JPH11143009A - Photographic element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a controllable sensitization range by properly selecting first and second blue sensitive dyes by forming one silver halide emulsion layer containing silver halide to be sensitized the first blue sensitizing dye and the second blue sensitizing dye each having a specified maximum absorption wavelength and separating each maximum absorption wavelength, by a specified energy gap. SOLUTION: The photographic element is provided with one silver halide emulsion layer containing the silver halide which is sensitized by using the first blue sensitive dye having the maximum absorption wavelength λ1 <=475 nm and the second blue sensitive dye having the maximum absorption wavelength λ2 (both dyes contain no selenium). λ1 is longer than λ2 and λ1 and λ2 are separated by an energy gap ΔE<=0.12 eV and ΔE is defined by the formula in which λ1 is the maximum absorption wavelength (nm) sensitized with the first sensitizing dye and λ2 is the maximum absorption wavelength (nm) sensitized with the second sensitizing dye.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

FIELD OF THE INVENTION The present invention relates to photographic elements, and more particularly, to photographic elements comprising a silver halide emulsion layer containing at least two sensitizing dyes.

[0002]

2. Description of the Related Art Cyanine dyes used for spectral sensitization are:
The formation of J-aggregates upon adsorption to silver halide crystals is generally well known in the practice of spectral sensitization of silver halide for color photographic applications. (This does not assert that J-aggregates are typical of cyanine dyes, but simply indicates that it is one property of such cyanine dyes that is useful for photographic purposes.) J aggregates ”
TH James, The theory of the Photographic Proc
ess, 4th edition, Macmillan Publishing Co. New York,
1977.

The discovery of two types of cyanine dyes that form so-called "mixed aggregates" when used simultaneously in emulsions has been a topic of great interest in photographic science research. For example, Y. Yonezawa, T. Miyama, and H. Ishizawa, J. Imaging Sci. Technol., 39 331 (1995);
Thin Solid Films, 261 by liznyuk and H. Mohwald
275 (1995); by TL Penner and D. Mobius, Thi.
n Solid Films, 132 185 (1985); and G. Scheibe, A.
See Naturwiss, 29 474 (1937) by Mareis, H. Ecker.

[0004] This phenomenon offers much to practice in photographic science. For example, the performance of spectral sensitization will no longer be forced by the location of one type of dye, but rather a mixture of dyes will be able to manipulate the location of spectral sensitization without difficulty. This will give the photo a very large utility. This is because the light output of the captured image or scene is often inconsistent with currently available sensitizing dye light capture locations.

[0005] However, the literature only isolated examples of dyes known to form mixed aggregates.
"However, little is known about the molecular properties that determine miscibility or immiscibility.
This is unfortunate. This is because mixed aggregates are very promising for various reasons. 'The physical laws governing this behavior are merely known in nature.

[0006] The dyes must be sufficiently sterically similar in their configuration so that the perceived extent of the property is only compatible in mixed aggregates. The only thing that must not be energetically separated from each other. For example, Yonezawa et al. Describe plausibly that "two individual aggregate locations at almost the same location prefer to form HA aggregates." (HA
Is defined as "homogeneous aggregates". )

[0007]

These obscure guidelines set forth above disclose that the dyes that form the so-called mixed aggregates are carefully designed and constructed, and furthermore, to attempt to place them at specific locations in the visible spectrum. Not useful to scientists and engineers. This obscure guideline has no choice, is a trial and error typified by Edison a century ago, and may never reach the desired goal.

[0008] Photographic elements generally contain a light-sensitive silver halide emulsion sensitive to blue light. Generally, a sensitizing dye is used to provide the desired sensitivity to blue light. Dyes for this use tend to be water-insoluble and are added to silver halide emulsions in a water / alcohol solution. The problem that arises with this operation is dye crystallization. For this reason, a large amount of dye must be used to secure the desired sensitivity.
Also, crystallization of dyes presents difficulties in the manufacture of photographic elements (before coating the emulsion on a support, clogs the filters used to purify the emulsion).

In the manufacture of photographic elements, the materials of construction used can have undesirable consequences. For example, it has been found to use certain gold compounds. However, certain gold compounds react with gelatin, which can vary between batches. It is also known to chemically sensitize silver halide using a gold compound that also contains sulfur. This limits the relative amounts of gold and sulfur to the stoichiometric amount of the compound. To obtain optimal sensitization for a particular photographic application, it is desirable to vary the amount of gold and sulfur.

The present invention also relates to the problems encountered in the manufacture of photographic elements, particularly the crystallization of sensitizing dyes, the reaction of gold compounds with gelatin, and the use of gold and sulfur to chemically sensitize silver halide. The problem is directed to the optimization of relative quantities.

[0011]

SUMMARY OF THE INVENTION The present inventors have found that sensitizing dyes (both spectral sensitizing dyes and chemical sensitizing dyes) are appropriately selected to avoid the problems of the prior art. In one embodiment of the present invention, the silver halide has a λ of 475 nm or less.
_At least one silver halide emulsion sensitized with a first blue sensitizing dye having ₁ and a second blue sensitizing dye having λ ₂ (provided that the first and second dyes do not contain selenium) A photographic element comprising a layer, wherein λ ₁ is λ ₂
Longer, and λ ₁ and λ ₂ are separated by an energy gap ΔE not exceeding 0.12 eV, where ΔE is a photographic element defined by:

(Equation 2) (Where λ ₁ is the maximum absorption wavelength expressed in nanometers (nm) of the silver halide emulsion sensitized with the first dye,
λ ₂ is the maximum absorption wavelength of the silver halide emulsion sensitized with the second dye).

In a preferred embodiment of the present invention, the silver halide is chemically sensitized with a gold (I) compound of formula (I): AuL ₂ ⁺ X ⁻ or AuL (L ¹ ) ⁺ X ⁻ (I) ( Where L is a mesoionic compound, X is an anion, and L ¹ is a Lewis donor ligand).

It is also preferred that the silver halide emulsion layer further comprises a disulfide compound of the formula (II):

Embedded image Wherein X ′ is independently —O—, —NH—, or —NR— (where R is an alkyl group, a fluoroalkyl group, an aryl group, or a sulfonyl group);
m and r are independently 0, 1 or 2;
And r are not simultaneously 0, M is —H or a cationic species, Ar is an aromatic group, and when p is 1, L ² is a linking group)].

[0014]

DETAILED DESCRIPTION OF THE INVENTION In the present invention, a silver halide emulsion is spectrally sensitized to blue light using a combination of two blue dyes. Preferred dyes are of the following classes:

[Table 1]

[0015]

[Table 2]

In the table, Z ₁ , Z ₂ and Z ″ independently represent
A hydrogen or halogen atom, or a substituted or unsubstituted alkyl, a substituted or unsubstituted alkoxy, a substituted or unsubstituted aromatic group and a substituted or unsubstituted heterocyclic group, and R ₁ and R ₂ are independently A substituted or unsubstituted alkyl, a substituted or unsubstituted alkenyl group or a substituted or unsubstituted aryl group. In a preferred embodiment of the present invention, at least one of R ₁ and R ₂ is a water solubilizing group, for example, sulfoalkyl, carboxyalkenyl, sulfoaryl and the like. These dyes can also have one or more substitutions at other positions on the benzo ring.

The approximate peak wavelength of each parent chromophore when optimally substituted to allow aggregation is shown. Generally, a set of dyes constituting a mixed aggregate composed of “long dyes” and “short dyes” is prepared. From top to bottom of the table,
Adjacent pairs of long and short dyes form mixed aggregates (when optimally displaced). That is, from about 470 dyes + about 450 dyes, about 450 dyes + about 440 dyes, etc., and up to about 420 dyes + about 410 dyes. Typically,
The difference in peak wavelength between the long dye and the short dye is at least 10 n
m is preferred. It has been found advantageous to use together the dye at the long wavelength end of the wavelength range of the dye of the relevant class and the dye at the short wavelength end of the wavelength range.
For example, a class F dye having a peak wavelength of about 470 nm,
A class F dye having a peak wavelength of about 460 nm or less can be combined.

