JP2001109095A - Silver halide photographic element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new method for inhibiting the growth of fog in a film. SOLUTION: The silver halide photographic element includes at least one silver bromoiodide emulsion layer. The silver bromoiodide emulsion has >=4 mol% average iodide content and has been chemically sensitized with a urea compound of formula I (where X, R1-R4 and A1-A4 are each a prescribed group).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to the use of silver halide photographic elements containing silver bromoiodide emulsion sensitized with a specific urea sensitizer.

[0002]

BACKGROUND OF THE INVENTION The halides used in photosensitive silver halide emulsions include chlorides, bromides and iodides and various combinations of these ions. Currently accepted theory of the formation of latent images in silver halide crystals is the theory that electrons transfer from silver halide to silver ions. Therefore, the performance of forming a latent image is considered to increase in order from chloride to iodide. This is because the oxidation potential of these ions decreases sequentially from chloride to iodide. However, at the same time, the solubility of silver halide decreases in the same order from chloride to iodide, so that the latent image developable in this order becomes smaller. In order to obtain the highest speed on photographic film, Solberg et al., US Pat.
For the reasons described in No. 8, silver bromoiodide has been reached as the best compromise for speed films for cameras. A composition having a high iodide content has, for example, 1) strong dye-adsorbing property, 2) the ability to release iodide which suppresses development to obtain an interimage effect,
Or 3) is advantageous for certain applications that require high efficiency latent image capture. However, higher iodide contents may increase fogging, especially when the coated emulsion is exposed to high temperatures for extended periods of time.

The problem of fogging of silver halide emulsions has plagued the photographic industry from its inception. Fog is defined as the developed density not associated with the effects of the imaging exposure and is usually expressed as "D-min", ie, the density obtained in the unexposed portions of the film. Commonly measured concentrations include those caused by fog,
Both concentrations that occur as a function of exposure to light are included. The appearance of photographic fog associated with the intentional or unintentional reduction of silver ions can be attributed to the production of silver halide emulsions, spectral / chemical sensitization of silver halide emulsions, melting and holding of liquid silver halide melts, halogenation It is known in the art that it can occur during a number of manufacturing steps of a photographic element, including subsequent coating of a silver emulsion and prolonged natural and artificial ripening of the coated halide emulsion.

[0004]

Therefore, suppressing fog is a significant concern when dealing with silver halide emulsions. Treatment with additives that function as weak oxidants, silver complexing agents or other methods is one way to address the above problems. Many compounds with many different chemical structures have been studied and used for the above purpose.
Examples include Research Disclosure ,
Item 38957, found in September 1996, and a few examples include mercaptotetrazoles, benzothiazoles, tetraazaindenes, disulfide compounds and mercury (II) chloride. Despite the large number of materials available, few can reduce fog without reducing sensitivity.

[0005] Therefore, there is a continuing need for a method of improving the storage stability of silver halide emulsions, especially emulsions with significant iodide content. The present inventors have discovered that certain classes of tetrasubstituted urea compounds are effective antifoggants for high iodide emulsions. This class of urea compounds is described in U.S. Pat. No. 4,810,626 as being useful for performing chemical sensitization, but these compounds are useful for preventing fogging of certain highly fogging emulsions. There is no indication that it can be used as an agent.

[0006]

SUMMARY OF THE INVENTION The present invention is a silver halide photographic element comprising at least one silver bromoiodide emulsion layer, wherein the silver bromoiodide emulsion has an iodide content of 4 mole%. And the following formula:

[0007]

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Wherein X is sulfur, selenium or tellurium, and R ₁ , R ₂ , R ₃ and R ₄ are each independently an alkylene, cycloalkylene, carbocyclic arylene, heterocyclic arylene R ₁ and R ₂ or R ₃ and R ₄ may form a 5- to 7-membered heterocycle with the nitrogen atom to which they are attached, or an alkarylene or aralkylene group; and A ₁ , A ₂ ,
A ₃ and A ₄ are each independently hydrogen or represent a carboxyl, sulfin, sulfone, hydroxam, mercapto, sulfonamide or primary or secondary amino nucleophilic group, provided that A ₁ R _{1 to} A ₄ R ₄
At least one of which contains a nucleophilic group bonded to the nitrogen atom of urea via a two- or three-membered chain). Provides the element. The present invention provides a new method for suppressing fog growth of aged films. Quite unexpectedly, coated silver bromoiodide emulsions having an average iodide content of 4 mol% or more show high storage stability when chemically sensitized with the specific urea compounds described above. It was discovered. These urea compounds can generally achieve equivalent fresh speed at the following fog levels when sensitized by more common sulfur sources such as thiosulfates.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The silver halide emulsion used in the present invention is a bromoiodide emulsion having an average iodide content of 4 mol% or more. The emulsion preferably has an iodide content of 4 mol% to about 10 mol%, more preferably 4 mol% to about 6 mol%. Various methods for producing bromoiodide emulsions having different iodide contents are well known in the art. A comprehensive summary of these methods can be found in Research
Disclosure , Item 38957, September 1996, Section I, Emulsion Grains.
found in and their Preparation. Silver halide emulsions can contain grains of any size and morphology. Thus, these grains can take the form of any of the cubic, octahedral, cubo-octahedral, or other naturally occurring forms of cubic lattice silver halide grains. Furthermore, these grains may be irregular, such as spherical grains or tabular grains.

Particularly useful in the present invention are emulsions of tabular grain silver bromoiodide grains. Tabular grain emulsions that can be specifically considered have an area exceeding 50% of the total projected area of the emulsion grains and a thickness of less than 0.3 μm (0.1 mm in the case of a blue-sensitive emulsion).
It is an emulsion occupied by tabular grains having a mean tabularity (T) of more than 25 (preferably more than 100) having a mean tabularity (T) of less than 5 μm. Note that the term “flatness” is used in the following formula in applications known in the art. In the equation T = ECD / t ² , ECD is the average equivalent circular diameter of the tabular grains (μm) and t is the average thickness of the tabular grains (μm).

The useful average ECD of a photographic emulsion is about 10 μm
In practice, the ECD of the emulsion is about 4
It rarely exceeds μm. Since both photographic sensitivity and granularity increase with increasing ECD, the smallest tabular grain E that is compatible with achieving the required target sensitivity.
It is generally preferred to employ a CD.

The tabularity of the emulsion increases significantly as the thickness of the tabular grains decreases. It is generally preferred that the projected area of the target tabular grains be satisfied by thin (t <0.2 μm) tabular grains. To achieve the lowest level of granularity, the target tabular grain projected area is very thin (t <0.
(6 μm).
Tabular grain thicknesses are generally in the low range, up to about 0.02 μm or less.

As noted above, tabular grains having a thickness less than the specified thickness provide at least 50% of the total grain projected area of the emulsion.
%. To maximize the benefits of high tabularity, it is preferred that tabular grains satisfying the thickness criterion account for the highest normally obtainable percentage of the total grain projected area of the emulsion. For example, in the case of a preferred emulsion, tabular grains satisfying the above thickness criterion account for at least 70% of the total grain projected area. For the highest performance tabular grain emulsions, tabular grains satisfying the thickness criteria above account for at least 90% of total grain projected area.

The tetrasubstituted urea compound used in the present invention is represented by the following structural formula.

[0015]

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Wherein X is sulfur, selenium or tellurium
Sulfur easily enters as a starting material for thiourea synthesis.
What can be done and the aqueous solution that sensitizes silver halide
Preferred due to the high solubility of the thiourea compound in
No. Where R₁, R_Two, R_ThreeAnd R_FourAre independent
, Alkylene, cycloalkylene, carbocyclic arylene
, Heterocyclic arylene, alkarylene or aral
The nitrogen that represents the radicals of kylene or to which they are attached
Together with the atom, R₁And R_TwoOr R_ThreeAnd R_FourIs 5 ~ 7
The member heterocycle may be completed. A₁, A_Two, A _Threeand
A_FourAre each independently hydrogen or carboxy
, Sulfin, sulfone, hydroxam, mercap
, Sulfonamide or primary or secondary amine
A nucleophilic group represented by₁R₁~ A_FourR_FourOut of
At least one of which is urea via a two or three membered chain
Contains a nucleophilic group attached to the nitrogen atom. Carbo
Xyl, sulfine, sulfone or hydroxam groups
Is a preferred nucleophilic group, and a carboxyl group is most preferred.
New

The term "nucleophilic" group, as used in the present invention, includes oxygen atoms of oxyacids, sulfur atoms of sulfur acids, and nitrogen acids or nitrogen atoms of primary or secondary amines. Means an atom. Such nucleophilic groups include, for example, carboxyl (—COOH), sulfine (—SO
₂ H), sulfone (—SO ₃ H), hydroxam (—N
HOH), mercapto (-SH), sulfonamide (-
SO ₂ NH—) and primary and secondary amine groups. Inorganic or organic salts of these acids are equally useful. At least one of R ₁ A _{1 to} R ₄ A ₄ is preferably an omega-bonded methyl- or ethyl-carboxylic acid or a salt thereof.

