or description of certain benzoazolium salts used to improve the color balance of the reversal element when using the "push treatment".

[0008]

SUMMARY OF THE INVENTION The present invention comprises a red sensitive cyan dye forming unit comprising a light sensitive silver halide emulsion layer and an image dye forming coupler; a light sensitive silver halide emulsion layer and an image dye forming coupler. A color-sensitive silver halide photographic element comprising a green-sensitive magenta dye-forming unit comprising; and a support having thereon a blue-sensitive yellow dye-forming unit comprising a light-sensitive silver halide emulsion layer and an image-dye-forming coupler. Wherein at least one of said dye-forming units comprises two or more emulsion layers spectrally sensitized to the same region of the visible spectrum but exhibiting different photographic speeds, each such emulsion layer comprising:
At least one (but not all) of the emulsion layers of the dye-forming unit containing an image dye-forming coupler,
Color silver halide photographic elements containing benzazolium compounds of formula (I) in hydrolyzed or non-hydrolyzed form:

[0009]

Embedded image

(Wherein Z represents S, Se, or Te; R ¹ is an anionic substituted alkyl group having 1 to 4 carbon atoms; R ² is an alkyl group or an aryl group; Hydrogen; and R ³ and R ⁴ are independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, a carboxy group, an alkyl or aryl group, an alkoxy group; an aryloxy group, an acylamino group, a sulfonamide group, Sulfamoyl group, sulfamide group, carbamoyl group, diacylamino group, aryloxycarbonyl group, alkoxycarbonyl group, alkoxysulfonyl group, aryloxysulfonyl group, alkylsulfonyl group, arylsulfonyl group, alkylthio group, arylthio group, alkoxycarbonylamino group, Aryloxycarbonylamino group, a Kirusuruhokishiru group, an aryl sulfoxylate group, alkylureido group, arylureido group, an alkylcarbonyl group, an arylcarbonyl group, perfluoroalkyl group, acyl group, thiocyano group,
Selected from a heterocyclic group and an acyloxy group). In one embodiment said photographic element is a reversal element. Generally, the dye-forming unit containing the benzoazolium compound is a green-sensitive, magenta dye-forming unit.

It has been found that the benzoazolium compounds of formula I provide an advantageous speed increase during push processing. This was particularly surprising as the compound does not increase speed at normal processing times. By incorporating this compound into one or more (but not all layers) of the silver halide emulsion layer of the color generating unit, it is possible to selectively control the density region of one color record during push processing. The color balance of photographic elements can be optimized.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The benzoazolium compounds of the present invention that provide an advantageous speed increase during push processing are of formula (I):

[0013]

Embedded image

Z represents S, Se, or Te, and most preferably S. R ¹ is an anionic C 1
~ 4 substituted alkyl groups. An anionic substituent is any anionic substituent that forms an intramolecular salt with the benzoazolium cation, maintains its anionic character even after hydrolysis of the benzoazolium ion, and does not destroy the intended function of the compound. Can also be Suitable anionic _{substituents, SO 3 -, CO 2 -} , or PO ₃ - includes.

R ² is an alkyl or aryl group or hydrogen. R ² can take the form of any substituent compatible with ring-opening hydrolysis of benzoazolim compounds. Preferably, the alkyl group has from 1 to 8 carbon atoms.
(For example, methyl, ethyl, propyl, i-propyl,
n-butyl, t-butyl or n-octyl) and the aryl group has 6 to 10 carbon atoms (eg phenyl or naphthyl). More preferably, R ²
Is hydrogen, an alkyl group having 1 to 4 carbon atoms, or a phenyl group.

R ³ and R ⁴ are hydrogen atom, halogen atom, nitro group, cyano group, carboxy group, alkyl or aryl group, alkoxy group; aryloxy group, acylamino group, sulfonamide group, sulfamoyl group,
Sulfamide group, carbamoyl group, diacylamino group,
Aryloxycarbonyl group, alkoxycarbonyl group, alkoxysulfonyl group, aryloxysulfonyl group, alkylsulfonyl group, arylsulfonyl group,
Alkylthio group, arylthio group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkylsulfoxyl group, arylsulfoxyl group, alkylureido group, arylureido group, alkylcarbonyl group, arylcarbonyl group, perfluoroalkyl group,
Independently selected from an acyl group, a thiocyano group, a heterocyclic group, and an acyloxy group. These groups may be substituted or unsubstituted.

Preferred R ³ and R ⁴ are independently selected from a hydrogen atom or an aryloxy or alkoxy group having 1 to 20 carbon atoms, more preferably less than 10 carbon atoms. Most preferably, at least one of R ³ and R ⁴ must be an alkoxy group. Examples of suitable substituents R ³ and R ⁴ include halogens (eg chlorine, bromine or fluorine); alkyl or aryl groups, including straight chain, branched chain or cyclic alkyl groups having 1 to 30 carbon atoms (eg , Methyl, trifluoromethyl, ethyl, t
-Butyl, phenyl, tetradecylphenyl, 4-t-
Butylphenyl, 2,4,6-trimethylphenyl and naphthyl); alkoxy groups having 1 to 30 carbon atoms (eg methoxy, ethoxy, 2-ethylhexyloxy and tetradecyloxy); aryloxy groups (eg phenoxy, α- or β-naphthyloxy, and 4-tolyloxy); an acylamino group (eg, acetamide, benzamide, butyramide, tetradecanamide, α- (2,4-di-t-amylphenoxy)-
Acetamide, α- (2,4-di-t-amyl-phenoxy) butyramide, α- (3-pentadecylphenoxy) hexanamide, α- (4-hydroxy-3-t-).
Butylphenoxy) tetradecanamide, 2-oxo-
Pyrrolidin-1-yl, 2-oxo-5-tetradecylpyrrolin-1-yl, N-methyltetradecanamide,
And t-butylcarbonamide); sulfonamide groups (for example, methanesulfonamide, benzenesulfonamide, p-toluenesulfonamide, p-dodecylbenzenesulfonamide, N-methyltetradecylsulfonamide, and hexadecanesulfonamide; sulfamoyl group) (For example, N-methylsulfamoyl, N-hexadecylsulfamoyl, N, N-dimethylsulfamoyl; N- [3- (dodecyloxy) propyl] sulfamoyl, N- [4- (2,4- Di-t-pentylphenoxy) butyl] -sulfamoyl, N-methyl-N-
Tetradecylsulfamoyl, and N-dodecylsulfamoyl); sulfamide group (for example, N-methylsulfamide and N-octadecylsulfamide); carbamoyl group (for example, N-methylcarbamoyl, N-octadecylcarbamoyl, N- [4- (2,4-di-t-
Pentyl-phenoxy) butyl] carbamoyl, N-methyl-N-tetradecylcarbamoyl, and N, N-dioctylcarbamoyl; diacylamino groups (eg N
-Succinimide, N-phthalimide, 2,5-dioxo-1-oxazolidinyl, 3-dodecyl-2,5-dioxo-1-imidazolyl, and N-acetyl-N-dodecylamino); aryloxycarbonyl groups (eg phenoxy) Carbonyl and p-dodecyloxyphenoxycarbonyl); alkoxycarbonyl group (alkoxycarbonyl group having 2 to 30 carbon atoms, for example, methoxycarbonyl, tetradecyloxycarbonyl, ethoxycarbonyl, benzyloxycarbonyl, and dodecyloxycarbonyl); alkoxysulfonyl group (Alkoxysulfonyl group having 1 to 30 carbon atoms, for example, methoxysulfonyl, octyloxysulfonyl, tetradecyloxysulfonyl, and 2-ethylhexyloxysulfonyl); aryl Kishisuruhoniru group (e.g., phenoxysulfonyl, 2,4-di -t- amylphenoxy sulfonyl); alkanesulfonyl group (having 1 to 30 carbon atoms
An alkanesulfonyl group of, for example, methanesulfonyl,
Octanesulfonyl, 2-ethylhexanesulfonyl,
And hexadecanesulfonyl); arenesulfonyl groups (eg, benzenesulfonyl, 4-nonylbenzenesulfonyl, and p-toluenesulfonyl); alkylthio groups (alkylthio groups having 1 to 22 carbon atoms, such as ethylthio, octylthio, benzylthio, tetradecylthio). , And 2- (2,4-di-t-amylphenoxy) ethylthio; arylthio groups (eg, phenylthio and p-tolylthio); alkoxycarbonylamino (eg, ethoxycarbonylamino, benzyloxycarbonylamino, and hexadecyloxycarbonyl). Amino); alkylureido group (for example, N-methylureido, N, N-dimethylureido, N-methyl-N-dodecylureido, N-hexadecylureido, N, N-dioctadecylureido , And N, N- dioctyl -N '
-Ethyl-ureido); an acyloxy group (for example, acetyloxy, benzoyloxy, octadecanoyloxy, p-dodecaneamidobenzoyloxy, and cyclohexanecarbonyloxy; a nitro group; a cyano group; a carboxy group, and nitrogen, oxygen, sulfur, 3 to 1 having at least one atom selected from selenium and tellurium
Heterocyclic group containing a 5-membered ring (eg, pyrrolidine ring, piperidine ring, pyridine ring, tetrahydrofuran ring, thiophene ring, oxazole ring, thiazole ring, imidazole ring, benzothiazole ring, benzoxazole ring, benzimidazole ring, selenazole Ring, benzoselenazole ring, tellurazole ring, triazole ring, benzotriazole ring, tetrazole ring, oxadiazole ring, or thiadiazole ring). The aforementioned organic substituents preferably have 10 or less, more preferably 5 or less carbon atoms. The benzoazolium compound is preferably soluble in an aqueous solvent. In a particularly suitable embodiment, R ³ and R ⁴ is methoxy, R ² is and R ¹ is hydrogen CH ₂ CH ₂ SO ₃ - a.