As is well known in the art, a wide variety of substituents can be used to provide J-aggregates primarily in AgBr emulsions. Where the dye is oxacyanine, thiacyanine, oxacarbocyanine, or thiacarbocyanine, there are abundant literature examples of aggregating cyanine dyes having lower alkyl, halo, lower alkoxy, aromatic and heterocyclic substituents.

Reference to a specific moiety as a “group” in this specification means that the specific moiety itself may be substituted or unsubstituted. For example, "alkyl group" is a substituted alkyl or unsubstituted alkyl, "alkoxy group" is a substituted alkoxy group or unsubstituted alkoxy group, "aromatic group" is a substituted aromatic group or unsubstituted aromatic group, and ""Heterocyclicgroup" means a substituted or unsubstituted heterocyclic group. Generally, unless otherwise specified, substituents that can be used on the molecules herein include any groups, whether substituted or unsubstituted, that do not impair the properties required for photographic utility. Examples of the substituents of the mentioned groups include known substituents such as: halogen (eg, chloro, fluoro, bromo, iodo); alkoxy, especially “lower alkoxy” (ie, having 1 to 1 carbon atoms).
6, for example, methoxy, ethoxy); substituted or unsubstituted alkyl, especially lower alkyl (eg, methyl,
Thioalkyl (eg, methylthio or ethylthio), especially any having 1 to 6 carbons; substituted and unsubstituted aryl, especially 6 to 20 carbons (eg, phenyl); Or unsubstituted heteroaryl, especially those having a 5- or 6-membered ring having 1 to 3 heteroatoms selected from N, O or S (eg, pyridyl, thienyl, furyl, pyrrolyl); acid or Acid bases, for example,
Those described below: as well as those known in the art. Alkyl substituents are especially “lower alkyl”
(Having 1 to 6 carbon atoms), for example, methyl, ethyl and the like. Furthermore, it will be understood that for any alkyl or alkylene group they may be branched or straight chain and include ring structures.

In embodiments of the present invention in which the emulsion used is primarily AgCl, (a) if one of the two dyes has a 5-position substituent, it must be aromatic;
(B) When both of the two dyes have a 5-position substituent, the present invention can be achieved by using a dye in which at least one must be aromatic.

Examples of the dyes of the present invention and comparative dyes are shown in Table B below.
Shown in Note that C (comparison) applies only for AgCl emulsions. These dyes are the AgCl
Neither coagulation nor the invention is performed above. The main feature of the present invention is to provide a set of dyes rather than a single dye.

[0022]

[Table 3]

The present invention provides a method for adjusting the maximum sensitization of an element.
A combination of at least two blue sensitizing dyes having distinctly different structures is used in combination with a silver halide emulsion. Thereby, improved color reproduction can be provided while maintaining high photographic sensitivity.

Preferred dye combinations include, for example: A. The first dye has the following structure:

Embedded image

The second dye has the following structure:

Embedded image

Or the following structure:

Embedded image

B. The first dye has the following structure:

Embedded image

The second dye has the following structure:

Embedded image

C. The first dye has the following structure:

Embedded image

The second dye has the following structure:

Embedded image

D. The first dye has the following structure:

Embedded image

The second dye has the following structure:

Embedded image

E. The first dye has the following structure:

Embedded image

The second dye has the following structure:

Embedded image

In the above formula, Z ₁ and Z ₂ are independently hydrogen or a halogen atom or substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted aromatic group and substituted or unsubstituted R ₁ and R ₂ are independently substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, or substituted or unsubstituted aryl.

Particularly preferred blue dyes are of the following structural formulas I and II:

Embedded image Wherein Z ₁ is a phenyl, pyrrolyl or fused benzene ring, Z ₂ is phenyl, pyrrolyl or halogen, R ₁ and R ₂ are an acid-substituted alkyl group, and A ⁺ Ion).

[0037]

Embedded image (Wherein X is O or S, Y ₁ is pyrrolyl or phenyl, and Y ₂ is 4, when X is O,
Is 5-benzo substituent, X is phenylcarbamoyl or phenyl carboxamide substituent when the S, R ₃ and R ₄ is an acid substituted alkyl group, and B ⁺ is a counterion).

In the above formula, A ⁺ and B ⁺ are counter ions necessary to balance the net charge of the dye. Any positively charged counterion can be used. Common counterions that can be used include sodium, potassium, triethylammonium (TEA ⁺ ), tetramethylguanidinium (TMG ⁺ ), diisopropylammonium (DI
PA ⁺ ) and tetrabutylammonium (TBA ⁺ )
Is included.

These dyes used in the present invention are described in the present specification or FM Hamer's The Cyanine and Related.
Compounds (Interscence Publishers, New York, 196
Those skilled in the art can easily synthesize according to the procedure described in 4).

Examples of preferred dyes are shown in Table C.

[Table 4]

The photographic elements of the present invention comprise a blue-sensitive emulsion layer chemically sensitized with a gold (I) compounds of formula (Ia) or ^{_{(Ib): AuL 2 + X}} - (Ia) or AuL (L ¹ ) ⁺ X ⁻ (Ib), where L is a mesoionic compound, X is an anion, and L ¹ is a Lewis donor ligand.

These compounds can be dissolved in various solvents including water or organic solvents (eg, acetone or methanol), but the most preferred compounds are water-soluble. As used herein, the term "water-soluble"
It means that the gold (I) compound is dissolved in water at a standard pressure and a temperature of 20 ° C. at a concentration of at least 10 ⁻⁵ mol / L.

The mesoionic compound L used herein is gold (I)
A) a compound capable of coordinating with an ion to form a gold (I) compound that is water-soluble and allows chemical sensitization of a silver halide photographic composition. Preferably, the mesoionic compound has the formula:

Embedded image (Where the circle with a + sign in the heterocycle symbolizes the six delocalized π electrons associated with the partial positive charge on the heterocycle).

A, b, c, d, and e are the unsubstituted or substituted atoms required to complete the mesoionic compound, for example, a mesoionic triazolium or tetrazolium 5-membered heterocycle. Carbon and nitrogen atoms. The constituents of the heterocycle (a, b, c, d and e) can be CR ₅ or NR ₅ ′ groups or chalcogen atoms. The minus sign indicates two additional electrons on the exocyclic group f conjugated to the six π electrons on the heterocycle. It will be seen that there is extensive delocalization and the charge shown is only a fraction of the charge. The exocyclic group f is
S, Se, or can be a R ₅ ".R _5,
R ₅ ′ and R ₅ ″ are a hydrogen atom, a substituted or unsubstituted alkyl, aryl or heterocyclic group;
₅ , R ₅ ′ and R ₅ ″ can be joined together to form another ring.

A different structural representation of mesoionic compound L from the above can be found in other documents, but the following is described in Ollis
And Ramsden to Advances in Heterocyclic Chemist
ry, vol. 19, Academic Press, London (1976). It is through the exocyclic group f that the mesoionic compound coordinates to the gold (I) of the compound used in the present invention. The exocyclic group f should not be O in the present invention. This is because oxygen ligands are not known to form stable compounds with gold (I).

In the gold (I) compound of the present invention, the partial charge on the mesoionic ligand is reduced to avoid being confused with the overall charge of the complex ion. It will be appreciated that the heterocyclic moiety has a circle representing the six delocalized π electrons, but does not imply aromaticity.

[0047]

Embedded image (Wherein, R ₆ , R ₇ , and R ₈ independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, an amino group, a substituted or unsubstituted aryl group,
And X ⁻ is a halogen or a BF ₄ ⁻ anion). Preferred compounds are shown in the following table.

[0048]

[Table 5]

[0049]

Embedded image Here, R ₆ , R ₇ and X ⁻ are as defined above.
Preferred compounds are shown in the following table.