For Successful Chemical Sensitization of Silver Halide
Urea nitrogen as required and via a two or three member chain
Other than the above nucleophilic group bonded to
The composition of the RA groups remaining in the tiger substituted urea compounds is broad
Box to achieve the desired chemical sensitization of the silver halide.
Can be R not bound to the required nucleophilic group ₁
~ R_FourCan be represented by at least one of
Alkylene groups are from 1 to 6 to obtain higher solubility.
Carbon atoms, preferably from 1 to about 4 carbon atoms
Contains offspring.

When the groups R _{1 to} R ₄ are cyclic alkylene,
The ring portion may contain about 3 to about 8 carbon atoms, preferably about 5 or 6 carbon atoms. When the required nucleophilic group is attached to a cyclic alkylene group, such a group must be 2 for successful operation of the present invention.
It is important that the bond be attached to one of the urea nitrogen atoms through a three or three membered chain. Some or all of the two or three membered chains may be atoms of the cyclic alkylene ring.

Where one of the R ₁ -R ₄ groups is an aromatic heterocyclic ring or an aromatic carbocyclic ring, such a ring system will have from about 5 to about 10 atoms in the ring. For example, pyrrole, phenyl, naphthyl, pyridinyl, quinolyl and naphthyl (na)
phthyl). When the required nucleophilic group is bonded to the aromatic heterocyclic group or the aromatic carbocyclic group, the chain separating the nucleophilic group from the nitrogen atom of urea contains 2 to 3 members. In. Some or all of the 2-3 membered chain may be an atom of the ring.

When the R ₁ -R ₄ groups are alkalylene or aralkylene, the alkylene portion may contain from about 1 to about 3 carbon atoms, and the aryl portion may be an aromatic group as described above. It is. When the required nucleophile is attached to an aralkylene group, the linkage separating the nucleophile from the urea nitrogen atom contains a few atoms. Some or all of the two or three membered chain may also be atoms of the ring.

The heterocyclic ring which can be formed by the nitrogen atom of urea and R ₁ and R ₂ or the nitrogen atom of urea and R ₃ and R ₄ may contain 5 or 6 ring members. . Representative heterocyclic rings thus formed include pyridine, morpholine, piperidine and diazine.

Preferably, the R _{1 to} R ₄ groups are independently
When the required nucleophilic group is not attached, it is an alkylene group containing from 1 to 6 carbon atoms, preferably containing from 1 to about 4 carbon atoms. Specific 1, useful in the present invention
As the 1,3,3-tetra-substituted-2-thiourea compound, there is a compound represented by the following formula.

[0024]

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The synthesis of the urea compound used in the present invention is as follows:
It can be performed by various techniques known in the art. For example, one method comprises reacting an aliphatic monoaminocarboxylic acid with a dialkylthiocarbamoyl halide. Specific examples of the synthesis of these urea compounds can be found in U.S. Pat. No. 4,810,626. This patent is incorporated herein by reference.

The silver halide emulsion used in the present invention is:
It is chemically sensitized by the urea compound. A comprehensive summary of conventional chemical sensitization methods can be found in Research Disclosure.
sure item 38957, September 1996, section
IV, found in Chemical Sensitization. U.S. Pat. No. 4,439,520 illustrates the application of these sensitization methods to tabular grain emulsions and introduces a spectral sensitizing dye into the emulsion followed by a heating step (finishing) to effect chemical sensitization. The advantage of the "dye at the time of finish sensitization" which gives a feeling is described. The dye at the time of finish sensitization is
It is particularly advantageous for practicing the invention. A comprehensive summary of useful spectral sensitizers can be found in Research Disclos
ure September 1996, item 38957, section V, Spectralsensitization and Desensitization, AS
Provided to pectral Sensitizing Dyes. A useful specific sensitization method using tetrasubstituted ureas is described in U.S. Pat.
No. 810,626. The disclosure of this patent is incorporated herein by reference.

The urea sensitizing compound can be added at a level of about 10 ^-6 to about 10 ^-2 mol per mol of silver halide.
Preferred concentrations of the urea compound to achieve silver halide sensitization are from about 10 ^-5 to about 10 ^-3 per mole of silver halide.
Is a mole.

The above urea sensitizing compounds may be added alone or in combination with other urea compounds or with other sensitizers. These urea sensitizing compounds are particularly useful when combined with a gold sensitizer. The gold sensitizer is a thiosulfate-free gold salt or gold complex. It is known various gold sensitizer in the art and examples Resear
ch Disclosure September 1996 Item 389
57, provided in Section IV. Particularly useful are gold complexes containing an organic mercapto ligand with a solubilizing group (compound GS-2a), as described in U.S. Patent Application No. 08 / 965,507 to Lok et al.
This patent application is incorporated herein by reference. Compound G
Consists of a mesoionic ligand like S-2b and Deat
The gold complexes described in on US Pat. No. 5,049,485 are equally useful. This patent is incorporated herein by reference.

[0029]

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As described in US Pat. No. 5,945,270, the water-soluble organic mercapto Au of the present invention is described.
(I) The complex can be represented by the following formula. [L-Au-L] M This complex is symmetric. L is an organic mercapto ligand having antifogging, stabilizing or sensitizing properties and suitable for use in silver halide photographic elements. A variety of such ligands are known in the art and are commercially available, or are available from Research Disc.
loss 274 (1984). Some suitable ligands include thiol ligands with hydrophilic substituents such as mercaptoazole, examples of which are described in U.S. Pat. Nos. 3,266,897 and 4,607,004. No. 3,266,897, No. 4,920,043,
Nos. 4,912,026 and 5,011,768
And British Patent No. 1,275,701. M is a counter ion of the cation.

The organic mercapto Au (I) complex of the present invention can be further represented by the following formula. [(M-SOL) _n
-AS-Au-SA- (SOL-M) _n ] M and this complex is symmetric. M is a counter ion of the cation. Preferably, M is an alkali metal such as potassium, sodium or cesium, or an ammonium cation such as a tetrabutylammonium or tetraethylammonium group. SOL is a water solubilizing group, suitable examples of which are the sulfato, sulfonato, sulfinato, phosphato and carboxy groups, wherein n is an integer from 1 to 4, more preferably n is 1
Or 2.

A is a substituted or unsubstituted divalent organic radical. A is preferably an aliphatic (cyclic or acyclic), aromatic or heterocyclic divalent group. When A is aliphatic, A is preferably a substituted or unsubstituted aliphatic group having from 1 to 20 carbon atoms, more preferably a substituted or unsubstituted containing from 1 to 8 carbon atoms. Is an aliphatic group. Examples of suitable groups include
Alkylene groups such as ethylene, methylene, propylene, butylene, pentylene, hexylene, octylene,
There are 2-ethylhexylene, decylene, dodecylene, hexadecylene, octadecylene, cyclohexylene, isopropylene and t-butylene groups.

Preferred aromatic groups contain 6 to 20 carbon atoms. Even more preferably, the aromatic groups contain from 6 to 10 carbon atoms and include, among others, phenylene and naphthylene. These groups may contain a substituent. The heterocyclic group is preferably a substituted or unsubstituted 3- to 15-membered divalent ring group, wherein the ring nucleus has at least one atom selected from nitrogen, oxygen, sulfur, selenium and tellurium. It contains. Even more preferably, the heterocyclic group is a 5- to 6-membered ring, having at least one, preferably two or more atoms selected from nitrogen. Examples of heterocyclic groups include the divalent radical pyrrolidine,
There are rings of piperidine, pyridine, tetrahydrofuran, thiophene, oxazole, thiazole, imidazole, benzothiazole, benzoxazole, benzimidazole, selenazole, benzoselenazole, tellurazole, triazole, benzotriazole, tetrazole, oxadiazole, or thiadiazole. A preferred heterocyclic group is tetrazole.