For example, "The Journal of Imaging Scien
ce and Technology '', Vol. 39, No. 1, 40-55 (1995) Figure 14
AH Herz, "Chemical Factors for the Contr
ol of Silver Halide Recrystallization and Growth ''
Benzazolium salts are hydrolyzed as shown below under the conditions usually used for emulsion preparation, such as high pH (> 3) and high temperature (> 25 ° C.). Receive. Such conditions may also exist during processing.

[0019]

Embedded image

This hydrolysis reaction transforms the benzoazolium salt (I) into the intermediate (II), and the final silver salt (I).
Change to II). The photographic emulsions of this invention can be prepared in any form (hydrolyzed or hydrolyzed) of the benzoazolium salts of this invention according to the method and timing of adding the benzoazolium compound during emulsion preparation and the method of processing the element. Not included) is also included.

The color silver halide photographic elements of this invention are:
It can have an imaging or non-imaging layer known in the art. The photographic element is a multilayer, multicolor element. Most preferred are reversal photographic elements. Multicolor elements have dye image-forming units sensitive to each of the three primary regions of the visible light spectrum. Each unit can consist of a single emulsion layer or multiple emulsion layers having spectral sensitivity in the same or substantially the same spectral region. The layers of the element can be arranged in various orders as known in the art.

In the present invention, a multicolor photographic element is a red-sensitive, cyan dye-forming unit comprising a light-sensitive silver halide emulsion layer and an image dye-forming coupler, preferably in order from the support; a light-sensitive halogenated. A green-sensitive, magenta dye-forming unit comprising a silver emulsion layer and an image dye-forming coupler; and a blue-sensitive, yellow dye-forming unit comprising a light-sensitive silver halide emulsion layer and an image dye-forming coupler are disposed thereon. It comprises a support. At least one of the dye-forming units of the photographic element is two or more emulsions in which each emulsion layer has an image dye-forming coupler and which are spectrally sensitized to the same region of visible light but exhibit different photographic sensitivities. Comprising layers. Photographic speed refers to what is known in the art as photographic speed. At least one (but not all) of the dye-forming units comprising two or more emulsion layers must contain the hydrolyzed or non-hydrolyzed form of the benzoazolium compound of formula (I). The compound of formula (I) can be contained in one or more dye-forming units of the photographic element, but cannot be present in all emulsion layers within the same unit. Preferably, the benzoazolium compound is not included in the slowest emulsion layer in the dye-forming unit. To improve granularity, the slowest emulsion layers of color reversal elements are often coated with excess silver halide compared to the couplers in the layers. Therefore, changes in the development of this layer will result in only slight changes on the dye scale, so the effect of the benzoazolium compounds will be largely unknown. Moreover, in reversal photographic elements, very low density areas do not require improved speed on push due to the effect of dissolution physical development on the slow emulsion.
On the other hand, if a benzoazolium compound is used for one or more layers of the photosensitive emulsion layer, it is possible to accelerate the concentration-ratio during the push processing, and therefore, those skilled in the art can change the other portion to a certain area of the characteristic curve. Color balance can be corrected. In order to influence only a certain part of the characteristic curve, it is better not to use the compound in all layers. Generally, only one color producing unit of a photographic element has formula (I)
Of the compound.

Preferably, the dye-forming unit containing the benzoazolium compound is a green-sensitive, magenta dye-forming unit. In one embodiment, the green-sensitive, magenta dye-forming unit consists of low, medium, and high speed silver halide emulsion layers, the middle speed layer containing a benzoazolium compound of formula (I). Useful levels of the compound are from 0.1 micromol to 10,000 micromol per silver mole. A preferable range is 1 micromol to 5,000 micromol per 1 mol of silver, and a more preferable range is 5 micromol to 1000 micromol per 1 mol of silver. The most preferred range is from 10 micromoles to 500 micromoles per silver mole.

The compound can be added to the photographic emulsion using any technique suitable for the purposes of this invention. This compound can be dissolved in any aqueous solvent such as water, alcohol or mixtures thereof. Combinations of one or more benzoazolium compounds of formula (I) can be used. Photographic emulsions are generally prepared by precipitating silver halide crystals in a colloidal matrix by conventional methods in the art. The colloid is typically a hydrophilic film forming agent such as gelatin, alginic acid or their derivatives.

The crystals produced in the precipitation step are washed, and then, a spectral sensitizing dye and a chemical sensitizer are added, and a chemical sensitization and a spectral sensitization are carried out by a heating step in which the emulsion temperature is raised and maintained for a certain period of time. The precipitation and spectroscopic and chemical sensitization methods utilized in preparing the emulsions used in the present invention can be methods known in the art. Chemical sensitization of such emulsions is generally accomplished by sulfur containing compounds (eg allylisothiothiocyanate, sodium thiosulfate and allylthiourea); reducing agents (eg polyamines and stannous salts); noble metal compounds (eg , Gold, platinum); as well as sensitizers such as polymeric reagents (eg, polyalkylene oxides). Preferably, the emulsion is sensitized with both gold and chalcogenide (most preferably gold and sulfur). Examples of sulfur sensitizers include sodium thiosulfate, alkyl or aryl thiourea compounds, or US Pat. No. 4,811.
Included are thiourea compounds having nucleophilic substituents as described in 0,626.