[0050]

[Table 6]

[0051]

Embedded image (Wherein R ₆ , R ₇ , R ₈ and R ₉ are independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, an amino group, a substituted or unsubstituted aryl group, X ^- is halogen or BF ₄ ^- is an anion). Preferred compounds are shown in the following table.

[0052]

[Table 7]

These gold (I) compounds have advantages over other sulfur-containing gold compounds known in the art (eg, trisodium gold dithiosulfate). Because
Because these compounds do not contain labile S atoms, the choice and amount of S sensitizer can be made free (not possible with trisodium gold dithiosulfate). The flexibility regarding the selection and amount of sulfur sensitizers used in photographic elements is
Required to achieve moderate gradation, desensitization to red light, and other sensitometric properties. In addition, the compounds of the present invention can also be used with other soluble gold (I
) Advantages over compounds. This is because the compounds of the present invention have a low dissociation constant and consequently have good solution stability.

For example, alkyl or aryl thiolates have a tendency to form high molecular weight gold (I) compounds having a 1: 1 ratio of thiolate to gold. The compounds of the present invention contain a discontinuous gold (I) complex having two ligands. Thus, this compound does not require a sulfonic acid or other solubilizing group to bind to the ligand,
It has convenient solubility for dispersion in emulsions. Also, the compounds of the present invention are more advantageous, more convenient and potentially free of explosives than conventional gold (I) compounds.

The mesoionic compound L used as a starting material for preparing a compound containing gold (I) was obtained from Altran
d, Dedio and McSweeney U.S. Pat. No. 4,378,42.
No. 4 (1983) or the method described above
It can be prepared in the manner described in Ollis and Ramsden, and the references cited therein. The synthesis of the gold (I) compound can be performed by various techniques known in the art. One convenient method consists in reacting a gold (I) precursor compound with a suitable amount of a mesoionic compound. Subsequent reactions, typically at room temperature (about 20 ° C.) or slightly above, displace the ligand of the gold (I) precursor compound with a mesoionic compound having a higher affinity than gold (I). The product is then separated and purified by crystallization techniques.

Various substituents on the mesoionic compound alter the solubility of the final product gold (I) compound. The most desirable gold (I) compounds are those that are soluble in water and can be made in water. Further, the aqueous emulsion can be sensitized by using one dissolved in an organic solvent such as acetone, or the emulsion can be sensitized by a non-aqueous medium.
No. 5,049,48 regarding this gold compound.
No. 5 is described in more detail, and is incorporated herein by reference.

The disulfide compound used in the photographic element of the present invention is preferably a compound represented by the following formula (II):

Embedded image Wherein X ′ is independently —O—, —NH—, or —NR— (where R is an alkyl group, a fluoroalkyl group, an aryl group or a sulfonyl group), m and r is independently 0, 1 or 2, but m and r are not both 0, M is -H or a cationic species, Ar is an aromatic group, p is 0
Or 1 and p is 1, L ² is a linking group).

Ar is a monocyclic or condensed ring aromatic group having preferably 6 to 10 carbon atoms, more preferably 6 carbon atoms. Examples of suitable aromatic groups include
Includes naphthyl and phenyl. Ar may be further substituted or unsubstituted;
More preferably, r is substituted. Examples of suitable substituents include alkyl groups (eg, methyl, ethyl, hexyl), fluoroalkyl groups (eg, trifluoromethyl), alkoxy groups (eg, methoxy, ethoxy, octyloxy), aryl groups (eg, Phenyl, naphthyl, tolyl), hydroxyl group, halogen atom, aryloxy group (eg, phenoxyl), alkylthio group (eg, methylthio, butylthio), arylthio group (eg, phenylthio), acyl group (eg, acetyl, propionyl, Butyryl, valeryl), sulfonyl groups (eg, methylsulfonyl, phenylsulfonyl), acylamino groups, sulfonylamino groups, acyloxy groups (eg, acetoxy, benzoxy), carboxyl groups, cyano groups, sulfo groups, and amino groups. Preferred are simple alkyl and acylamino groups.

X 'is independently -O-, -NH-, or -NR-. Most preferred X 'is -NH-. When X 'is -NR-, R is a substituent that does not interfere with the intended function of the disulfide compound in the photographic element and maintains the compound's water solubility. Examples of suitable substituents include alkyl groups (eg, methyl, ethyl, hexyl), fluoroalkyl groups (eg, trifluoromethyl), aryl groups (eg, phenyl, naphthyl, tolyl), sulfonyl groups (eg, methyl Sulfonyl, phenylsulfonyl). Preferred are simple alkyl groups and simple fluoroalkyl groups.

R and m are independently 0, 1 or 2
It is. Thus, included are compounds in which only one of the aromatic groups has been substituted. Preferably, m and r are both 1. X ′ may each be anywhere in the aromatic nucleus with respect to sulfur. More preferably, the molecule is symmetric and X 'is in the para or ortho position.

L ² is a linking group. p is 0 or 1. Preferably, L ² is an unsubstituted alkylene group, usually — (CH ₂ ) _n — (where n is 0
To 11, but preferably 1 to 3).
Then shows another example of L ^2.

[0062]

Embedded image

M is a hydrogen atom or a cationic chemical species (when the ionized form has a carboxyl group). The cationic species can be a metal ion or an organic ion. Examples of organic cations include ammonium ions (eg, ammonium, tetramethylammonium, tetrabutylammonium), phosphonium ions (eg, tetraphenylphosphonium), and guanidyl groups. Preferably, M is hydrogen or an alkali metal cation, most preferably a sodium or potassium ion.

Examples of the disulfide compound of the present invention are shown below. Compounds IA to IH are preferred, and compounds ID and IE are most preferred.

Embedded image

[0065]

Embedded image

[0066]

Embedded image

[0067]

Embedded image

[0068]

Embedded image

[0069]

Embedded image

[0070]

Embedded image

The soluble disulfides of the present invention are readily prepared using readily available starting materials. The majority of soluble disulfides are obtained by reacting aminophenyl disulfide or hydroxyphenyl disulfide with a suitable cyclic anhydride and then converting the free diacid to its anionic form using a substance such as sodium bicarbonate. Can be. Aminophenyl disulfide or hydroxyphenyl disulfide was reacted with the monochloride of a dicarboxylic acid monoester, which was then hydrolyzed to the carboxylic acid to give other soluble disulfides. Disulfide compounds are disclosed in U.S. Pat.
No. 418,127, which is incorporated herein by reference.

The emulsion layers of the photographic element of the present invention can comprise any one or more photosensitive layers of the photographic element. Photographic elements made in accordance with the present invention include black and white elements,
It can be a single color element or a multicolor element. Multicolor elements have dye image-forming units sensitive to each of the three primary colors of the spectrum. Each unit can comprise a single emulsion layer or multiple emulsion layers sensitive to a given region of the spectrum. The layers of the element, including the layers of the image-forming units, can be arranged in various orders as known in the art. In another format, an emulsion sensitive to each of the three primary colors of the spectrum is
It can be arranged as a single segmented layer.

A typical multicolor photographic element comprises a cyan dye image-forming unit comprising one or more red-sensitive silver halide emulsion layers combined with at least one cyan dye-forming coupler, and at least one magenta A magenta dye image-forming unit comprising one or more green-sensitive silver halide emulsion layers combined with a dye-forming coupler, and one or more blue-sensitive silver halide layers combined with at least one yellow dye-forming coupler And a support carrying a yellow dye image forming unit including an emulsion layer.
The element comprises a filter layer, an intermediate layer, an overcoat layer,
It may have additional layers such as a subbing layer, an antihalation layer, and the like. All of these can be coated on a support which can be transparent or reflective (eg, a paper support).

The photographic element of the present invention is used for research discography.
Jar (Research Disclosure) , item 34390,
No. 4,279,945 and U.S. Pat. No. 4,30,945.
It may be useful to include a transparent magnetic recording layer, such as a layer containing magnetic particles under a transparent support as described in US Pat. No. 2,523. The overall thickness of the element (excluding the support) is typically in the range of 5 to 30 μm. The order of the color-sensitive layers can vary, but generally, on a transparent support, the order of the red-sensitive layer, the green-sensitive layer, and the blue-sensitive layer (ie, the blue-sensitive layer is furthest from the support); The opposite order is common on a reflective support.