Unless otherwise stated, substituents that can be substituted on the molecules of the present invention, whether substituted or unsubstituted, include any groups that do not destroy the properties required for photographic utility. When the term "group" is used to identify a substituent that contains a substitutable hydrogen, not only the unsubstituted form of that substituent, but also the group or groups mentioned herein. It shall include the substituted form. Suitably, the groups may be attached to the rest of the molecule by carbon, silicon, oxygen, nitrogen, phosphorus or sulfur atoms. Suitable substituents for A include, for example: That is, a halogen, for example,
Chlorine, bromine or iodine; nitro; hydroxyl; cyano; carboxyl; or a group which may be further substituted;
Alkyl, including, for example, straight or branched chain alkyl,
For example, methyl, trifluoromethyl, ethyl, t-butyl, 3- (2,4-di-t-pentylphenoxy) propyl and tetradecyl; alkenyl, such as ethylene, 2-butene; alkoxy, such as methoxy, ethoxy, propoxy, butoxy. , 2-methoxyethoxy, s
ec-butoxy, hexyloxy, 2-ethylhexyloxy, tetradecyloxy, 2- (2,4-di-t-
Pentylphenoxy) ethoxy and 2-dodecyloxyethoxy; aryl, for example, phenyl, 4-t-butylphenyl, 2,4,6-trimethylphenyl, naphthyl; aryloxy, for example, phenoxy, 2-methylphenoxy, α- or β- Naphthyloxy and 4-
Tolyloxy; carbonamide, such as acetamide,
Benzamide, butyramide (butyramid)
o), tetradecaneamide, α- (2,4-di-t-pentyl-phenoxy) acetamide, α- (2,4-di-t-pentylphenoxy) butylamide, α- (3-
Pentadecylphenoxy) -hexaneamide, α- (4
-Hydroxy-3-tert-butylphenoxy) -tetradecaneamide, 2-oxo-pyrrolidin-1-yl, 2-
Oxo-5-tetradecylpyrolin-1-yl, N-methyltetradecaneamide, N-succinimide, N-phthalimide, 2,5-dioxo-1-oxazolidinyl, 3-dodecyl-2,5-dioxo-1-imidazolyl, And N-acetyl-N-dodecylamino, ethoxycarbonylamino, phenoxycarbonylamino, benzyloxycarbonylamino, hexadecyloxycarbonylamino, 2,4-di-t-butylphenoxycarbonylamino, phenylcarbonylamino, 2,5-
(Di-t-pentylphenyl) carbonylamino, p-
Dodecyl-phenylcarbonylamino, p-toluylcarbonylamino, N-methylureido, N, N-dimethylureido, N-methyl-N-dodecylureido, N-
Hexadecyl ureide, N, N-dioctadecyl ureide, N, N-dioctyl-N'-ethyl ureide, N-
Phenylureido, N, N-diphenylureido, N-
Phenyl-Np-toluylureido, N- (m-hexadecylphenyl) ureido, N, N- (2,5-di-
t-pentylphenyl) -N'-ethylureido and t-butylcarbonamide; sulfonamides such as methylsulfonamide, benzenesulfonamide, p-
Toluylsulfonamide, p-dodecylbenzenesulfonamide, N-methyltetradecylsulfonamide,
N, N-dipropylsulfamoylamino and hexadecylsulfonamide; sulfamoyl such as N-methylsulfamoyl, N-ethylsulfamoyl,
N-dipropylsulfamoyl, 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; carbamoyl such as N-methylcarbamoyl, N-
Dibutylcarbamoyl, N-octadecylcarbamoyl, N- [4- (2,4-di-t-pentylphenoxy) butyl] carbamoyl, N-methyl-N-tetradecylcarbamoyl and N, N-dioctylcarbamoyl; acyl, for example, acetyl , (2,4-di-t-amylphenoxy) acetyl, phenoxycarbonyl, p-
Dodecyloxyphenoxycarbonyl, methoxycarbonyl, butoxycarbonyl, tetradecyloxycarbonyl, ethoxycarbonyl, benzyloxycarbonyl, 3-pentadecyloxycarbonyl and dodecyloxycarbonyl; sulfonyl such as methoxysulfonyl, octyloxysulfonyl, tetradecyloxysulfonyl, 2-ethylhexyloxysulfonyl,
Phenoxysulfonyl, 2,4-di-t-pentylphenoxysulfonyl, methylsulfonyl, octylsulfonyl, 2-ethylhexylsulfonyl, dodecylsulfonyl, hexadecylsulfonyl, phenylsulfonyl,
4-nonylphenylsulfonyl and p-toluylsulfonyl; sulfonyloxy, such as dodecylsulfonyloxy and hexadecylsulfonyloxy; sulfinyl, such as methylsulfinyl, octylsulfinyl, 2-ethylhexylsulfinyl, dodecylsulfinyl, hexadecylsulfinyl, phenylsulfinyl, 4 -Nonylphenylsulfinyl and p-toluylsulfinyl; thio such as ethylthio, octylthio, benzylthio, tetradecylthio, 2- (2,
4-di-t-pentylphenoxy) ethylthio, phenylthio, 2-butoxy-5-t-octylphenylthio and p-tolylthio; acyloxy such as acetyloxy, benzoyloxy, octadecanoyloxy,
p-dodecylamidobenzoyloxy, N-phenylcarbamoyloxy, N-ethylcarbamoyloxy and cyclohexylcarbonyloxy; amines such as phenylanilino, 2-chloroanilino, diethylamine, dodecylamine; iminos such as 1 (N-phenylimido) ethyl Phosphates such as dimethyl phosphate and ethyl butyl phosphate; phosphites such as diethyl- and dihexyl-phosphite; heterocyclic groups, heterocyclic oxy groups or heterocyclic thio groups Is optionally substituted and comprises a plurality of carbon atoms and at least one heteroatom selected from the group consisting of oxygen, nitrogen and sulfur.
Containing from 7 to 7 membered heterocyclic rings). For example, 2
-Furyl, 2-thienyl, 2-benzimidazolyloxy; quaternary ammonium, such as triethylammonium; and silyloxy, such as trimethylsilyloxy. One particularly suitable substituent for A is a benzamide group.

In general, the above groups and their substituents include
Some contain up to 48 carbon atoms, generally from 1 to 36 carbon atoms and usually less than 24 carbon atoms, but even more may be subject to specially selected substituents. sell.

When A is substituted, (SOL-M)
_n may be bonded to the substituent. One suitable embodiment of A- (SOL-M) _n (where n = 1) is represented by the following formula:

[0037]

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Specific examples of the Au (I) complex include, but are not limited to, those represented by the following formula.

[0039]

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One particularly suitable complex is the compound S, potassium bis (1- [3- (2-sulfonatobenzamido) phenyl] -5-mercaptotetrazole potassium) aurate (I) pentahydrate. is there.

One of the advantages of the complexes of the present invention is that they are water-soluble. These complexes preferably have a solubility at 22 ° C. of 2 g / L, more preferably 5 g / L and most preferably 10 g / L.
Particularly suitable compounds have a solubility greater than 20 g / L.

As described in US Pat. No. 5,049,485, the mesoionic compound is a compound represented by the following formula. AuL ₂ + X ⁻ or AuL (L ¹ ) ⁻ X ^{− wherein} L is a mesoionic compound, X is an anion, and L ¹ is a Lewis donor ligand.

The compounds may be soluble in various solvents, including water or organic solvents such as acetone or methanol, but the most preferred compounds are water-soluble. The term water-soluble for the mesoionic compound means that the gold (I) compound is soluble in water at normal pressure and at a temperature of 20 ° C. in a concentration of at least 10-5 mol / l of water.

The mesoionic compound L can form a gold (I) compound which is water-soluble and can be subjected to the above-mentioned chemical sensitization of a photographic silver halide composition through coordination bond with gold (I) ion. Compound. The mesoionic compound is preferably represented by the following formula.