Examples of gold sensitizers are potassium tetrachloride gold, potassium dithiocyanate gold (I), and US Pat. Nos. 5,049,484, 5,049,485, and 5,252. Included are the gold (I) compounds described in Nos. 455, 5,220,030, and 5,391,727. Heat treatment is performed to complete chemical sensitization as described. Spectral sensitization is performed using a combination of dyes designed for wavelengths of interest in the visible or infrared spectral range. It is well known to add such dyes before or after heat treatment.

After spectral sensitization, the emulsion is coated on a support. Various coating techniques include dip coating, air knife coating, bead coating, curtain coating, and extrusion coating. The compounds of the present invention are added to the halogen compound at any time during emulsion preparation, i.e. during precipitation, during or before chemical sensitization, or during final melting and co-mixing of the emulsion with additives for coating. It can be added to a silver halide emulsion. More preferably, these compounds are added during or after chemical sensitization. Most preferably, it is added during chemical sensitization.

In one embodiment of the invention, at least one of the emulsion layers of the dye-forming unit having a benzoazolium compound of formula (I) also contains a benzoazolium salt of formula (II), Compounds of formula (I) and formula (II)
The compound (1) is not contained in the same emulsion layer.

[0029]

Embedded image

In the formula (II), Z ′, R ^{2 ′} , R ^{3 ′} and R ^{4 ′} are respectively Z, R ² , R ³ and R in the formula (I).
Same as ⁴ R ^{1 ′} has ^{1 to} 4 carbon atoms,
It is an unsubstituted or non-ionic substituted alkyl group. This non-ionic substituent must never form an inner salt with the benzoazolium cation and must maintain its non-ionic character even after the benzoazolium ion is hydrolyzed. It furthermore does not interfere with the intended use of the compound. Preferred non-cationic substituents are represented by the formula: :

[0031]

[Chemical 6]

Where T and T'are independently carbon
Nyl or sulfonyl. If m is greater than 1
, T'is in each case unrelated to the other beings.
It can be carbonyl or sulfonyl.
m is an integer of 1 to 3, preferably m is 1.
You. R is also a hydrocarbon residue which is optionally substituted
It is an amino group. R is preferably a primary if
A secondary amino group, an alkyl group having 1 to 8 carbon atoms (for example,
For example, methyl, ethyl, propyl, i-propyl, n-bu
Tyl, t-butyl or n-octyl), or carbon
An aryl group of the number 6 to 10 (for example, phenyl or
It is a futile). X^-Is a suitable anion. X^-
Suitable examples of include halide ions, p-toluenesulfur.
Honate, NO _Three ^-, ClO_Four ^-, Methylsulfate
Ion or BF_Four ^-But is not limited to these
Not.

In one preferred embodiment, the compound of formula (II) is a 3- (methylsulfamoylethyl) -benzothiazolium salt having tetrafluoroborate as an anion. The compound of formula (II) can be added to the emulsion layer of the dye-forming unit in the manner and in the amounts described for the compound of formula (I). The compound of formula (II) is generally added to the lowest sensitivity layer of the dye-forming unit, provided that it is not added to the emulsion layer (s) containing the compound of formula (I). Can be added to another layer. Preferably, these compounds are used in a green-sensitive, magenta dye-forming unit. In one aspect, the green-sensitive, magenta dye-forming unit consists of low, medium and high speed silver halide emulsion layers, the middle speed layer containing a benzoazolium compound of formula (I),
The compound of formula (II) is added to the slow silver halide.

In a particularly preferred embodiment of the present invention, the compound of formula (I)
The layer coated with the compound and the compound of formula (II) contains a development accelerator or inhibitor, or a precursor thereof. Suitable development accelerators and inhibitors are described in US Pat. Nos. 3,535,487, 5,041,367, 5,460,932, and Research Disclosure, December 1989, Item 08119, Section XX
I BD and Research Disclosure, September 1994,
Item 36544, as described in Section XVIII 5-10.

Throughout the specification and claims, substituents by asserting groups with substitutable hydrogen (eg alkyl, amine, aryl, alkoxy,
Heterocyclic, etc.) refer to the advantages of the invention as well as the unsubstituted form of the substituents, unless stated to be unsubstituted or substituted with certain substituents only. It is understood to include forms substituted with substituents that do not nullify. Examples of the substituents are the same as those described for R ³ and R ⁴ . Furthermore, any reference to an alkyl group includes a cyclic group.

In one embodiment of the invention, the blue sensitivity of the silver halide photographic element, the yellow dye-forming unit and the green sensitivity,
Between the magenta dye-forming unit is a layer containing colloidal silver and / or yellow filter dye, or a combination thereof. Suitable dyes include U.S. Pat. Nos. 2,538,008, 2,538,009,
4,420,555, 4,950,586, 4,948,718, 4,948,717, 4,940,654, 4,923,788, 4 , 900,653, 4,861,700, 4,857,446, 4,855,221, 5,213,956, 5,213,957, and 5, respectively. 298,377, and British Patent No. 695,8.
73 and 760,739, and those described in European Patent Application No. 430,186.

In another embodiment, an interlayer is placed between the blue-sensitive, yellow dye-forming unit and the layer containing the colloidal silver or yellow filter dye. Such a layer can be present between the green-sensitive layer and the layer containing colloidal silver, or between the red-sensitive layer and the layer containing colloidal silver, or a combination thereof. .

In photographic elements, intermediate layers such as those described above can be hydrophilic colloid layers known in the art. Therefore, they are gelatin (eg ossein)
Alternatively it can consist of a gelatin derivative. Other specific compatible hydrophilic colloid materials that can be used alone or in combination include cellulose derivatives, polysaccharides such as dextran, gum arabic and the like; water soluble polyvinyl compounds such as polyvinylpyrrolidone, acrylamide polymers and the like. Includes synthetic polymeric materials. Other materials are described in US Pat. No. 5,298,369 and Research Disclosure, December 1989, Item
308119, IXA.

This intermediate layer is typically 260-220.
0 mg gelatin / m ² , preferably 500 to 1000 m
It is characterized in that a level of g gelatin / m ² is applied. As mentioned above, it is placed closer to the blue sensitive unit than the second layer, and preferably immediately adjacent to such a blue sensitive unit. This intermediate layer includes a thickener, a surfactant, a hardener, a coupler, an oxidized developing agent, a scavenger,
Additional additives such as development inhibitors, development accelerators, absorbing dyes and the like can also be included. These compounds can be added in amounts and methods known in the art. This interlayer is generally free of colloidal silver.

Preferably, this intermediate layer contains a scavenger for the oxidized developing agent. Examples of this type of scavenger include disulfonamidophenols and US Pat. No. 2,33.
6,327, 2,728,659, and 2,4
Included are ballasted or non-diffusible antioxidants specifically set forth in 03,721. Others are
Research Disclosure, December 1989, Item 30
8119, VII, I and Research Disclosure, 1994
Listed in September, Item 36544, X.D. 10
1,000 mg / m ² , preferably 50-200 mg
It is preferred to mix the scavenger with the intermediate layer in an amount of / m ² , optimally between 75 and 125 mg / m ² .