The present invention also contemplates the use of the photographic elements of the present invention in applications often referred to as single-use cameras (or "lenses with film" units). These cameras are commercially available preloaded with film, and the entire camera is returned to the processor with the exposed film remaining inside the camera. Such cameras may have glass or plastic lenses through which the photographic elements are exposed.

In the following description of materials suitable for use in the elements of the present invention, reference is made to Research Disclosure, September 1996, No. 389, available as above.
, Item 38957. In this specification, this document is hereinafter referred to as "Research Disclosure I".
Called. Unless otherwise specified, the following sections refer to this section of Research Disclosure I. Research Disclosure
Kenneth Mason Publications, UK (Dudley Annex, 1
2a North Street, Emsworth, Hampshire, P010 7DQ). The foregoing references and all other references cited herein are hereby incorporated by reference.

The silver halide emulsions used in the photographic elements of this invention can be either internal emulsions (fogged during processing), whether negative-working emulsions such as surface-sensitive emulsions or unfogged internal latent image-forming emulsions. A positive emulsion of the type may be used.
Suitable emulsions and their preparation as well as chemical and spectral sensitizations are described in Sections IV. Sections V to XX for coloring materials and development regulators
It is described in. Vehicles that can be used in the photographic element include Section II, optical brighteners, antifoggants,
Various additives such as stabilizers, light absorbing and scattering agents, hardeners, coating aids, plasticizers, lubricants and matting agents are described, for example, in Sections VI-XIII. The preparation method is in all sections, the layer arrangement is particularly in section XI, the alternative exposure method is in section XVI,
The processing methods and agents are described in sections XIX and XX, respectively. The use of negative working silver halide can form a negative image. A positive (or reversal) image can be formed if desired, but generally a negative image is formed first.

The photographic elements of the present invention are described in EP 213
No. 490, JP-A-58-172647, U.S. Pat. No. 2,983,608, German Patent Application Publication No. 2,706,117C, British Patent 1,530,27.
No. 2, JP-A-58-113935, U.S. Pat. No. 4,070,191, and German Patent Application No. 2,643,965 (for example, an interlayer correction method). Combinations of colored couplers (to adjust the level) and masking couplers can also be used. The masking coupler may be shifted or blocked as desired.

Photographic elements can have improved image quality by containing materials that promote or improve the processing steps of bleaching and fixing. European Patent 193,389
No. 301,477, US Pat. No. 4,163,6.
Nos. 69, 4,865,956 and 4,92
The bleaching accelerators described in 3,784 are particularly useful. Further, a nucleating agent, a development accelerator or a precursor thereof (British Patent Nos. 2,097,140 and 2,131,188); a development inhibitor and a precursor thereof (US Pat. No. 5,460,932;
478,711); electron transfer agents (U.S. Pat. Nos. 4,859,578; 4,912,025); antifoggants and color mixing inhibitors, for example, hydroquinone, aminophenol, amine, The use of derivatives of gallic acid; catechol; ascorbic acid; hydrazide; sulfonamidophenols;

The element of the present invention comprises a filter dye layer comprising a colloidal silver sol or a yellow and / or magenta filter dye and / or an antihalation dye as an oil-in-water dispersion, a latex dispersion or a solid particle dispersion (especially In the undercoat below all photosensitive layers or on the side of the support opposite to the side on which all photosensitive layers are disposed. In addition, they can be coupled to "smearing" couplers (eg, US Pat. No. 4,366,2).
37, EP 096,570, U.S. Pat.
420,556 and U.S. Pat. No. 4,543,323). Further, the coupler can be coated or blocked in a protected form as described in, for example, Japanese Patent Application No. 61-258249 or U.S. Pat. No. 5,019,492.

The photographic elements of the present invention can further contain other image improving compounds such as "development inhibitor releasing" (DIR) compounds. Additional DIRs useful in the elements of the present invention are known in the art and examples thereof are described in the following patents: U.S. Patent Nos. 3,137,578; No. 148,022, No. 3,148,062, No. 3,227,554,
No. 3,384,657, No. 3,379,529
No. 3,615,506 and No. 3,617,29
No. 1, No. 3,620,746, No. 3,701,7
No. 83, No. 3,733, 201, No. 4,049,
No. 455, No. 4,095,984, No. 4,12
No. 6,459, No. 4,149,886, No. 4-1
No. 50,228, No. 4,211,562, No. 4,
Nos. 248,962, 4,259,437, 4,362,878, 4,409,323, 4,477,563, 4,782,012,
Nos. 4,962,018 and 4,500,634
No. 4,579,816 and No. 4,607,00
No. 4, No. 4,618,571, No. 4,678,7
No. 39, No. 4,746,600, No. 4,746
No. 601, No. 4,791,049, No. 4,85
No. 7,447, No. 4,865,959, No. 4,8
No. 80,342, No. 4,886,736, No. 4,
No. 937,179, No. 4,946,767, No. 4,948,716, No. 4,952,485, No. 4,956,269, No. 4,959,299,
Nos. 4,996,835 and 4,985,336
No. 1,560,240, No. 2,007,662, No. 2,032,914 and No. 2,099,167; German Patent No. 2,560,240; 8
No. 42,063, No. 2,937,127, No. 3,
636,824 and 3,644,416; and European Patent Publications 272,573 and 33.
No. 5,319, No. 336,411, No. 346,8
No. 99, No. 362,870, No. 365, 252
Nos. 365 and 346, 373 and 382, 376 and 212, 377 and 463, and 37
8,236, 384,670, 396,4
Nos. 86, 401,612 and 401,613
Issue specification.

For the DIR compound, see “Developer-In
hibitor-Releasing (DIR) Couplersfor Color Photogra
phy '' (CR Barr, JR Thirtle and PW Vittum, Pho
tographic Science and Engineering, Vol. 13, p. 174
(1969)), which is hereby incorporated by reference.

Research Disclosure, 1979 11
It is also contemplated that reflective color prints may be obtained utilizing the concepts of the present invention, as described in the month, item 18716, which is incorporated herein by reference. Emulsions and materials for forming the elements of the present invention are described in U.S. Pat. No. 4,917,99.
On a pH-adjusted support as described in US Pat. No. 4,164,961 together with an epoxy solvent as described in EP 164,961, for example US Pat.
46,165, 4,540,653 and 4,906,559 together with other stabilizers to reduce the sensitivity to multivalent cations such as calcium. U.S. Pat. No. 4,994,35
Stain reducing compounds with ballasting chelators as described in US Pat. No. 9 and US Pat. Nos. 5,068,171 and 5,096,805 In addition, it can be applied.

Other compounds useful in the photographic elements of the present invention include:
JP-A-58-09959; JP-A-58-62586; JP-A-02-072629; JP-A-02-072630;
No. 02-073232; No. 02-073233; No. 02-073234; No. 02-077822; No. 0
2-078229; 02-0278230; 02
No. 079336; No. 02-079338; No. 02-
No. 079690; No. 02-079691; No. 02-0
No. 80487; No. 02-080489; No. 02-08
No. 0490; No. 02-080491; No. 02-080
No. 492; No. 02-080494; No. 02-0859
No. 28; No. 02-086669; No. 02-08667
No. 0; 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. 02-009668
No. 02-094055; No. 02-094056
No. 02-101937; No. 02-103409
No. 02-151577.

The silver halide used in the photographic element includes silver iodobromide, silver bromide, silver chloride, silver chlorobromide, silver chloroiodobromide,
And so on. The types of silver halide grains preferably include polymorphs, cubes and octahedrons. The grain size of the silver halide can have any distribution known to be useful in photographic compositions, and can be polydispersed or monodispersed.