[0045]

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Where the + -marked circle on the heterocyclic ring indicates six delocalized π electrons with a partial positive charge on the heterocyclic ring. a, b, c, d and e are the unsubstituted or substituted atoms required to complete the mesoionic compound, such as the mesoionic triazolium or tetrazolium 5
Represents the carbon and nitrogen atoms required to complete the membered heterocyclic ring. Members of the heterocyclic ring (a,
b, c, d and e) may be CR or NR 'groups or chalcogen atoms. The one (minus) sign indicates the two additional electrons of the exocyclic group f conjugated to the six π electrons of the heterocyclic ring. It is understood that there is extensive delocalization and the charges shown are only partial charges. The exocyclic group f may be S, Se or NR ″. The groups R, R ′ and R ″ may be hydrogen atoms, substituted or unsubstituted alkyl, aryl or heterocyclic groups, or R, R ′ and R ″ may be linked by a bond to form another ring. (Note: The structural formula of the mesoionic compound L different from the above structural formula can be found elsewhere in the literature, but in this application Olis and Ra
Advances in Heterocyclic Chemistry Volume 19, 19 by msden
Use the one described in Academic Press, London, 1976). In the novel compounds of the present invention, the mesoionic compound is coordinated to gold (I) via an exocyclic group f.
The exocyclic group f must not be 0 in the present case.
This is because it is not known that oxygen ligands form stable compounds with gold (I).

Examples of the mesoionic gold (I) compound of the present invention are shown in the following table. In the structural formula of the gold (I) compound, the partial charge of the mesoionic ligand is excluded to avoid confusion with the gold charge of the chain ion. It should be understood that a ring indicating the six delocalized π electrons of the heterocyclic moiety is retained but does not imply aromaticity.

[0048]

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The urea sensitizing compound is particularly useful when combined with a specific class of isothiazolin-one compounds represented by the following formula.

[0050]

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Z contains the carbon atoms necessary to form a substituted or unsubstituted non-aromatic ring. Z is preferably a substituted or unsubstituted 5- or 6-membered non-aromatic ring, and more preferably a substituted or unsubstituted 5-membered non-aromatic ring. In one suitable embodiment, Z is an unsubstituted non-aromatic five-membered ring.

R ⁷ may be any substituent that is suitable for use in silver halide photographic elements and does not interfere with the antifoggant activity of the isothiazolin-one compound. R ⁷ is preferably a substituted or unsubstituted aliphatic, aromatic or heterocyclic group.

When R ⁷ is an aliphatic group, R ⁷ is preferably an alkyl group having 1 to 20 carbon atoms, or an alkenyl or alkynyl group having 2 to 20 carbon atoms. R ⁷ is more preferably 1 to
An alkyl group containing 6 carbon atoms or an alkenyl or alkynyl group containing 3-5 carbon atoms. R ⁷ is most preferably an alkyl group containing 1 to 3 carbon atoms. These groups may or may not have substituents. Examples of alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, 2-ethylhexyl, decyl, dodecyl, hexadecyl, octadecyl, cyclohexyl,
There are isopropyl and t-butyl groups. Examples of alkenyl groups include allyl and butenyl, and
Examples of alkynyl groups include propargyl and butynyl.

Preferred aromatic groups have from 6 to 20 carbon atoms, especially phenyl and naphthyl. More preferably, the aromatic groups have from 6 to 10 carbon atoms, and most preferably, the aromatic groups are phenyl. These groups may be substituted or unsubstituted. The heterocyclic group is a 3- to 15-membered or fused ring having at least one atom selected from nitrogen, oxygen, sulfur, selenium and tellurium. More preferably, the heterocyclic group has 5-6 atoms having at least one atom selected from nitrogen.
It is a member ring. Examples of heterocyclic groups include pyrrolidine, piperidine, pyridine, tetrahydrofuran, thiophene,
There are oxazole, thiazole, imidazole, benzothiazole, benzoxazole, benzimidazole, selenazole, benzoselenazole, tellurazole, triazole, benzotriazole, tetrazole, oxadiazole or thiadiazole ring.

Non-limiting examples of substituents for R ⁷ and Z include alkyl groups (eg, methyl, ethyl, hexyl), aryl groups (eg, phenyl, naphthyl, tolyl), acyl groups (eg, acetyl, propionyl, butyryl). , Valeryl), sulfonyl groups (eg, methylsulfonyl, phenylsulfonyl), ether groups (eg, methoxy, ethoxy, propoxy, butoxy), hydroxyl groups, and nitrile groups. Preferred substituents are lower alkyl groups, i.e. alkyl groups having 1 to 4 carbon atoms (e.g. methyl), hydroxyl groups and halogen atoms (e.g. chloro).

The isothiazolin-one compounds are known as Shroot
U.S. Pat. No. 4,708,959, Maignan et al. U.S. Pat. No. 4,851,541, Moffat U.S. Pat. No. 5,082,966, Moffat et al. U.S. Pat.
No. 6,777 and Moffat et al., US Pat.
No. 814. These patents are incorporated herein by reference.
Some of these compounds are also available from Zeneca Biocides, I
nc. (Wilmington, Delaware, USA, 19850-5457).

Useful levels of isothiazolin-one compounds are from about 0.02 to 50 mmol, more preferably 0.05 to 20 mmol, per mole of silver;
And most preferably it is 0.10-5.0 mmol. Isothiazolin-one compounds can be used in addition to conventional emulsion stabilizers or antifoggants commonly used in the art. Two or more isothiazolines
Combinations of on compounds can also be used.

The photographic emulsions of the present invention are generally prepared by precipitating silver halide crystals in a colloidal matrix by methods commonly used in the art. The colloid is generally a hydrophilic film former, such as gelatin, alginic acid or a derivative thereof.

The crystals formed in the above precipitation step are washed,
Next, chemical sensitization and spectral sensitization are performed by adding a spectral sensitizing dye and a chemical sensitizer, and then a heating step is performed, during which the temperature of the emulsion is generally raised to 40 ° C to 70 ° C for a predetermined period. Maintain at that temperature. The precipitation method, spectral sensitization method and chemical sensitization method used for producing the emulsion used in the present invention may be a method known in the art.

After spectral sensitization, the emulsion is coated on a support. Various coating methods include dip coating, air knife coating, curtain coating and extrusion coating.

The silver halide emulsion of the present invention is chemically sensitized in the presence of an isothiazolin-one compound. Thus, the isothiazolin-one compound can be added before or during the precipitation. For example, the compound may be added to a container containing an aqueous solution of gelatin and salt prior to initiating precipitation, and may be added to the salt solution or silver nitrate solution during precipitation, or It may be added directly to the kettle from a separate jet. Further, after the precipitation of the isothiazolin-one compound,
It may be added to the silver halide emulsion before or during the heat treatment used to perform chemical sensitization. The isothiazolin-one compound is preferably added after precipitation, before or during heat treatment, and more preferably before heat treatment.

The isothiazolin-one compound is usually added directly to the emulsion. This compound can be added to the photographic emulsion using any method suitable to achieve its purpose. Generally, the compound is dissolved in an aqueous solution and added to the emulsion.

Certain dopants, such as copper, thallium,
Lead, bismuth, cadmium and Group VIII noble metals
They may be added during precipitation and growth of the silver halide grains, or these dopants may be present during the chemical sensitization step utilized in the present invention. Other dopants include U.S. Pat. Nos. 4,981,781 and 4,932.
There are transition metal complexes as described in 7,180 and 4,933,272. Reduction sensitizer,
It is specifically contemplated to be used individually or in combination.

The photographic emulsions incorporating the present invention can be incorporated into color negative or color reversal photographic elements. Further, the photographic element of the present invention may be a Research element.
Disclosure , November 1992, item 34.
390 (published by Kenneth Mason Publications, Ltd., Dudsley Annex, Emsworth 12a, Hampshire, England, P0107DQ), which supports a transparent magnetic recording layer such as a layer containing magnetic particles. It may be provided on the lower side of the body. Generally, the element is the full thickness (excluding the support)
Is about 5 to about 30 μm. Further, the photographic element of the present invention is disclosed in Invention Technical Report No. 94-6023 (Japan Patent Office and Japan Diet Library) may comprise an annealed polyethylene naphthalate film base as described in
And England P0107DQ Emsworth, Hampshire 12a North Street, Dudley Annex whereabouts of Kenneth Mason Publications, Ltd. issued R
essearch Disclosure June 1994, item 36230, and Adv
advanced Photo System, especially Kodak
Available in small format systems such as ADVANTIX film or cameras.