The colloidal silver layer can also be selected from layers known in the art. Colloidal silver can be colloidal elemental silver of the type commonly used in the photographic art. For example, it can be yellow colloidal silver (ie, Kelly Lee silver) or black or gray / black colloidal silver. Generally, such colloidal silver contains silver particles of about 5 to about 10 nm (about 50 to about 100 angstroms) in size. The silver colloid is generally formed in gelatin or other hydrophilic colloid of the type described above.
For example, Kelly Lee silver is generally prepared by a method consisting of silver reduction in a basic solution obtained by reacting dextrin with silver nitrate. Often, phthalated gelatin is added to facilitate washing of silver products.

For the purposes of this invention, a colloidal silver concentration sufficient to achieve a favorable color balance in the midscale range (D = 0.6-1.4) is used. Typically, the amount of colloidal silver will be 5-500 mg / m ² . More typically, 25 to 250 mg / m ²
And will typically be 50-150 mg / m ² . Other additives can be added to this colloidal silver layer. They can be any additives as described when added to the first layer. Such compounds can be added in amounts and methods known in the art.

The elements of the present invention can include layers in addition to those described above. Such layers include filter layers,
(In particular, a yellow and magenta filter dye layer), an intermediate layer, an overcoat layer, an undercoat layer and the like are included. The photographic element is Research Disclosure, item 3439.
0, November 1992, (Kenneth Mason Publications, Ltd., D
udley Annex, 12a North Street, Emsworth, Hampshire
A transparent magnetic recording layer may also be included, such as a layer containing magnetic particles on the back side of a transparent support as described in PO10 7DQ, published by England). Generally, the element has a total thickness of about 5 to about 30 μm. Further, the photographic element is the Technical Bulletin No. 94-6023 (19
A flexible polyethylene naphthalate film base as described in (March 15, 1994),
Research Disclosure, Item 36230, 1994
It can be used in small format systems such as those described in June, and like the Advanced Photo System (especially Kodak Advantages film or camera).

The silver halide emulsion used in the dye-forming unit of the present invention can contain grains of any size and morphology. Thus, the grains can be cubic, octahedral, cubic-octahedral, or any other naturally occurring shape of cubic lattice type silver halide grains. Further, the grains can be irregular such as spherical grains or tabular grains. Particularly preferred are grains having a tabular morphology. Preferably, such tabular grains have a tabularity (equivalent circular diameter of the grain divided by the square of its thickness) of greater than 10, more preferably greater than about 25.

The silver halide emulsion can be either monodisperse or polydisperse during precipitation. The grain size distribution of this emulsion can be controlled by a silver halide grain separation technique or by blending silver halide emulsions having different grain sizes. These grains include silver chloride, silver bromide, silver bromochloride, silver chlorobromide, silver iodochloride, silver iodobromide,
It can be silver bromoiodochloride, silver chloroiodobromide, silver iodobromochloride and silver iodochlorobromide emulsions. In the present invention, it is preferred that the grains of each dye-forming unit are at least 75%, more preferably at least 90%, and optimally completely silver bromoiodide. The iodide content of such emulsions is
It is preferably 1 to 15 mol%, preferably 2 to 6 mol%, optimally 2 to 4 mol%.

The grains can be contained in conventional dispersing media that can be used in photographic emulsions. Specifically, the dispersion medium is contemplated to be an aqueous gelatin-peptizer dispersion medium, which may be, for example, alkali-treated gelatin (livestock bone and hide gelatin) or acid-treated gelatin (pigskin gelatin) and gelatin derivatives (acetyl). Gelatinized, phthalated gelatin) are especially considered. When used, gelatin is preferably from 0.01 to 10 based on total silver moles.
The level is 0 g. Dispersion media consisting of synthetic colloids are also conceivable.

Silver halide color reversal films are generally accompanied by the designation of development by color reversal processing. For films with color reversal development designations (the most common method is the film, its container, or packaging containing printed leaflets provided with the film), the film is developed by color reversal processing. There should be an indication that it should. Such an indication may be, for example, that the film is a "reversal film" or that it should be developed in a color reversal process, or "Process
It is a simple printed presentation that simply refers to known color reversal processes such as "E-6".

The "color reversal" process here is
Treatment with a non-color-developing agent (that is, a developer that does not produce color imagewise upon reaction with other compounds in the film: black and white developer) is used. This is followed by overexposure of unexposed silver halide, usually chemically or by exposure to light. The element is then treated with a color developer (ie, a developer that reacts with other compounds in the film to produce imagewise color).

In a typical construction, the reversal film contains no masking coupler. Furthermore, reversal films generally have a gamma of between 1.5 and 2.0, which is much higher than that for typical negative-working materials. The references in the following table are: (1) Research Disclosure, December 1978, Item 17643, (2) Research Disclosure, 1989.
December 1994, Item 308119, (3) Research Disclosure, September 1994, Item 36544, (Kenneth Mason
Publications, Ltd., Dudley Annex, 12a North Stree
t, Emsworth, Hampshire PO10 7DQ, published by England).

This table and the references cited therein should be understood as describing specific components suitable for use in photographic elements according to the present invention. This table and the references cited therein also describe suitable methods for exposing, processing and manipulating the element and the images contained therein.
Ingredients particularly suitable for use in the photographic elements of this invention are described in Research Disclosure, February 1995, Item 37038.

[0051] Reference number Section Subject 1 I, II Grain composition, morphology and preparation; Dura 2 I, II, IX, X, including agents, coating aids, additives XI, XII, XIV, XV Emulsion preparation 3 I, II , III, IX A & B 1 III, IV Chemical sensitization and spectral sensitization / desensitization 2 III, IV 3 IV, V 1 V UV dye, fluorescent whitening agent, 2 V fluorescent dye 3 VI 1 VI Antifoggant and stable Agents 2 VI 3 VII 1 VIII Absorption and scattering materials; Antistatic layers 2 VIII, XIII, XVI; Matting agents 3 VIII, IX C & D 1 VII Image couplers and image-modifying couplers 2 VII colorants; Dye stabilizers and hues Modified 3 X Good agent 1 XVII Support 2 XVII 3 XV 3 XI Specific layer arrangement 3 XII, XIII Negative emulsion; Direct positive emulsion 2 XVIII Exposure 3 XVI 1 XIX, XX Chemical treatment; Developer 2 XIX, XX, XXII 3 XVIII, XIX, XX 3 XIV scanning and digital processing methods

The photographic element supports of the present invention include cellulose esters (eg, cellulose triacetate and cellulose diacetate) and polyesters of dibasic aromatic carboxylic acids and dihydric alcohols (eg, polyethylene terephthalate, polyethylene naphthalate). Phthalates), papers and polymer coated papers. Such supports are described in detail in Research Disclosure 3, Section XV.

The photographic elements can also contain additional materials which enhance or improve the bleaching or fixing processing steps to enhance image quality. European Patent Application No. 193,38
9 and 301,477; U.S. Patent No. 4,163.
669, 4,865,956, and 4,92.
The bleaching accelerators described in 3,784 are particularly useful. Further, nucleating agents, development accelerators or precursors thereof (British Patent Nos. 2,097,140 and 2,131,188); electron transfer agents (US Pat. No. 4,859,578 and No. 4,912,025); antifoggants and color mixture inhibitors such as hydroquinones, aminophenols, amines, and gallic acid derivatives; catechol; ascorbic acid; hydrazides; sulfonamidephenols; The use of color producing couplers is also contemplated.