A tabular grain silver halide emulsion can also be used. Tabular grains are those having two parallel major faces, each of which is clearly larger than the remaining grain faces.
0%, more typically at least 50%, preferably 7%
Emulsions that account for more than 0% and optimally more than 90%. Tabular grains have substantially all of the total grain projected area (9
(More than 7%). The tabular grain emulsion is a high aspect ratio tabular grain emulsion, ie, ECD
/ T> 8 (ECD is the diameter of a circle having an area equal to the grain projected area, and t is the thickness of the tabular grains); medium aspect ratio tabular grain emulsions, ie, ECD /
t = 5-8; or low aspect ratio tabular grain emulsions, ie, ECD / t = 2-5. The emulsions typically have a high tabularity (T) (T = ECD / t ² ), ie, ECD / t ² > 25 (ECD and t are both measured in μm).

The tabular grains can be of any thickness compatible with achieving the desired average aspect ratio and / or average tabularity of the tabular grain emulsion.
Tabular grains satisfying the projected area requirement are preferably those having a thickness of less than 0.3 μm, especially thin (<0.2 μm) tabular grains, which maximize tabular grain performance. To be ultra-thin (<0.07 μm)
Tabular grains are contemplated. For blue speeds, relying on the intrinsic blue absorption of iodohalide tabular grains, thicker tabular grains (typically up to 0.5 μm)
m thickness).

High iodide tabular grain emulsions are disclosed in US Pat. No. 4,490,458 to House, US Pat. No. 4,459,353 to Maskasky and European Patent No. 0 to Yagi et al.
No. 410,410. Tabular grains formed from silver halide forming a face-centered cubic (rock salt type) crystal lattice structure can have either {100} or {111} major faces. Emulsions with {111} major tabular grains (including controlled grain dispersity, halide distribution, twin plane spacing, edge structure and grain dislocations and adsorbed {111} grain plane stabilizers)
Research Disclosure I , Section I. B.
This is specifically described in (3) (page 503).

The silver halide grains used in the present invention are:
Research Disclosure I and James' The Theor
It can be manufactured according to methods known in the art as described in the y of the Photographic Process . These methods include methods for making ammoniacal emulsions, methods for making neutral or acidic emulsions, and others known in the art. In these methods, a water-soluble silver salt is mixed with a water-soluble halide salt in the presence of a protective colloid, and the temperature is adjusted during precipitation to form silver halide.
It is generally necessary to control PAg, pH value, and the like to appropriate values.

At the time of grain precipitation, one or more dopants (grain occlusion other than silver and halide) can be introduced to improve grain properties. For example, Research Disclosure
Jar , item 38957, section I. Emulsion grains and their properties, subsection G. Various conventional dopants described in Grain Improvement Conditions and Adjustments, paragraphs (3), (4) and (5) can be present in the emulsions of the present invention. Further, U.S. Pat.
As described in US Pat. No. 712 (Olm et al.), It is conceivable to dope the particles with a hexacoordination complex of a transition metal having one or more organic ligands.

Research Disclosure, Item 36
736, published in November 1994, shallow electron traps (hereinafter referred to as "SE
In particular, it is conceivable to incorporate a dopant that can form a "T") to increase the speed of image formation. It is effective to dispose the SET dopant at any position in the grain. In general, good results have been obtained with the SET dopant incorporated within the outer 50% (relative to silver) of the grains. The optimal particle range for SET integration is
The range formed in the silver range of 50 to 85% of the total silver forming the grains. The SET may be introduced all at once, or may be introduced into the reaction vessel over time while continuing the particle precipitation. Generally, it is contemplated that the SET-forming dopant will be introduced at a concentration of at least 1 × 10 ⁻⁷ mole / silver mole, up to its solubility limit, typically up to about 5 × 10 ⁻⁴ mole / silver mole. .

SET dopants are known to be effective in reducing reciprocity failure. In particular, iridium hexa coordination complex or I
The r ⁺⁴ complex is advantageous.

Iridium dopants that are not effective in providing shallow electron traps (non-SET dopants)
It can be introduced into the grains of the silver halide grain emulsion to reduce reciprocity failure. Ir can be anywhere in the particle structure to be effective in reciprocity improvement. The preferred position in the grain structure of the Ir dopant that produces the reciprocity improvement is after the first 60% and before the final 1% (most preferably before the final 3%) of all the silver forming the grain precipitates. ) Is within the range of particle generation. The dopant may be introduced all at once or may be mixed into the reaction vessel over a period of time during which the grain precipitation is continued. Generally, it is contemplated that the reciprocity improving non-SET Ir dopant is incorporated at its lowest effective concentration.

The contrast of a photographic element can be increased by using a nitrosyl or thionitrosyl ligand (N) as disclosed in US Pat. No. 4,933,272 to McDugle et al.
This can be further enhanced by doping the particles with a hexacoordination complex containing a (Z dopant).
Contrast enhancing dopants can be incorporated into the grain structure at convenient locations. However, if the NZ dopant is present on the grain surface, the grain sensitivity may be reduced. Therefore, it is preferred to position the NZ dopant so that it is separated from the grain surface by at least 1% (most preferably at least 3%) of the total silver precipitated in the silver iodochloride grain formation. The preferred contrast enhancing concentration of the NZ dopant is from 1 × 10 ⁻¹¹ mol to
4 × 10 ⁻⁸ mol / silver mol, and particularly preferably 1
0 ^-10 mol to 10 ^-8 mol / silver mol.

Various SET, non-SET Ir and NZ
While the generally preferred concentration ranges of the dopants are set forth above, certain optimal concentration ranges within these general ranges are:
Routine testing can be linked to specific applications. It is specifically contemplated to use SET, non-SET Ir and NZ dopants alone or in combination.
For example, grains containing a combination of a SET dopant and a non-SET Ir dopant can be specifically considered. Similarly, SET and NZ dopants can be used in combination. In addition, NZ and Ir dopants that are not SET dopants can also be used in combination. Finally, the non-SET Ir dopant is
It can be combined with T dopant and NZ dopant. In the latter case of the three dopant combinations,
It is generally most convenient with respect to precipitation to introduce the NZ dopant first, then the SET dopant, and finally the non-SET Ir dopant.

The photographic elements of the present invention generally provide the silver halide in the form of an emulsion. Photographic emulsions generally include a vehicle for coating the emulsion as one layer of a photographic element. Useful vehicles include proteins, protein derivatives, cellulose derivatives (eg, cellulose esters), gelatin (eg, alkali-treated gelatin such as bovine bone or hide gelatin, or acid-treated gelatin such as pork skin gelatin), deionized gelatin. Natural substances, such as gelatin derivatives (eg, acetylated gelatin, phthalated gelatin, etc.), as well as other vehicles, such as those described in Research Disclosure I. Also,
Useful as vehicles or vehicle extenders are
It is a hydrophilic permeable colloid. These are the research
Synthetic polymeric peptizers, carriers and / or polymers of polyvinyl alcohol, polyvinyl lactam, acrylamide polymers, polyvinyl acetal, alkyl and sulfoalkyl acrylates and methacrylates, as described in Closure I.
Contains binders such as hydrolyzed polyvinyl acetate, polyamide, polyvinyl pyridine, methacrylamide copolymers. The vehicle can be present in the emulsion in an amount useful for photographic emulsions. The emulsion can also contain any of the addenda known to be useful in photographic emulsions.

The silver halide used in the present invention can be advantageously chemically sensitized. Compounds and techniques useful for chemical sensitization of silver halide are known in the art and are described in Research Disclosure I and the references cited therein. Compounds useful for chemical sensitization include, for example, active gelatin, sulfur, selenium, tellurium, gold, platinum, palladium, iridium, osmium, rhenium, phosphorous acid, or combinations thereof. Chemical sensitization is available in Research Disclosure I ,
Generally, as described in Section IV (pages 510-511) and the references cited therein, pAg
Level 5-10, pH level 2-8, and temperature 30-
Performed at 80 ° C.