The following table shows (1) Research D
isclosure , item 1964 , December 1978
3, (2) Research Disclosure ,
Item 308119, December 1989, (3) Research
rc Disclosure September 1994 Item 36
544 and (4) Research Disclos
ure September 1996 item 38957 is cited. All of these documents are in England P0107D
Q Kenneth Mason Publi-ca, Emsworth 12a North Street Dudley Annex, Hampshire
Published by tions, Ltd., the disclosures of which are incorporated by reference. The following table and the references cited in that table,
It is intended to read the description of specific components suitable for use in the elements of the present invention. The following table and the references cited therein also provide suitable methods for making, exposing, processing and manipulating the elements of the present invention and for processing the images contained therein. Has been described. Photographic elements and their processing that are particularly suitable for use in the present invention are described in Research Disclos.
ure February 1995 item 37038 and Research
rch Disclosure September 1997 Item 40
145. Both are England P0
107DQ Kenneth Mason Pu, Emsworth, Hampshire 12a North Street Dudley Annex
published by blications, Ltd., the disclosures of which are incorporated herein by reference. The high chloride components described in the above two publications are particularly suitable for use in the present invention.

Reference No. Section Theme 1 I, II Particle composition, morphology and preparation; Emulsion preparation including hardener, 2 I, II, IX, X, coating aids, additives, etc. XI, XII, XIV, XV 3 & 4 I, II, III, IX A & B 1 III, IV Chemical sensitization and spectral sensitization / desensitization 2 III, IV 3 & 4 IV, V 1V UV dye, fluorescent brightener, fluorescent dye 2 V 3 & 4 VI 1 VI Antifogging Agents and stabilizers 2 VI 3 & 4 VII 1 VIII Absorbing and scattering materials; antistatic layer; 2 VIII, XIII, XVI matting agents 3 & 4 VIII, IX C & D 1 VII image couplers and image modifying couplers 2 VII; dye stabilizers And hue improver 3 & 4 X1 XVII support 2 XVII 3 & 4 XV 3 & 4 XI specific layer arrangement 3 & 4 XII, XIII negative emulsion; direct positive emulsion 2 XVIII exposure 3 & 4 XVI 1 XIX, XX chemical treatment; developing agent 2 XIX, XX, XXII 3 & 4 XVIII, XIX, XX 3 & 4 XIV Scanning and digital processing method

The photographic element of the present invention can be used in an exposure structure intended for repeated use, or an exposure structure intended for limited use which is variously called a single-course camera, a lens with a film or a photosensitive material package unit Can be incorporated into

The photographic elements of the present invention can be used in the ultraviolet, visible and infrared regions of the electromagnetic spectrum as well as electron beams, β-radiation, γ-radiation, X-rays, α-particles, neutron radiation and lasers. It can be exposed to various forms of energy, including other forms of non-coherent (random phase) or coherent (in-phase) particle-like and wave-like radiant energy. The photographic elements of this invention can include features found in conventional radiographic elements when exposed to X-rays.

The photographic elements of the present invention are generally preferably exposed to actinic radiation in the visible region of the spectrum to produce a latent image and then processed to produce a visible dye image. Generally, development is performed followed by the usual steps of bleaching, fixing or bleach-fixing to remove silver or silver halide.
Wash and then dry.

[0070]

The following examples illustrate the practice of the present invention.
These examples are for the purpose of illustration and should not be considered as limiting the invention to the particular embodiments disclosed.

Production of Emulsion Emulsion 1 This emulsion was prepared by preparing Emulsion 2 on a large scale. Thus, grains similar to Emulsion 2 are produced, but 10 times or more. In this manufacturing method, two modifications were made: 1) growth with pBr 1.71 and 2) K ₄ R
A change was made to reduce u (CN) ₆ to 128 μg.

Emulsion 2 This emulsion was a tabular, dumped iodide bromoiodide emulsion, all of which contained about 68% of the manufacturing process.
At this point, the silver iodide seed emulsion was added all at once by placing it in a reaction vessel and then performing an over-run of silver. Contains 18.4 g of oxidized and lime-treated bone gelatin, 32.2 g of sodium bromide and 4.6 L of distilled water maintained at 40 ° C. containing an antifoam, which is well stirred. A 0.84 M silver nitrate solution was added to the reaction vessel at a rate of 35 L / min for 7.5 minutes. Following nucleation, ammonia ripening was performed at pH 10 with 0.45 moles of ammonia for 1 hour.
Minutes. An additional 222 g of oxidized and lime-treated bone gelatin and 3.0 L of distilled water containing 11.4 g of sodium bromide and an additional defoamer are added, and then the pH is increased.
Was adjusted to 5.8. 7.3 mL / mi of 0.84 M silver nitrate
Growth was initiated by addition at a flow rate of n and the flow rate was increased to 15.5 mL / min over 6.5 minutes. pBr 1.82
The growth was continued by adding an equimolar amount of 0.84 M silver nitrate together with sodium bromide in the double jet mode for 8.5 minutes while maintaining the temperature. The silver nitrate flow was increased from 15.5 mL / min to 26.2 mL / min during this period. The silver nitrate solution was then changed to 3.0M and growth was increased to 45.
Continue for 5 minutes, during which the flow rate is 7.3 mL / min to 15
Increased to 6 mL / min. 314 during the last minute of growth
μg of K ₄ Ru (CN) ₆ was added to the reaction vessel. Stop the flow and add 0.4 L of 4.1 M sodium bromide,
Subsequently, 2.5 mg of KSeCN and 0.565 mol of silver iodide seeds were added. 3.0 M silver nitrate at a flow rate of 40 mL / min.
A silver overrun was performed by addition for 3.2 minutes. Using a balanced flow rate of sodium bromide, the reduction in bromide concentration was limited to pBr 2.70. Excess salt was removed by ultrafiltration, containing an average of 4.5% iodide and a particle size of 0.65 × 0.11.
12.6 mol of a 9 μm emulsion was obtained.

Emulsion 3 This emulsion was prepared by preparing Emulsion 2 on a medium scale. Accordingly, grains similar to those of the emulsion 2 are produced, but the production amount is 10 times or more. Important changes are that growth was performed with pBr 1.71 and K ₄ Ru (CN) ₆ was reduced to 128 μg.

Emulsion 4 This emulsion was a tabular, dumped iodide bromoiodide emulsion, all of which contained about 70% of the manufacturing process.
At the time, the seed emulsion of silver iodide was put into the reaction vessel at once,
The silver was then rapidly added by performing an overrun of silver. Bone gelatin oxidized and treated with lime 1
8.4 g; 4.6 L of distilled water containing 32.2 g of sodium bromide and an antifoaming agent and kept at 51.5 ° C. are placed in a well-stirred reaction vessel.
A 42 M silver nitrate solution was added at a rate of 35 mL / min for 15 minutes. Following nucleation, ammonia aging was performed at 0.35
Performed at pH 10 with molar ammonia for 5 minutes. An additional 222 g of oxidized and lime treated bone gelatin and 3.0 L of distilled water containing 11.4 g of sodium bromide and an additional defoamer were added, and then the pH was adjusted to 5.8. Growth was carried out in double jet mode with addition of 3 M silver nitrate in equimolar amount with sodium bromide while maintaining pBr at 1.71. The flow rate of the silver nitrate is 45.
It was increased from 7.3 mL / min to 156 mL / min over 9 minutes. During the last minute of growth, 88 μg of K ₄ Ru (C
N) ₆ was added to the reaction vessel. Stop the flow of silver nitrate,
3M sodium bromide was added at a rate of 40 mL / min for 3.16 minutes, followed by 2.5 mg of KSeCN and 0.464 mole of silver iodide seeds. 40 mL of 3.0 M silver nitrate
A silver overrun was performed by addition at a rate of 28.2 minutes / min. Using a balanced flow rate of sodium bromide, the reduction in bromide concentration is reduced by pBr2.
Limited to 55. Excess salt was removed by ultrafiltration to give 12.4 moles of an emulsion containing an average of 3.7% iodide and having a grain size of 1.68 x 0.124 µm.