The element also includes a filter dye layer comprising colloidal silver sol and / or yellow and / or magenta filter dyes, either as oil-in-water dispersions, latex dispersions or solid particle dispersions. be able to. In addition, "smear" them
Couplers (eg US Pat. No. 4,366,237;
European Patent Application No. 96,570; US Patent No. 4,42
0,556 and 4,543,323). Further, the coupler is described in, for example, Japanese Patent Application No. 61-25824.
Protective forms can be blocked or coated as described in US Pat. No. 9, or US Pat. No. 5,019,492.

The photographic elements can further contain other image-modifying compounds such as "Development Inhibitor Releasing" compounds (DIR's). The DIR compound is, for example, Photograph
ic Science and Engineering, 13: 174 (1969).
CR Barr, JR Thirtle and PW Vittum's "Devel
oper-Inhibitor-Releasing (DIR) Couplers for ColorPh
otography ”. DIRs with particular application to color reversal elements are described in US Pat.
9,465, 5,380,633, 5,39
9, 466, and 5,310,642.

It is also conceivable to obtain a reflective color print using the concept of the invention. The emulsions and materials forming the elements of this invention were formulated with an epoxy solvent (described in European Patent Application 0164961), additional stabilizers (eg, US Pat.
40,653, and 4,906,559), and ballast as described in U.S. Pat. No. 4,994,359, which reduces the sensitivity to polyvalent cations such as calcium. Chelating agents and stain reducing compounds as described in US Pat. Nos. 5,068,171 and 5,096,805,
It can be coated on a pH adjusted support as described in US Pat. No. 4,917,994. Other compounds useful in the elements of the invention are described in the following publications: JP-A-58-09959;
-62586; JP-A-02-072629;
No. 072630; No. 02-072632; No. 02-
No. 072633; No. 02-072634; No. 02-0.
77822; 02-0278229; 02-07.
No. 8230; No. 02-079336; No. 02-079.
No. 338; No. 02-079690; No. 02-0796.
No. 91; No. 02-080487; No. 02-08048.
No. 9; No. 02-080490; No. 02-080491.
No. 02-080492; No. 02-080494.
No. 02-0885928; No. 02-0866669.
No. 02-0886670; No. 02-087361.
No. 02-087362; No. 02-087363.
No. 02-087364; No. 02-088096.
No. 02-088097; No. 02-093662.
No. 02-093663; No. 02-093664
No. 02-093665; No. 02-093666.
No. 02-094668; No. 02-094055.
No. 02-094056; No. 02-101937.
No. 02-103409; No. 02-151577.
issue.

The silver halide grains used in the present invention were obtained by researching disclosure 3 and James, The Theory.
It can be prepared according to methods known in the art, such as those described in of the Photographic Process. These methods include methods such as ammoniacal emulsion making, neutral or acidic emulsion making, and others known in the art. In these methods, generally, a water-soluble silver salt is mixed with a water-soluble halide salt in the presence of a protective colloid, and when the silver halide is produced by precipitation, the temperature, pAg, pH value, etc. are adjusted to appropriate values. It takes control.

The silver halide used in the present invention may be combined with noble metal (eg, gold) sensitizers, intermediate chalcogen (eg, sulfur) sensitizers, reduction sensitizers and other sensitizers known in the art. It can be advantageously used for chemical sensitization. Compounds and techniques useful in chemical sensitization of silver halide are known in the art and are described in Research Disclosure 3
And the references cited therein.

The emulsion can also include any of the addenda known to be useful in photographic emulsions. These additives include, for example, chemical sensitizers such as activated gelatin, sulfur, selenium, tellurium, gold, platinum, palladium, iridium, osmium, rhenium, phosphorus, or combinations thereof. Chemical sensitization is generally performed with a pAg of 5-10, as illustrated by Research Disclosure, June 1975, Item 13452, and US Pat. No. 3,772,031.
Levels, pH levels of 5-8 and temperatures of 30-80 ° C.

The silver halide can be sensitized with a sensitizing dye by any method known in the art as described in Research Disclosure 3. Examples of such dyes are cyanines, merocyanines, cyanines and complexes of merocyanines (ie tri-, tetra- and polynuclear cyanines and merocyanines), oxonols, hemioxonols, styryls, merostyrils. , And dyes of various dye classes, such as the polymethine dye class including streptocyanins.
The dyes can be added to emulsions of silver halide grains and hydrophilic colloids at any time prior to (eg, during or after chemical sensitization) coating of the emulsion in a photographic element, or at the same time as coating. The dye / silver halide emulsion can be mixed with a dispersion of color image-forming coupler immediately before coating or before coating.

Photographic elements of this invention can be imagewise exposed using any of the techniques known in the art, including those described in Research Disclosure 3. This generally requires exposure to light in the visible region of the spectrum, such exposure being a live image through a lens. However, the elements of the invention can be exposed in a film writer as described above. Exposure in a film writer is by means of a light emitting device (eg, light controlled by a light valve, CRT, etc.) stored image (eg, computer stored image)
Exposure.

Preferably, the photographic element comprising the composition of this invention is a color reversal element. This element can be processed with any color reversal process. As noted above, such treatment involves first treating the element with a black and white developer, then fogging unexposed particles with chemical or light fog, and then treating with a color developer. It costs.

Preferred non-color developing agents (ie black and white developing agents) are hydroquinones (eg hydroquinone sulphonates). Preferred color developing agents are p-phenylenediamines. Particularly preferred developing agents are: 4-amino-N, N-diethylaniline hydrochloride, 4
-Amino-3-methyl-N, N-diethylaniline hydrochloride, 4-amino-3-methyl-N-ethyl-N- (β-
Methanesulfonamido) ethylaniline sesquisulfate hydrate, 4-amino-3-methyl-N-ethyl-N- (β
-Hydroxyethyl) aniline sulfate, 4-amino-3
-Β- (methanesulfonamido) ethyl-N, N-diethylaniline hydrochloride, and 4-amino-N-ethyl-N
-(2-methoxyethyl) -m-toluidine di-p-
It is toluene sulfonic acid.

Development is followed by bleach-fixing to remove silver or silver halide, washing and drying. Bleaching and fixing can be done using any of the materials known to be used for this purpose. Bleaching baths are generally iron (I
II) water-soluble salts and complexes (eg potassium ferricyanide, ferric chloride, ammonium or potassium salts of iron ethylenediaminetetraacetate), water-soluble persulfates (eg potassium persulfate, sodium or ammonium), water-soluble It consists of an aqueous solution of an oxidizing agent such as organic dichromates (eg potassium dichromate, sodium, and lithium). Fixing baths are generally compounds that form water-soluble salts with silver ions, such as sodium thiosulfate, ammonium thiosulfate, potassium thiocyanate,
It consists of an aqueous solution of sodium thiocyanate and thiourea. Details of the bleaching and fixing baths are described in Research Disclosure 3.

The photographic element can be incorporated into an exposure structure intended for repeated use or an exposure structure intended for a limited number of applications such as disposable cameras, camera with lenses or photosensitive material packaging units. However, the color reversal element of the present invention may also be used for exposure with an electronic film writer, such film writer typically exposing the film with a laser, laser diode, or other controlled light source. it can.