Silver halide is used in research disclosure.
Sensitizing dyes can be sensitized by techniques known in the art, such as described in Table I. This dye,
An emulsion consisting of silver halide grains and a hydrophilic colloid at any time before the emulsion is coated on the photographic element (eg, during or after chemical sensitization) or simultaneously with the application of the emulsion to the photographic element. May be added. The dye can be added, for example, as a solution in water or alcohol. The dye / silver halide emulsion can be mixed with the dispersion of the color image-forming coupler immediately before coating or prior to coating (eg, 2 hours).

The photographic element of the present invention is used for research discography.
Preferably, imagewise exposure is performed using any known technique, including those described in Table I , section XVI. This typically requires exposure in the visible region of the spectrum, and typically such exposure is a raw image through a lens, but a stored image (as stored on a computer). Can be exposed using a light emitting device (light emitting diode, CRT, etc.).

A photographic element containing the composition of the present invention can be produced, for example, by using Research Disclosure I or TH Jam.
es, The theory of the Photographic Process , No. 4
Edition, Macmillan, New York, 1977, can be processed by well-known photographic processes using any of several well-known processing compositions. When processing a negative working element, the element is treated with a color developing agent (i.e., one that forms a color image dye with a color coupler) and then treated with an oxidizing agent and a solvent to remove silver and silver halide. . When processing a reversal color element, the element is first treated with a black and white developing agent (ie, a developing agent that does not form a color image dye with the coupler compound) and then fogged with silver halide (generally, chemical fogging). Or light fog) and then processing with a color developing agent.

Preferred color developing agents are p-phenylenediamines. Particularly preferred developing agents are:
Amino-N, N-diethylaniline hydrochloride, 4-amino-3-methyl-N, N-diethylaniline hydrochloride,
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-toluenesulfonic acid.

Bissonette, US Pat. No. 3,748,13
No. 8, 3,826, 652, 3, 862, 842
No. 3,989,526 and Travis 3,7
U.S. Pat. No. 3,674,490 to Matejec, described in U.S. Pat.
Research Disclosure, Volume 116, December 1973, Item 11660 and Bissonette's Research Disclosure, Volume 148, August 1976, Items 14836, 14846, and 14847 use a combination of peroxide oxidizers. A dye image can be created or enhanced.

No. 3,822,129 to Dunn et al.
Nos. 3,834,907 and 3,9 of Bissonette
02,905, Bissonette et al., 3,847,619.
No. 3,904,413 of Mowrey, 4,880,725 of Hirai et al., And 4,954,425 of Iwano
No. 4,983,504 to Marsden et al., No. 5,246,822 to Evans et al., And No. 5,324,62 to Twist.
No. 4, Fyson's EPO04887616, Tannahill et al., WO90 / 13059, Marsden et al., WO90 / 1.
No. 3061, WO 91/16666 by Grimsey et al., Fy
WO91 / 17479 by son, WO92 by Marsden et al.
/ 01972, WO92 / 05471 from Tannahill
No. WO92 / 07299 of Henson, WO9 of Twist
No. 3/01524, and WO 93/11460, and OLS No. 4,211,460 in Germany, such as Wingender et al.
The photographic element is particularly suitable for forming a dye image by processing as described in US Pat. After the development, bleach-fix is carried out to remove silver or silver halide, washed and dried.

[0104]

The following examples illustrate the use of the dye combinations of the present invention. Example 1 This example demonstrates the use of a dye combination of the present invention using a cubic AgCl emulsion. In this test, a pure AgCl emulsion consisting mainly of cubic morphology was used. The median particle diameter was 0.39 μm on one side of the cube (CEL). This emulsion was melted at 40 ° C. and colloidal gold sulfide was
0.0177 mole was added per mole of gCl, and the emulsion was heated at 65 ° C. for 55 minutes, then cooled and chemically sensitized.

The emulsion was melted again at 40 ° C. and dye was added from a methanol solution at a concentration of 0.000471 mole per liter to bring the dye to silver ratio to 3.8 × 10 ^-4 mole of dye per mole of silver. The sensitizing dye was added. This emulsion was held for 20 minutes while stirring, and then cooled while stirring. A specific combination of the two dyes was each independently added to the emulsion, and they were also premixed, 75% dye 1, 25% dye 2, 50%
This dye combination was tested by simultaneously adding to the emulsion from a solution of dye 1, 50% dye 2; 25% dye 1, 75% dye 2.

The colored emulsion was coated on an ESTAR ^™ support using a coater equipped with an extruder to distribute the molten emulsion to the support. The applied melt is emulsion, gelatin,
It consisted of water, the dye solution, the surfactant saponin (natural glycoside), and the hardener 1,1 ′-(oxybis- (methylenesulfonyl) bis-) ethene (BVSME).

The total "wet" laydown is 1
It was 57 g / m ² (14.6 g / ft ² ). After cooling drying, the resulting single layer coatings, silver 3299mg / m ^2, gelatin 7319mg / m ^2, BVSME122.6mg
/ M ² , and saponin 144.8 mg / m ² .

The spectrum of the coated material was obtained using a scanning spectrophotometer equipped with an integrating sphere. The coated material was exposed using a sensitometer equipped with a tungsten light source filtered through a collection of Wratten filters designed to approximate exposure through a color film negative. Using a step tablet, the photographic speed at 0.8 density units above Dmin was measured to obtain a DLogE curve (well known to those skilled in the art).

The exposed test piece was developed at 20 ° C. according to the following processing. 1. 1. KODAK DK-50 ^TM developer 6 minutes 0 seconds 2. KODAK INDICATOR STOP ^TM stop bath 15 seconds 3. Kodak F-5 ^TM fixation 5 minutes 0 seconds Distilled water cleaning 10 minutes 0 seconds

The data for these tests on the various dye sets of the present invention and comparison are shown in Table I.

[Table 8]

[Table 9]

Since this emulsion is predominantly AgCl, the structural requirements for the practice of this invention are much more stringent than when the substrate is predominantly AgBr. In particular, (a) two 5
When it has a substituent at the position, at least one of the substituents must be aromatic, and (b) a symmetrical dinaphthoxazole coloring group is excluded from the present invention. This is because they do not aggregate on the AgCl emulsion.

From the above data, it can be seen that the combination of dyes of the present invention maintains the height of the combined aggregation peak, produces a stable development of the peak wavelength between the long and short dyes, and preserves photographic sensitivity. It is clear that all three characteristics are achieved much larger than the comparative dye combinations.

Example 2 In this example, an AgBr three-dimensional emulsion mainly having a cubic morphology was used. The nominal halide composition is AgBr
(97.4%) I (2.6%). The median particle size was 0.20 μm in equivalent spherical diameter (ESD). This emulsion was melted, and the chemical sensitizer, NaSCN, was added at a concentration of 44 mol / mol silver.
mg of Na ₂ S ₂ O ₃ .5H ₂ O per mole of silver.
mg of KAuCl ₄ and 6.6 mg / mol of silver
In addition, it was chemically sensitized.

This emulsion was melted again at 40 ° C., and
Methanol solution at a concentration of 0.00035 mol / l
And a dye to silver ratio of 8 × dye per mole of silver.
10 ^-FourThe sensitizing dye was added by mol.
The emulsion was held for 20 minutes with stirring and then stirred.
While cooling. A specific combination of two dyes
Each independently added to the emulsion, and also premixed them
75% dye 1, 25% dye 2, 50% dye 1, 5
0% dye 2; 25% dye 1, 75% dye 2 solution
This dye combination by simultaneously adding
Tested.

The cubic emulsion melt was coated as a single layer onto an ESTAR ^™ support on a machine equipped with an extruder that distributed the molten emulsion to the support. This melt is converted to silver 1
0.8 mg / dm ² , gelatin 77 mg / dm ² , hardener bis (vinylsulfonyl) methyl ether (BVSM
E) Coating was performed at 0.08%.