Emulsion 5 This emulsion was tabular and had run / dum
p) is an emulsion of bromoiodide, wherein a portion of the iodide is added continuously with the bromide during growth, and a portion is added to the reaction vessel at 70% of the manufacturing process. The emulsion was added all at once and then added rapidly by performing a silver overrun. A reaction containing 18.4 g of oxidized and lime-treated bone gelatin, 32.2 g of sodium bromide, and 4.6 L of distilled water maintained at 48 ° C. and containing an antifoaming agent, which was thoroughly stirred. Place 0.
A 21 M silver nitrate solution was added at a rate of 35 mL / min for 15 minutes. Following nucleation, ammonia ripening was performed with 0.40 mole of ammonia at pH 10 for 5 minutes. An additional 222 g of oxidized and lime-treated bone gelatin and 3.0 L of distilled water containing an additional defoamer were added, and then the pH was adjusted to 5.8. Growth was performed in double jet mode by adding 3M silver nitrate with an equimolar amount of NaBr _0.97 I _0.03 , while maintaining pBr at 1.71. The flow rate of silver nitrate was 7.67 over 46.7 minutes.
It was increased from 3 mL / min to 160 mL / min. The flow of silver nitrate was stopped and 3M sodium bromide was added at a rate of 40 mL / min for 6.3 minutes, followed by 2.4 mg of KSeCN and 0.38 mol of silver iodide seeds. Silver overrun was performed by adding 3.0 M silver nitrate at a rate of 40 mL / min for 28.2 minutes. Use a balanced flow of sodium bromide to reduce the bromide concentration,
Restricted to pBr 2.59. Excess salt was removed by ultrafiltration to yield 12.1 moles of an emulsion containing an average of 3.9% iodide and having a grain size of 2.17 x 0.124 µm.

Emulsion 6 This emulsion was a tabular, dumped iodide bromoiodide emulsion, all of which contained about 70% of the manufacturing process.
At this point, the silver iodide seed emulsion was added all at once by placing it in a reaction vessel all at once and then performing an overrun of silver. Oxidized and lime treated bone gelatin 18.4
g, 32.2 g of sodium bromide, and 4.6 L of distilled water containing an antifoaming agent and kept at 49 ° C. in a well-stirred reaction vessel. It was added at a rate of 35 mL / min for 15 minutes. Following nucleation, ammonia ripening was carried out at pH 10 for 5 minutes with 0.35 mol of ammonia. An additional 222 g of oxidized and lime-treated bone gelatin and 3.0 L of distilled water containing an additional defoamer were added, and then the pH was adjusted to 5.8. While maintaining pBr at 1.69, growth was carried out in double jet mode by adding equimolar 3M silver nitrate with sodium bromide. The flow rate of silver is 4
It was increased from 7.3 mL / min to 170 mL / min over 6 minutes. During the last minute of the growth period, 98 μg of K ₄ Ru
(CN) ₆ was added to the reaction vessel. The flow of silver nitrate was stopped and 3M sodium bromide was added at a rate of 175.5 mL / min for 2.51 minutes, followed by 2.5 mg of KSeCN
Was added with 0.462 moles of silver iodide seeds. 3.0M
A silver overrun was performed by adding silver nitrate at a rate of 40 mL / min for 28.8 minutes. Using a balanced flow rate of sodium bromide, the reduction in bromide concentration was limited to pBr 2.55. Excess salt was removed by ultrafiltration to give 12.5 moles of an emulsion containing an average of 3.7% iodide and having a grain size of 2.10 x 0.113 µm.

Emulsion 7 This emulsion is a tabular, run-doped iodide bromoiodide emulsion in which the iodide contains 68% of the first 68% of the process.
Over time with bromide. A reaction containing 18.4 g of oxidized and lime-treated bone gelatin, 32.3 g of sodium bromide and 4.6 L of distilled water containing an antifoam and kept at 40 ° C., which is well stirred. In a container, add 0.617 M silver nitrate solution
It was added at a rate of 5 mL / min for 12.5 minutes. Following nucleation, ammonia ripening was performed for 1 minute at pH 10 using 0.45 moles of ammonia. An additional 222 g of oxidized and lime treated bone gelatin and 1 sodium bromide
3.0 L of distilled water containing 1.4 g and additional defoamer was added, and then the pH was adjusted to 5.8. 0.61
Growth was started by adding 7 M silver nitrate at a flow rate of 7.3 mL / min, and the flow rate was increased to 19.3 mL over 9.5 minutes.
/ Min. The pBr was maintained at 2.13 and the flow rate was from 19.3 mL / min to 26.3 mL / min for 5.5 minutes.
Growth was continued by adding the same silver nitrate solution with an equimolar solution of NaBr _0.96 I _{0.04 in} double jet mode while increasing the temperature. 3.0 g of silver nitrate solution
M solution and then continued to grow in the same manner, increasing the flow rate of silver from 7.3 mL / min to 156 mL / min over 45.5 minutes. During the last minute of the growth period, 38
μg of K ₄ Ru (CN) ₆ was fed into the reaction vessel. The flow was stopped and 1.72 mol of sodium bromide was added, followed by 2.5 mg of KSeCN. 3.0M
A silver overrun was performed by adding silver nitrate at a rate of 40 mL / min for 28 minutes. Using a balanced flow rate of sodium bromide, the reduction in bromide concentration was limited to pBr 2.59. Emulsion 12.6 containing an average of 2.8% iodide and having a grain size of 0.60 × 0.130 μm, after removing excess salt by ultrafiltration.
Obtained a mole.

Emulsion 8 This emulsion is a tabular, run iodide bromoiodide emulsion, the iodide, with bromide, being added continuously throughout the first 80% of the manufacturing process. A reaction containing 18.4 g of oxidized and lime-treated bone gelatin, 32.3 g of sodium bromide, and 4.6 L of distilled water maintained at 50 ° C. and containing an antifoaming agent, and being sufficiently stirred. In a container, add 35 mL of the 0.21 M silver nitrate solution.
/ Min at a rate of 14.83 minutes. Following nucleation, the emulsion was held for 11.5 minutes and then an additional 222 g of oxidized and lime treated bone gelatin and 2.4 L of distilled water containing an antifoam were added. 3.9 M silver nitrate with an equimolar solution of NaBr _0.94 I _0.06 solution in double jet mode, maintaining pBr at 1.91 and the flow rate of the silver nitrate from 7.3 mL / min to 1 to 48.2 minutes.
Growth was carried out by adding the solution while increasing the concentration to 69.4 mL / min. The flow was reduced and 2.5 mg of KSeCN was added, followed by 187 mL of 3.9 M NaBr _0.74 I _0.06 . 3.9 M silver nitrate was added at a rate of 50 mL / min.
A silver overrun was performed by addition for 6.3 minutes. Using a balanced flow rate of sodium bromide, the reduction in bromide concentration was limited to pBr 2.57. Excess salt was removed by ultrafiltration and contained an average of 4.8% iodide and a particle size of 1.26 x 0.12.
15.8 mol of a 7 μm emulsion was obtained.

Emulsion 9 This emulsion is a tabular, run iodide bromoiodide emulsion, the iodide, along with the bromide, is added continuously throughout the first 80% of the manufacturing process. 18.4 g of bone gelatin, oxidized and treated with lime, sodium bromide 3
A 0.21 M silver nitrate solution was charged at 35 mL / mi into a reaction vessel containing 2.3 g and 4.6 L of distilled water containing a defoamer and maintained at 55 ° C. and thoroughly stirred.
Added at a rate of n for 14.83 minutes. Following nucleation,
The emulsion was held for 11.5 minutes, then an additional 222 g of oxidized and lime treated bone gelatin and 2.4 L of distilled water containing an antifoam were added. 3.9 M silver nitrate is added along with an equimolar solution of NaBr _0.94 I _0.06 solution while maintaining the pBr at 1.72 in double jet mode and increasing the flow rate of the silver nitrate from 7.4 mL / min to 22 mL / min in 15 minutes. It started growth. Next, while maintaining the pBr at 1.86, the flow rate of the silver nitrate was adjusted to 3
3. Raised from 22 mL / min to 169 mL / min over 24 minutes. The flow was stopped and 2.5 mg of KSeCN was added followed by 3.9 M silver nitrate at 50 mL / min at 1 mL.
A silver overrun was performed by adding for 6 minutes. Using a balanced flow of sodium bromide, the reduction in bromide concentration was limited to pBr2.5. Emulsion 1 containing an average of 4.8% iodide and having a grain size of 2.29 × 0.126 μm, after removing excess salts by ultrafiltration.
5.8 mol were obtained.