The practice of the present invention is described in detail below with reference to specific specific examples, but the present invention is not limited thereto.

[0067]

EXAMPLE 1 The invention is illustrated in a green-sensitive magenta dye-forming layer that requires more speed when pushed within a multilayer photographic element. The green-sensitive layer was coated in three layers with a conventional color reversal multicolor element, a high speed layer (FM), a medium speed layer (MM) and a low speed layer (SM). In particular, the invention has been described in the high and medium sensitivity green sensitive layers.

The imaging emulsions were all iridium doped tabular AgBrI grains. Iodide content of green-sensitive emulsion, grain size (equivalent circular diameter (ECD)), average thickness t
(Mm) and average tabularity (T) were as follows:

Emulsion I Mol% ECD t T FM A 2 1.2 0.13 71 MM B 3 0.6 0.11 50 SM A 4 0.3 0.075 53

The green-sensitive emulsion (C) having the lowest sensitivity was prepared by adding 94 μmol / Ag mol of B selected from the formula (II).
Sensitized with TA-II. High and medium speed green sensitive layer emulsions were sensitized with BTA-I selected from formula (I) and compared with BTA-II showing the present invention. Green sensitive layer emulsions A and B were optimally sensitized with the following sensitizers:

S-1: 4,5-dihydroxybenzene
1,3-disulfonic acid, disodium salt S-2: P-acetamidophenyl disulfide S-3: sodium thiocyanate S-4: the following formula S-5: the following formula S-6: dithiosulfatogold (I) trisodium S -7: Sodium thiosulfate

Emulsions A-1 to A-5 and Emulsions B-1 to B-
3 was prepared from Emulsions A and B by adding varying amounts and types of benzoazolium salts as sensitizers. A benzoazolium compound was added during chemical sensitization before heat aging.

Benzazolium salt emulsion number (μmol / Agmol) FM A-1 None (0) FM A-2 BTA-I (21) FM A-3 BTA-I (43) FM A-4 BTA- I (64) FM A-5 BTA-II (49) MM B-1 BTA-II (94) MM B-2 BTA-I (82) MM B-3 BTA-I (164)

[0074]

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[0075]

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Samples 101-106 were prepared using a cellulose triacetate film support with an undercoat layer.
As shown below, each sample was coated by changing only the types of emulsions A and B coated on the medium-speed or high-speed magenta layer (green sensitive layer). The coating amount of the composition of each layer is g /
m ² .

First layer: Antihalation layer Black colloidal silver 0.43 (silver amount) Gelatin 2.44 Second layer: Intermediate layer Gelatin 1.22 Third layer: Low sensitivity red sensitive layer Silver iodobromide emulsion 0 .32 (amount of silver) Fine grain silver bromide 0.05 (amount of silver) Cyan coupler C-1 0.12 Solvent-2 0.06 Gelatin 1.08 Fourth layer: middle-sensitive red-sensitive layer Silver iodobromide emulsion 0 .28 (silver amount) Fine grain silver bromide 0.04 (silver amount) Cyan coupler C-1 0.36 Solvent-2 0.18 Gelatin 0.65 Fifth layer: high-sensitivity red-sensitive layer Silver iodobromide emulsion 0 .48 (silver amount) Fine grain silver iodobromide 0.05 (silver amount) Fine grain silver bromide 0.03 (silver amount) Cyan coupler C-1 0.78 Solvent-2 0.39 Gelatin 1.28

Sixth layer: Magenta filter layer Competitor-1 0.16 Solvent-2 0.16 Dye-1 0.06 Gelatin 0.81 Seventh layer: Intermediate layer Additive-2 0.001 Gelatin 0.61 Eighth layer: low sensitivity green sensitive layer (SM) Silver iodobromide emulsion C 0.35 (silver amount) Fine grain silver bromide 0.05 (silver amount) Coupler M-2 0.04 Coupler M-1 0.08 Solvent-1 0.06 Gelatin 0.52 9th layer: Medium sensitivity green sensitive layer (MM) Silver iodobromide emulsion B 0.36 (silver amount) shown in Table I Coupler M-2 0.15 Coupler M-1 0.34 Solvent-1 0.25 Gelatin 0.86 10th layer: High-sensitivity green-sensitive layer (FM) Silver iodobromide emulsion A 0.50 (silver amount) shown in Table I Fine grain silver iodobromide 0.04 (Amount of silver) Coupler M-2 0.29 Coupler M-1 0.69 Solvent-1 0.4 9 gelatin 1.64

11th layer: intermediate layer gelatin 0.61 12th layer: yellow filter layer Kelly Lee silver 0.07 gelatin 0.68 13th layer: intermediate layer Competitor-1 0.11 gelatin 0.61 14th layer : Low-sensitivity blue-sensitive layer Silver iodobromide emulsion 0.43 (silver amount) Coupler Y-1 0.98 Additive-1 0.004 Solvent-2 0.33 Solvent-3 0.01 Gelatin 1.43 15th Layer: High-sensitivity blue-sensitive layer Silver iodobromide emulsion 0.57 (silver amount) Coupler Y-1 1.45 Additive-1 0.003 Solvent-2 0.44 Solvent-3 0.01 Gelatin 1.87th 16th layer: First protective layer Competitor-1 0.06 Gelatin 1.40 UV absorbing dye 0.50 17th layer: Second protective layer Fine grain silver bromide 0.12 (silver amount) Matting agent 0.02 Bix (Vinylsulfonylmethane) 0.26 Zera Chin 0.97

[0080]

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[0081]

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Solvent-1 Di-n-butylphthalate Solvent-2 Tricresyl Phosphate Solvent-3 N, N-Diethyllauramide

[0083]

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[0084]

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[0085]

[Table 1]

As can be seen from Table I above, the photographic elements of this invention showed no speed increase in the green sensitive layer at a typical processing time of 6 minutes. However, at 11 minutes of development, the inventive samples show an increased speed change over the comparative samples at one or more concentrations in the green sensitive layer. The change in speed during push processing is specific to the emulsion layer containing the present invention. B is the highest sensitivity layer for green light
Addition of TA-I (Samples 102 and 103) increases the speed in the high density range, and addition to the mid-sensitivity layer to green light (Samples 105 and 106) accelerates the speed of the mid to low density. When BTA-1 was added to both the high sensitivity layer and the medium sensitivity layer for green light (Sample 10
4) Speed up the maximum density range when pushing.

Example 2 Eighth, ninth and tenth layers (magenta or green sensitive layer)
Samples 201-204 and Sample 301 as described in Example 1 except that was coated as shown below.
~ 307 was prepared and processed. The coating amount of the composition of each layer is g
/ M ² .