A spectrum of the coated material was obtained using a scanning spectrophotometer equipped with an integrating sphere. Exposure was performed using a single-grating transmission sensitometer to create independent DLogE curves at 10 nm intervals with visible light. The result is "wedge spectroscopy". This is well known in the art. For example, "Use of Spectral Sensitizing DyesTo
Extimate Effective Energy Levels of Silver Halide
Substrates "(PB Gilman, Jr., in Photographic
Science and Engineering, Volume 18, No. 5, September 10, 1974
Month). The exposed test pieces were developed at 35 ° C. on an Eastman KODAK RP X-OMAT ^™ developer.

The data from these tests for the various dye sets of the present invention and comparison are shown in Table II.

[Table 10]

[Table 11]

From the above data, it can be seen that the dye combinations of the present invention maintain the combined aggregation peak height, produce a stable development of the peak wavelength between the long and short dyes, and maintain photographic sensitivity. It is readily apparent that
And it is also clear that all three features are achieved much larger than the comparative dye combinations.

Example 3 In this example, an AgBr three-dimensional emulsion mainly having an octahedral morphology was used. The nominal halide composition is AgB
r (97.0%) I (3.0%). The median particle size was 0.30 μm in equivalent spherical diameter (ESD). This emulsion was melted, and a chemical sensitizer, NaSCN, was added in an amount of 1 per mole of silver.
Chemical sensitization was performed by adding 50 mg, 8 mg of Na ₂ S ₂ O ₃ .5H ₂ O per mol of silver, and 5 mg of KAuCl ₄ per mol of silver.

The octahedral emulsion melt was coated as a single layer onto an ESTAR ^™ support on a machine equipped with an extruder to distribute the molten emulsion to the support. This melt is converted to silver 2
1.5 mg / dm ² , gelatin 86 mg / dm ² , hardener bis (vinylsulfonyl) methyl ether (BVSM
E) Coating was performed at 0.08%.

The emulsion was melted again at 40 ° C., and dye was added from a methanol solution at a concentration of 0.00032 mole per liter to give a dye to silver ratio of dye per mole of silver of 4.
The sensitizing dye was added by making it 0 × 10 ⁻⁴ mol. This emulsion was held for 20 minutes while stirring, and then cooled while stirring. A specific combination of two dyes,
Each solution was added independently to the emulsion and they were also premixed in a 75% dye 1, 25% dye 2; 50% dye 1, 50% dye 2; 25% dye 1, 75% dye 2 ratio solution. This dye combination was tested by adding it simultaneously to the emulsion.

A spectrum of the coated material was obtained using a scanning spectrophotometer equipped with an integrating sphere. Exposure was performed using a single-grating transmission sensitometer to create independent DLogE curves at 10 nm intervals with visible light. The result is "wedge spectroscopy". The exposed test pieces were developed at 35 ° C. on an Eastman KODAK RP X-OMAT ^™ developer.

The data from these tests for the various dye sets of the present invention and comparison are shown in Table III.

[Table 12]

From the above data, it can be seen that the dye combinations of the present invention maintain the combined aggregation peak height, produce a stable development of the peak wavelength between the long and short dyes, and maintain photographic sensitivity. It is readily apparent that
And it is also clear that all three features are achieved much larger than the comparative dye combinations.

Example 4 The emulsion used was mainly a silver chloride, ruthenium-doped (1.0.0) tabular emulsion. Average particle size is 0.6
The equivalent circular diameter (ECD) was 0 μm. The average grain thickness was 0.17 μm. The exact halide percentage was 99.404% chloride and 0.596% iodide. This emulsion was doped with 125 ppm of ruthenium hexacyanide.

Sensitization This emulsion was heated to 39 ° C. and added in the following proportions per mole of silver: potassium bromide 50 mg, potassium tetrachloroaurate 1.7 mg, sensitizing dye in the amount indicated in Table V F
2 and E1 and 3.4 mg of sodium thiosulfate. The emulsion was heated to 60 ° C and maintained for 25 minutes before cooling to 39 ° C. 100 mg of 1- (3-acetamidophenyl) -5-mercaptotetrazole was added. This emulsion was coated on a triacetate film together with a yellow coupler of the formula YC. Thereafter, the film was dried.

[0127]

Embedded image

Testing The film was exposed to 3000K white light for 0.004 seconds. And ECP-2 ^™ at 36.7 ° C (98 ° F)
The treatment was performed for 3 minutes. It was measured with a spectral absorption spectrophotometer of the coated film sample. The results were obtained with various amounts of sensitizing dye. The results are shown in Table IV.

[0129]

[Table 13]

The amount of the dye is a percentage of the number of millimoles per mole of silver. As can be seen from the table, the dye peak shifts from 471 nm to 456 nm as the dye ratio changes.

Example 5 Dye combinations (Table V) were tested at 75/25, 50/50 and 2
Prepared from two dyes (Table B) formulated in a 5/75 ratio. 3.8 × 10 ^-4 mol / Ag mol of dye and dye combination were added to 0.39 μm containing 1.0% of gold sulfide sensitized bromide.
m (cube edge length) added to silver chloride cubic emulsion. These emulsions were coated on a polyester support in black and white format. The coating was exposed for 1/10 second with a wedge spectrophotometer covering a wavelength range of 350 to 750 nm. The photometer has a tungsten light source and a step tablet over a density of 0 to 3 density steps. Variations in irradiance with respect to the wavelength of the photometer of the device were corrected by a computer. The exposed coatings were processed as described below. The variation in sensitivity of each formulation was measured as follows.
The variation in sensitivity of each formulation was measured against the most sensitive parent dye. λmax was determined from spectrophotometric measurements of these colored coatings.

Processing temperature 20 ° C. (68 ° F.) Processing time Processing time DK-50 developer 6 min 0 sec Stop bath * 15 sec Fixing ** 5 min 0 sec Washing 10 min 0 sec Note) * Composition is 128 mL of acetic acid 8L diluted with distilled water. ** Composition is sodium sulfite 15.0 g, sodium thiosulfate 240.0 g, glacial acetic acid 13.3 mL, boric acid 7.
5 g and 15.0 g of aluminum potassium sulfate. Distilled water was added to make 1 liter.

[0133]

[Table 14]

As can be seen from Table V, the dye combinations of the present invention can be adjusted to their maximum sensitization by changing the ratio. The dye combination of the present invention has a smaller decrease in sensitivity than the dye combination of the comparative example.

Example 6 Emulsion (invention) was prepared using gelatin, antifoam, dithio-3,6
NaCl and AgN in the presence of octane-1,8-diol and glutaryldiaminophenyldisulfide
O ₃ were combined and precipitated, cubic edge length of 0.5Myuemu～0.8Myuemu, to form a particle of less than the aspect ratio of 1.2. After desalting, orthosuccinamidophenyl disulfide, gold (I) bis (1,4,5-trimethyl-1,2,2,
(4-Triazolium-3-thiolate) gold (I) fluoroborate, dye F2, dye E1 and sodium thiosulfate were added and then subjected to a heating cycle to chemically and spectrally sensitize the emulsion.

After the heating cycle, 1- (3-acetamidophenyl) -5-mercaptotetrazole (about 70 m
g / Ag mole) and potassium bromide (0.005 mole bromide / Ag mole).

[0137]Contrast The emulsion (control) was prepared using gelatin, antifoam, dithio-3,6-
In the presence of octane-1,8-diol, nitric acid and Hg
With NaCl and AgNO_Three Together and settle,
Forming particles having a cubic edge length of 0.0 μm to 0.8 μm
Was. Iridium (K _TwoIrCl₆), Sulfur gold (I) /
Sulfur compounds (AuO₆ S_Four ・ H_Two O 3Na), 1-
(3-acetamidophenyl) -5-mercaptotetra
Add sol and thiourea and then heat cycle.
After that, the comparative dyes COMP-1, 1- (3-acetoa
(Midophenyl) -5-mercaptotetrazole, KB
This emulsion was finished by adding r and gelatin.

[0138]

Embedded image

In the control emulsion, a portion of the dye COMP-1 crystallized, requiring that the emulsion be filtered before storage and / or use. In addition, an excess of dye is needed to supplement the dye crystallizing from the emulsion. In the emulsions of the present invention, the combination of dye F2 and dye E1 does not crystallize in solution or in sensitized emulsion. Spectroscopic analysis of these emulsions showed no free dye. Therefore, it is not necessary to filter the emulsion before storage. Dyes F2 and E1 are completely introduced into the emulsion.