[0080]

[Table 1]

Preparation of Sample Sample 1 (Comparative Sample) Emulsion 1 was prepared by adding sodium thiocyanate;
M: spectral sensitizing dyes SD-1 and SD for cyan spectral sensitization
-2; Gold sensitizer, GS-1; Sulfur sensitizer, treated with SS-1 in that order, then heated to 60 ° C. over 15 minutes,
C., and then the antifoggant AF-1 was added.

Sample 2 (sample of the present invention) Emulsion 1 was prepared by adding sulfur sensitizer, SS-2a and gold sensitizer GS
-2a and treated identically to Sample 1 except heated to 58 ° C over 12 minutes.

Sample 3 (comparative sample) Emulsion 2 was treated with an antifoggant, AF-2; sodium thiocyanate; a finish improver, FM; sensitizing dyes SD-3 and SD-4 for yellow spectral sensitization; Sensitizer, GS-1; treated sequentially with sulfur sensitizer, SS-1, then heated to 61 ° C over 12 minutes, cooled to 40 ° C, then added antifoggant AF-1 Subsequently, a speed additive (speed)
adda) SA was added.

Sample 4 (Sample of the Present Invention ) Emulsion 2 was prepared by adding sulfur sensitizer SS-2a and gold sensitizer GS-
Treated identically to Sample 3, except treated with 2b and heated to 55 ° C. over 8 minutes.

Sample 5 (Comparative sample) Emulsion 3 was prepared by using an antifoggant, AF-2; sodium thiothiate; a finish improver, FM; sensitizing dyes SD-5 and SD-6 for magenta spectral sensitization; Sensitizer, GS-1; treated sequentially with sulfur sensitizer, SS-1 and then
Heat to 0 ° C., cool to 40 ° C., then add antifoggants AF-3 and AF-4.

Sample 6 (sample of the present invention) Emulsion 3 was prepared by using a sulfur sensitizer, SS-2a and a gold sensitizer, GS-
Treated identically to Sample 5, except treated with 2b and heated to 60 ° C. over 4 minutes.

Sample 7 (Inventive Sample) Emulsion 3 was processed identically to Sample 6, except that SS-2b was used in place of SS-2a.

Sample 8 (Sample of the Invention) Emulsion 3 was processed identically to Sample 7, except that GS-2a was used in place of GS-2b.

Sample 9 (comparative sample) Emulsion 4 was prepared by using an antifoggant, AF-2, sodium thiothiate; a finish improver, FM; sensitizing dyes SD-3 and SD-4 for performing yellow spectral sensitization; Agent, AF-
3: treated sequentially with gold sensitizer, GS-1; sulfur sensitizer SS-1, then heated to 61 ° C over 12 minutes, cooled to 40 ° C, then added antifoggant AF-1 Then, a sensitivity additive, SA, was added.

Sample 10 (Comparative Sample) Emulsion 4 was mixed with sulfur sensitizer SS-2a and gold sensitizer GS-2.
Treated identically to sample 9 except treated in b.

Sample 11 (Comparative Sample) Emulsion 5 was prepared by using an antifoggant, AF-2; sodium thiocyanate; a finish improver, FM; sensitizing dyes SD-3 and SD-4 for performing yellow spectral sensitization; Agent AF-3;
Gold sensitizer, GS-1; treated with sulfur sensitizer, SS-1 in order, then heated to 61 ° C over 8 minutes, cooled to 40 ° C, then added antifoggant AF-1 Then the sensitivity additive SA was added.

Sample 12 (Comparative Sample) Emulsion 5 was mixed with sulfur sensitizer SS-2a and gold sensitizer GS-
Treated identically to sample 11, except treated with 2b and heated to 55 ° C. over 16 minutes.

Sample 13 (comparative sample) Emulsion 6 was treated with an antifoggant, AF-2; sodium thiocyanate; a finish improver, FM; sensitizing dyes SD-1 and SD-2 for cyan spectral sensitization; Sensitizer, GS-1; treated with sulfur sensitizer, SS-1 in that order, then 56
C., cooled to 40.degree. C. and then antifoggant A
F-4 was added.

Sample 14 (Comparative Sample) Emulsion 6 was treated with sulfur sensitizer, SS-2a and gold sensitizer, G
Treated identically to Sample 13, except treated with S-2a and heated to 56 ° C over 12 minutes.

Sample 15 (Comparative Sample) Emulsion 7 was treated with an antifoggant, AF-2; sodium thiocyanate; a finish improver, FM; a sensitizing dye for performing yellow spectral sensitization, SD-5; GS-1; a sulfur sensitizer,
Treated sequentially with SS-1, then heated to 63 ° C over 8 minutes, then antifoggant AF-4 was added followed by sensitivity additive SA.

Sample 16 (Comparative Sample) Emulsion 7 was prepared using 20% less dye and
Sample 1 except heated to 63 ° C. over 6 minutes
Treated identically to 5.

Sample 17 (Comparative Sample) Emulsion 7 was treated with sulfur sensitizer, SS-2a and gold sensitizer, G
Processed identically as sample 15, except that S-2a was used and the emulsion was heated to 62 ° C over 8 minutes.

Sample 18 (Comparative Sample) Emulsion 7 was mixed with a sulfur sensitizer, SS-2a and a gold sensitizer, GS-
Processed identically to Sample 15, except that 2a was used, SA was added in 25% increments, and the emulsion was heated to 62 ° C over 12 minutes.

Sample 19 (Comparative Sample) Emulsion 8 was prepared by using an antifoggant AF-2; sodium thiocyanate; a finish improver; FM; sensitizing dyes SD-3 and SD-4 for yellow sensitization; , GS-1; treated sequentially with sulfur sensitizer, SS-1 and then at 5O <0> C for 5 minutes.
And cooled to 40 ° C, then antifoggant AF
-4 was added.

Sample 20 (Comparative Sample) Emulsion 8 was prepared except that the dye level was increased by 10%, the sulfur and gold sensitizer levels were reduced by 20%, and the emulsion was heated to 64 ° C. for 10 minutes. And processed in the same manner as Sample 19.

Sample 21 (Sample of the Present Invention ) Emulsion 8 was prepared by mixing a sulfur sensitizer, SS-2a with a gold sensitizer, GS-
Processed identically to sample 19 except that 2a was used and the emulsion was heated to 62 ° C over 4 minutes.

Sample 22 (sample of the present invention) Emulsion 8 was prepared by adding sulfur sensitizer, SS-2a and gold sensitizer, GS-
Processed identically to sample 19 except that 2a was used and the emulsion was heated to 62 ° C over 12 minutes.

Sample 23 (Comparative Sample) Emulsion 9 was treated with antifoggant AF-2; sodium thiocyanate; a finish improver, FM; sensitizing dyes SD-3 and SD-4 for performing yellow spectral sensitization; Agent, GS-1; sulfur sensitizer, SS-1 in turn, then heated to 65 ° C. over 12 minutes, cooled to 40 ° C., and then antifoggant AF-4 was added.

Sample 24 (sample of the present invention) Emulsion 9 was prepared by adding sulfur sensitizer, SS-2a and gold sensitizer, GS-
Processed identically as sample 23 except that 2a was used and the emulsion was heated to 58 ° C over 20 minutes.

Sample 25 (Comparative Sample) Emulsion 1 was prepared by adding sodium thiocyanate;
M: sensitizing dyes SD-1 and SD- for cyan spectral sensitization
2; treated with gold sensitizer, GS-1; sulfur sensitizer, SS-1 in order, then heated to 60 ° C. over 15 minutes,
C. and then the antifoggant AF-1 was added.

Sample 26 (Comparative Sample) Emulsion 1 was processed identically to Sample 25 except that the antifoggant, AF-3, was added immediately following the dye.

Sample 27 (Sample of the Invention) Emulsion 1 was treated the same as Sample 2 except that the antifoggant, AF-3, was added immediately following the dye.