Eighth Layer: Low-Sensitivity Green Sensitive Layer Silver Iodobromide Emulsion C 0.36 (Silver Amount) Silver Bromide Lippmann Emulsion 0.05 Coupler M-2 0.04 Coupler M-1 0.08 Solvent-1 0.06 Gelatin 0.54 9th layer: Medium-sensitive green sensitive layer Silver iodobromide emulsion B 0.36 (silver amount) shown in Table II or III Coupler M-2 0.16 Coupler M-1 0.32 Solvent -1 0.24 Gelatin 0.86 10th layer: High-sensitivity green-sensitive layer Silver iodobromide emulsion C 0.47 (silver amount) shown in Table II or III Fine grain silver iodobromide emulsion 0.04 (silver amount) Coupler M-2 0.33 Coupler M-1 0.66 Solvent-1 0.50 Gelatin 1.66

[0089]

[Table 2]

[0090]

[Table 3]

Tables II and III demonstrate that the photographic elements of the present invention showed no speed increase in the green sensitive layer at a typical processing time of 6 minutes. However, at 11 minutes of development, the inventive samples show an increased speed change over the comparative samples at one or more concentrations in the green sensitive layer. It also demonstrates the selective unique nature of the increased speed obtained during push processing, which is layer dependent with the compounds of the invention of formula (I).

Other preferred aspects of the invention are described below in connection with the claims. Aspect 1 is claim 1
Is the same as (Aspect 1) Red-sensitive, cyan dye-forming unit comprising a light-sensitive silver halide emulsion layer and an image dye-forming coupler; Green-sensitive, magenta dye-forming comprising a light-sensitive silver halide emulsion layer and an image dye-forming coupler. A color silver halide photographic element comprising a unit; and a support having thereon a light sensitive silver halide emulsion layer and an image dye-forming coupler and a blue-sensitive, yellow dye-forming unit disposed thereon. At least one of the generating units comprises two or more emulsion layers spectrally sensitized to the same region of the visible spectrum but exhibiting different photographic sensitivities;
Each such emulsion layer contains an image dye-forming coupler and at least one (but not all) of the emulsion layers of said dye-forming unit is of the formula (I) in hydrolyzed or non-hydrolyzed form. Color silver halide photographic elements containing benzoazolium compounds:

[0093]

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(In the formula, Z represents S, Se, or Te; R ¹ is an anionic substituted alkyl group having 1 to 4 carbon atoms; R ² is an alkyl group or an aryl group; Hydrogen; and R ³ and R ⁴ are independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, a carboxy group, an alkyl or aryl group, an alkoxy group; an aryloxy group, an acylamino group, a sulfonamide group, Sulfamoyl group, sulfamide group, carbamoyl group, diacylamino group, aryloxycarbonyl group, alkoxycarbonyl group, alkoxysulfonyl group, aryloxysulfonyl group, alkylsulfonyl group, arylsulfonyl group, alkylthio group, arylthio group, alkoxycarbonylamino group, Aryloxycarbonylamino group, a Kirusuruhokishiru group, an aryl sulfoxylate group, alkylureido group, arylureido group, an alkylcarbonyl group, an arylcarbonyl group, perfluoroalkyl group, acyl group, thiocyano group,
Selected from a heterocyclic group and an acyloxy group).

(Aspect 2) The photographic element according to aspect 1, wherein the photographic element is a reversal element. (Aspect 3) The photographic element according to aspect 1, wherein the dye-forming unit containing the benzoazolium compound is a green-sensitive, magenta dye-forming unit. (Aspect 4) The photographic element according to aspect 1, wherein the benzoazolium compound is not contained in the low-speed emulsion layer of the dye-forming unit.

(Aspect 5) R^Three And R^Four But independently, water
Elementary atom or alkoxy group having 1 to 20 carbon atoms or ant
A photographic element according to aspect 1 selected from the group oxy groups. (Aspect 6) R¹ The above anionic substituent is SO_Three -, C
O_Two -Or PO _Three -Requires the photograph according to Aspect 1
Elementary. (Aspect 7) R^Two Is hydrogen, an alkyl group having 1 to 4 carbon atoms,
Alternatively, the photographic element of embodiment 1 which is a phenyl group.

(Aspect 8) R^Three And R^Four Is methoxy
R^Two Is hydrogen and R ¹ But CH_Two CH_Two 
SO_Three A photographic element according to aspect 1, which is (Aspect 9) Containing a benzoazolium compound of formula (I)
At least one of the emulsion layers of the dye-forming unit
It also contains a benzoazolium salt of formula (II)
Emulsion layer in which the compound of (I) and the compound of formula (II) are the same
A photographic element according to aspect 1, which is not contained in:

[0098]

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(In the formula, Z ′ is S, Se, or Te.
R ^{1 ′} is an unsubstituted or nonionic substituted alkyl group having 1 to 4 carbon atoms; R ^{2 ′} is an alkyl group or an aryl group or hydrogen; R ^{3 ′} and R
^4'is independently a hydrogen atom, a halogen atom, a nitro group,
Cyano group, carboxy group, alkyl or aryl group, alkoxy group; aryloxy group, acylamino group, sulfonamide group, sulfamoyl group, sulfamide group, carbamoyl group, diacylamino group, aryloxycarbonyl group, alkoxycarbonyl group, alkoxysulfonyl group , An aryloxysulfonyl group, an alkylsulfonyl group, an arylsulfonyl group, an alkylthio group, an arylthio group, an alkoxycarbonylamino group,
Aryloxycarbonylamino group, alkylsulfoxyl group, arylsulfoxyl group, alkylureido group, arylureido group, alkylcarbonyl group, arylcarbonyl group, perfluoroalkyl group, acyl group,
Selected from thiocyano groups, heterocyclic groups, and acyloxy groups; and X is a suitable anion).

Embodiment 10 A photographic element according to Embodiment 9 wherein the compound of formula (II) is a 3- (methylsulfamoylethyl) -benzothiazolium salt having tetrafluoroborate as an anion. (Aspect 11) A red-sensitive and cyan dye-forming unit comprising a photosensitive silver halide emulsion layer and an image dye-forming coupler in order from the support; each contains an image dye-forming coupler and has the same visible spectrum. A green-sensitive, magenta dye-forming unit comprising two or more emulsion layers spectrally sensitized to regions but exhibiting different photographic speeds; and a light-sensitive silver halide emulsion layer and an image dye-forming coupler. A color reversal photographic element comprising a support having thereon a blue-sensitive, yellow dye-forming unit, wherein at least one (but not all) of the emulsion layers of said green-sensitive magenta dye-forming unit comprises:
Color reversal photographic elements containing benzazolium compounds of formula (I) in hydrolyzed or non-hydrolyzed form:

[0101]

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(In the formula, Z represents S, Se, or Te; R ¹ is an anionic substituted alkyl group having 1 to 4 carbon atoms; R ² is an aliphatic group or an aromatic group. R ³ and R ⁴ are independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, a carboxy group, an alkyl or aryl group, an alkoxy group; an aryloxy group, an acylamino group, a sulfonamide. Base,
Sulfamoyl group, sulfamide group, carbamoyl group,
Diacylamino group, aryloxycarbonyl group, alkoxycarbonyl group, alkoxysulfonyl group, aryloxysulfonyl group, alkylsulfonyl group, arylsulfonyl group, alkylthio group, arylthio group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkylsulfoxyl Group, arylsulfoxyl group, alkylureido group, arylureido group,
Selected from an alkylcarbonyl group, an arylcarbonyl group, a perfluoroalkyl group, an acyl group, a thiocyano group, a heterocyclic group, and an acyloxy group).

(Aspect 12) Colloidal silver or yellow filter dye, or both colloidal silver and yellow dye-forming units are contained between the blue-sensitive and yellow-sensitive dye-forming units and the green-sensitive and magenta dye-forming units. A photographic element according to aspect 11 wherein a layer consisting of is present. (Aspect 13) An aspect in which there is an intermediate layer disposed between the blue-sensitive, yellow dye-forming unit and a layer containing colloidal silver or a yellow filter dye or both colloidal silver and a yellow dye-forming unit. 1
The photographic element as described in 2.