The new emulsion was evaluated in the multilayer format shown in Table VI to demonstrate that the new emulsion provided the same sensitometric performance as the control emulsion.

Table VI: Multilayer coating format layer 1: Antihalation layer Layer 2: blue-sensitive layer Gelatin silver Y-1 Dibutyl phthalate UV-1 Layer 3: Intermediate layer Gelatin SC-1 SF-1 Layer 4: Red sensitivity Layer Gelatin Silver C-1 Tolitol phosphate Tris (2-ethylhexyl phosphate) SC-1 Layer 5: Intermediate layer Gelatin SC-1 SF-1 Layer 6: Green-sensitive layer Gelatin Silver M-1 Tolitril phosphate SC-1 Layer 7 : Overcoat

[0142]

Embedded image SC-1 = 1,4-isododecylhydroquinone

[0143]

Embedded image

Embedded image

A film sample was exposed to white light and subjected to Kodak ECP-2B treatment (a well-known trademark, Kodak H-
24 manual). The results are described in Table VI (a).

[0145]

[Table 15]

Other preferred embodiments of the present invention will be described below in connection with the claims. (Aspect 1) The photographic element according to claim 1, wherein the dye is selected from the group consisting of compounds represented by the following structural formulas:

Embedded image

Embedded image (Wherein Z ₁ , Z ₂ and Z ″ independently represent a hydrogen or halogen atom, or a substituted or unsubstituted alkyl,
Substituted or unsubstituted alkoxy, substituted or unsubstituted aromatic group and substituted or unsubstituted heterocyclic group, and R ₁ and R ₂ are independently substituted or unsubstituted alkyl, substituted or unsubstituted alkyl. A substituted alkenyl group or a substituted or unsubstituted aryl group).

(Embodiment 2) The photographic element according to claim 1, wherein the first dye and the second dye are selected from the group consisting of the following dyes: The first dye has the following structure:

Embedded image The second dye has the following structure:

Embedded image Or the following structure:

Embedded image B. The first dye has the following structure:

Embedded image And the second dye has the following structure:

Embedded image C. The first dye has the following structure:

Embedded image And the second dye has the following structure:

Embedded image D. The first dye has the following structure:

Embedded image And the second dye has the following structure:

Embedded image And E. The first dye has the following structure:

Embedded image And the second dye has the following structure:

Embedded image (In the above formula, Z ₁ and Z ₂ independently represent a hydrogen or halogen atom or a substituted or unsubstituted alkyl, a substituted or unsubstituted alkoxy, a substituted or unsubstituted aromatic group and a substituted or unsubstituted heterocyclic group. A cyclic group; and R ₁ and R ₂ are independently substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, or substituted or unsubstituted aryl).

(Embodiment 3) A photographic element according to claim 1, wherein at least one dye has structural formula I:

Embedded image Wherein Z ₁ is a phenyl, pyrrolyl or fused benzene ring, Z ₂ is phenyl, pyrrolyl or halogen, R ₁ and R ₂ are an acid-substituted alkyl group, and A ⁺ Ion).

(Embodiment 4) The photographic element according to claim 1, wherein at least one dye has the structural formula II:

Embedded image (Wherein X is O or S, Y ₁ is pyrrolyl or phenyl, and Y ₂ is 4, when X is O,
Is 5-benzo substituent, X is phenylcarbamoyl or phenyl carboxamide substituent when the S, R ₃ and R ₄ is an acid substituted alkyl group, and B ⁺ is a counterion).

(Embodiment 5) The photographic element according to claim 1, wherein L of the gold (I) compound is a mesoionic compound represented by the following formula:

Embedded image (Wherein a, b, c, d and e represent an unsubstituted or substituted atom necessary to complete a heterocyclic ring, preferably a triazolium or tetrazolium 5-membered ring. The circle that has is a symbolic representation of the six delocalized π electrons associated with a partial positive charge on the heterocycle).

(Embodiment 6) A gold (I) compound represented by the following formula:

Embedded image (Wherein, R ₆ , R ₇ , and R ₈ independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, an amino group, a substituted or unsubstituted aryl group,
And X ^- is a halogen or a BF ₄ ^- anion) or the following formula:

Embedded image (Wherein, R ₆ , R ₇ , and R ₈ independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, an amino group, a substituted or unsubstituted aryl group,
And X ^- is a halogen or a BF ₄ ^- anion) or the following formula:

Embedded image (Wherein R ₆ , R ₇ , R ₈ and R ₉ are independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, an amino group, a substituted or unsubstituted aryl group, X ^- is halogen or BF ₄ ^- photographic element of claim 1 having an anion).

(Embodiment 7) A disulfide compound represented by the following formula (I)
A photographic element according to claim 1, represented by I):

Embedded image Wherein X ′ is independently —O—, —NH—, or —NR— (where R is an alkyl group, a fluoroalkyl group, an aryl group, or a sulfonyl group);
m and r are independently 0, 1 or 2;
And r are not simultaneously 0, M is —H or a cationic species, Ar is an aromatic group, p is 0 or 1, and when p is 1, L ² is a linking group. Although the preferred embodiments of the invention have been described in particular detail, it will be understood that various changes and modifications can be made within the spirit and scope of the invention.

[0153]

The present invention provides a sensitization range which can be adjusted by appropriately selecting Dye 1 and Dye 2. The inventor has also found that when the first dye provides a maximum sensitization of less than 475 nm and the structural features of these dyes result in the formation of mixed aggregates, the sensitivity loss is very small. Further, the present invention provides (1) an adjustable sensitization range by appropriately selecting Dye 1 and Dye 2,
(2) provides tunable gold / sulfur chemical sensitization by using appropriate amounts of the gold compound of formula (I) and the disulfide compound of formula (II), and (3) provides improved manufacturability. .

Continued on the front page (72) Inventor David Alan Stegman New York, United States 14428, Churchville, Steans Road 618 (72) Inventor Teresa A. Smith United States, Massachusetts 02178, Belmont, Belmont Street 837 (72) Inventor John Derek Lewis United States of America, New York 14580, Webster, Mill Creek Run 1310 (72) Inventor Karen Jay. Clingman United States, New York 14534, Pittsford, Framingham Lane 63 (72) Inventor Bruce E. Kern United States, New York 14618, Rochester, Vienna Wood Drive 265

Claims (3)

[Claims] 1. The method according to claim 1, wherein the silver halide has a λ ₁
And a second blue sensitizing dye having λ ₂ (however, the first and second dyes do not contain selenium)
A photographic element comprising at least one silver halide emulsion layer sensitized with λ ₁ , wherein λ ₁ is longer than λ ₂ , and λ ₁ and λ ₂ have an energy gap not exceeding 0.12 eV. A photographic element separated by ΔE, where ΔE is defined by: (Where λ ₁ is the maximum absorption wavelength expressed in nanometers (nm) of the silver halide emulsion sensitized with the first dye,
λ ₂ is the maximum absorption wavelength of the silver halide emulsion sensitized with the second dye). 2. The photographic element according to claim 1, wherein the silver halide is chemically sensitized with a gold (I) compound of the formula (Ia) or (Ib): AuL ₂ ⁺ X ⁻ (Ia) or AuL (L ¹ ) ⁺ X ⁻ (Ib), where L is a mesoionic compound, X is an anion, and L ¹ is a Lewis donor ligand. 3. A photographic element according to claim 1, further comprising a disulfide compound of the formula (II): ## STR1 ## Wherein X ′ is independently —O—, —NH— or —NR— (where R is an alkyl group, a fluoroalkyl group, an aryl group or a sulfonyl group), and m and r are Independently 0, 1 or 2 but m
And r are not simultaneously 0, M is —H or a cationic species, Ar is an aromatic group, and when p is 1, L ² is a linking group)].