(Aspect 14) The photographic element according to aspect 11, wherein the benzoazolium compound is not contained in the low-speed emulsion layer of the dye-forming unit. (Aspect 15) A photographic element according to aspect 14 wherein said green-sensitive, magenta dye-forming unit comprises low-, medium-, and high-sensitivity halide emulsion layers. (Aspect 16) The photographic element according to aspect 11, wherein R ³ and R ⁴ are independently selected from a hydrogen atom, an alkoxy group having 1 to 20 carbon atoms or an aryloxy group.

(Aspect 17) A photographic element according to aspect 11, wherein the anionic substituent on R ¹ is SO ₃ —, CO ₂ —, or PO ₃ —. (Aspect 18) The photographic element according to aspect 11, wherein R ² is hydrogen, an alkyl group having 1 to 4 carbon atoms, or a phenyl group. (Aspect 19) R ³ and R ⁴ are methoxy, and R ²
Is hydrogen and R ¹ is CH ₂ CH ₂ SO ₃ —
A photographic element according to aspect 11, which is

(Embodiment 20) At least one of the emulsion layers of the dye-forming unit containing the benzoazolium compound of the formula (I) also contains a benzoazolium salt of the formula (II), A photographic element according to aspect 11 wherein the compound and the compound of formula (II) are not contained in the same emulsion layer:

[0107]

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(In the formula, Z ′ is S, Se, or Te.
The expressed; R 1 ^'is of 1 to 4 carbon atoms, unsubstituted or nonionic substituted alkyl group; R ^2' is an alkyl group or aryl group or hydrogen; R 3 ^'and R
^4'is independently a hydrogen atom, a halogen atom, a nitro group,
Cyano group, carboxy group, alkyl or aryl group, alkoxy group; aryloxy group, acylamino group, sulfonamide group, sulfamoyl group, sulfamide group, carbamoyl group, diacylamino group, aryloxycarbonyl group, alkoxycarbonyl group, alkoxysulfonyl group , An aryloxysulfonyl group, an alkylsulfonyl group, an arylsulfonyl group, an alkylthio group, an arylthio group, an alkoxycarbonylamino group,
Aryloxycarbonylamino group, alkylsulfoxyl group, arylsulfoxyl group, alkylureido group, arylureido group, alkylcarbonyl group, arylcarbonyl group, perfluoroalkyl group, acyl group,
Selected from thiocyano groups, heterocyclic groups, and acyloxy groups; and X is a suitable anion).

(Aspect 21) A photographic element according to aspect 20, wherein the compound of formula (II) is a 3- (methylsulfamoylethyl) -benzothiazolium salt having tetrafluoroborate as an anion. (Aspect 22) Red-sensitive, cyan dye-forming unit comprising a photosensitive silver halide emulsion layer and an image dye-forming coupler in order from the support; each containing an image dye-forming coupler and having the same visible spectrum A green-sensitive, magenta dye-forming unit comprising two or more emulsion layers spectrally sensitized to regions but exhibiting different photographic speeds; and a light-sensitive silver halide emulsion layer and an image dye-forming coupler. A color reversal photographic element comprising a support having thereon a blue-sensitive, yellow dye-forming unit, wherein at least one (but not all) of the emulsion layers of said green-sensitive magenta dye-forming unit comprises:
A hydrolyzed or non-hydrolyzed benzoazolium compound of formula (I) is contained, and colloidal silver or a yellow filter is provided between the blue-sensitive, yellow dye-forming unit and the green-sensitive, magenta dye-forming unit. There is a dye or a layer comprising both colloidal silver and a yellow dye-forming unit, and said blue-sensitive, yellow dye-forming unit and a colloidal silver or yellow filter dye or a colloidal silver and a yellow dye-forming unit. A color reversal photographic element in which there is an intermediate layer positioned between said layers comprising both:

[0110]

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(In the formula, Z represents S, Se, or Te; R ¹ is an anionic substituent of SO ₃ —, CO _2;
-Or PO _3- , which has an anionic carbon number of 1 to
4 is a substituted alkyl group; R ² is hydrogen, an alkyl group having 1 to 4 carbon atoms or a phenyl group; and R ³ and R ⁴ are independently a hydrogen atom or 1 to 4 carbon atoms.
20 alkoxy or aryloxy groups).

(Embodiment 23) The photographic element according to embodiment 22, wherein the benzoazolium compound is not contained in the low-speed emulsion layer of the dye-forming unit. (Aspect 24) R ³ and R ⁴ are methoxy, and R ²
Is hydrogen and R ¹ is CH ₂ CH ₂ SO ₃ —
A photographic element according to aspect 22, which is (Aspect 25) At least one of the emulsion layers of the dye-forming unit containing a benzoazolium compound of the formula (I) has tetrafluoroborate as an anion.
-(Methylsulfamoylethyl) -benzothiazolium salt is also included, but the compound of formula (I) and 3- (methylsulfamoylethyl) -benzothiazolium salt are not contained in the same emulsion layer Photographic element according to Item 22.

While the preferred embodiments of the invention have been described in particular detail, it will be appreciated that various changes and modifications can be made within the spirit and scope of the invention.

 ─────────────────────────────────────────────────── ─── Continued Front Page (72) Inventor Arlis Tolman Bowen 14612, New York, USA 14612, Rochester, Ellington Circle 44 (72) Inventor San Hyun Kim United States, New York 14534, Pittsford, Sutton Point 19

Claims (1)

[Claims] 1. A red-sensitive, cyan dye-forming unit comprising a light-sensitive silver halide emulsion layer and an image dye-forming coupler; a green-sensitive, magenta dye comprising a light-sensitive silver halide emulsion layer and an image dye-forming coupler. Generation unit;
And a color silver halide photographic element comprising a support having thereon a light sensitive silver halide emulsion layer and an image dye-forming coupler and a blue-sensitive, yellow dye-forming unit disposed thereon. At least one of the emulsions is spectrally sensitized to the same region of the visible spectrum but exhibits two or more emulsion layers exhibiting different photographic speeds, each such emulsion layer containing an image dye-forming coupler, A color silver halide photographic element containing a benzazolium compound of formula (I) in hydrolyzed or non-hydrolyzed form in at least one (but not all) of the emulsion layers of the dye-forming unit: ] (In the formula, Z represents S, Se, or Te; R ¹
Is an anionic substituted alkyl group of 1 to 4 carbon atoms; R ² is an alkyl group or aryl group or hydrogen; and R ³ and R ⁴ are independently hydrogen atom, a halogen atom , Nitro group, cyano group, carboxy group, alkyl or aryl group, alkoxy group; aryloxy group, acylamino group, sulfonamide group, sulfamoyl group, sulfamide group, carbamoyl group, diacylamino group, aryloxycarbonyl group, alkoxycarbonyl group , Alkoxysulfonyl group, aryloxysulfonyl group, alkylsulfonyl group, arylsulfonyl group, alkylthio group, arylthio group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkylsulfoxyl group, arylsulfoxyl group, alkylurei Group, arylureido group, an alkylcarbonyl group, an arylcarbonyl group, perfluoroalkyl group, an acyl group, a thiocyano group, a heterocyclic group,
And an acyloxy group).