Sample 28 (Comparative Sample) Emulsion 1 stored with biocide B-1 was sensitized by antifoggant AF-2; sodium thiocyanate; finish improver FM; cyan spectral sensitization. Dye SD-1
And SD-2; gold sensitizer GS-1; sulfur sensitizer, SS-1
, Then heated to 60 ° C. over 10 minutes, cooled to 40 ° C., and the antifoggant AF-1 was added.

Sample 29 (Comparative Sample) Emulsion 1 was processed identically to Sample 28 except that biocide B-2 was used for storage and this emulsion was heated to 60 ° C. for 15 minutes. did.

Chemical structural formula

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Photographic Evaluation The sensitized emulsion samples described above were coated into a simple single layer format. The format consists of a pad of gelatin on a cellulose acetate film support with an antihalation backing, and a layer over the pad containing the emulsion and a cyan or yellow imaging coupler. The emulsion was coated with a single cyan coupler, C-1 in some examples, but in other examples with a yellow image forming coupler, C-2 and a yellow development inhibitor releasing coupler, C-3. did. The emulsion layer was protected against abrasion by a gelatin overcoat containing a hardener. Details of the laminated structure are shown in the table below.

[0112]

[Table 2]

Example 1 This example illustrates the utility of the present invention with various sensitizing dyes and couplers. Sample 1 shown in Table 1 below contains an emulsion chemically sensitized with a commonly used thiosulfate sulfur source SS-1 in combination with gold thiosulfate GS-1;
And 48.9 ° C (120 ° F) / 50 under accelerated storage conditions
It shows a large increase in D-min (fog) when held at% RH. Thiourea SS instead of thiosulfate
-2a and using gold complex GS-2 instead of GS-1
In Sample 2 using a, the increase in the D-min is significantly reduced. This observation result is repeated for the sample 3: 4 containing the yellow sensitizing dye and the sample 5: 6 containing the magenta sensitizing dye. The sensitization by the thiourea and the gold complex caused the fresh sensitivity ((fresh)
It should be noted that this is twice that of the thiosulfate example, except for minor adjustments such as less heating during chemical ripening to equalize speed.

Sample 7 shows that the similar thiourea SS-2b also significantly reduces storage fog, while sample 8
Combines SS-2b with the gold complex GS-2b,
Excellent preservation fog.

[0115]

[Table 3]

Example 2 The unexpected attributes of the present invention are shown in Table 2. That is, emulsions with relatively low iodide content (<4%) show no improvement when sensitized with thiourea and gold complexes.

[0117]

[Table 4]

Example 3 In this example, we utilize different types of silver bromoiodide emulsions. That is, the run iodide emulsion is compared to the dumped iodide emulsion or run / dump iodide emulsions (1-6) described above. Samples 15 and 16
Emulsion 7 was sensitized slightly different using SS-1 and GS-1, while samples 17 and 18 were sensitized very slightly different from each other. I have. In this example with an emulsion having a low iodide content, no improvement in storage fog is seen even when using thiourea and a gold complex. It should be noted that the emulsions tested in this example are similar in size to emulsions 1, 2 and 3 of Example 1 and small, indicating that the emulsion particle size is not an important feature.

[0119]

[Table 5]

Example 4 This example compared the storage fog that occurred on two run iodide emulsions with high iodide content. Samples 19 and 2
0 is a sample of Emulsion 8 which had undergone slightly different sensitizations using a thiosulfate-based sulfur source and a gold source. Sample 21
And 22 are samples of Emulsion 8 which were slightly sensitized using thiourea and a gold complex. It should be noted that samples 19 and 20 show an increase in storage fog, whereas samples 21 and 22 using thiourea and gold complex show no increase in storage fog. Observation that storage fog is reduced by sensitization with thiourea and a gold complex is repeated for samples 23 to 24 using different emulsions. It should be noted that the grain sizes of these emulsions in this example are about the same as those of the emulsion used in Example 2 where the comparative sample showed no improvement in storage fog. This again shows that the grain size of the emulsion is not an important feature.

[0121]

[Table 6]

Example 5 Samples 25 and 26 in Table 5 show that the commonly used antifoggant AF-3 has only a small effect on reducing the increase in storage fog. Also, it should be noted that all the samples used the antifoggant AF-2, but this antifoggant also failed to suppress the increase in storage fog. Sample 27 shows that AF-3 can be used in the present invention when compared to Sample 2, and further slightly reduces storage fog.

[0123]

[Table 7]

Example 6 The effect of the present invention is further shown in Table 6. When the biocide used to preserve the emulsion was changed from B-1 to B-2 (samples 28 vs. 29), storage fog increased significantly. However, when the sensitizer was changed to SS-2a and GS-2a (Sample 2), the storage fog was greatly reduced.

[0125]

[Table 8]

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

Hereinafter, additional embodiments of the present invention will be described. (Embodiment 1) A silver halide photographic element comprising at least one silver bromoiodide emulsion layer, wherein the silver bromoiodide emulsion has an average iodide content of 4 mol% or more, and has the following formula :

Embedded image Wherein X is sulfur, selenium or tellurium, and R ₁ ,
R ₂ , R ₃ and R ₄ each independently represent an alkylene group, a cycloalkylene group, a carbocyclic arylene group, a heterocyclic arylene group, an alkarylene group or an aralkylene group, or a nitrogen atom to which they are bonded; R ₁ and R ₂ or R ₃ and R ₄ together with the atom may form a 5- to 7-membered heterocycle, and A ₁ , A ₂ , A ₃ and A ₄
Each independently is hydrogen or represents a carboxyl, sulfine, sulfone, hydroxam, mercapto, sulfonamide or primary or secondary amino nucleophilic group, provided that A ₁ R _{1 to} A ₄ R Wherein at least one of the _four contains a nucleophilic group attached to the nitrogen atom of the urea via a two or three membered chain). Silver photographic element. (Aspect 2) The silver halide element according to aspect 1, wherein X is sulfur. (Aspect 3) The silver halide element according to aspect 1, wherein the nucleophilic group is a carboxyl, sulfine, sulfone or hydroxam group. (Aspect 4) The silver halide element according to aspect 2, wherein the nucleophilic group is a carboxyl, sulfine, sulfone or hydroxam group. (Aspect 5) The silver halide element according to aspect 3, wherein the nucleophilic group is a carboxyl group. (Aspect 6) The silver halide element according to aspect 4, wherein the nucleophilic group is a carboxyl group. (Aspect 7) R _1, R _2, silver halide element as defined in aspect 1 represents an alkylene group which R ₃ and R ₄ each contain independently 1 to 6 carbon atoms. (Embodiment 8) Embodiment ₂ in which R ₁ , R ₂ , R ₃ and R ₄ each independently represent an alkylene group having 1 to 6 carbon atoms.
The silver halide element described in above. (Aspect 9) A silver halide emulsion represented by the following formula:

Embedded image Wherein R ⁷ is a substituent, and Z contains the carbon atoms necessary to form a 5- or 6-membered substituted or unsubstituted non-aromatic ring. The silver halide element of embodiment 1 which has been chemically sensitized in the presence of (Embodiment 10) The silver halide photographic element according to embodiment 9, wherein Z contains a carbon atom necessary to form a 5-membered substituted or unsubstituted non-aromatic ring. (Embodiment 11) The silver halide photographic element according to embodiment 10, wherein Z contains a carbon atom necessary to form an unsubstituted 5-membered non-aromatic ring. (Aspect 12) R ⁷ is a hydrogen atom, a substituted or unsubstituted alkyl group containing 1 to 6 carbon atoms, a substituted or unsubstituted aryl group containing 6 to 10 carbon atoms, or a substituted or unsubstituted aryl group. The silver halide photographic element according to embodiment 9, which is an unsubstituted 5- or 6-membered heterocyclic ring. (Aspect 13) R ⁷ is a hydrogen atom, a substituted or unsubstituted alkyl group containing 1 to 6 carbon atoms, a substituted or unsubstituted aryl group containing 6 to 10 carbon atoms, or a substituted or unsubstituted aryl group. The silver halide photographic element according to embodiment 11, which is an unsubstituted 5- or 6-membered heterocyclic ring. (Embodiment 14) A silver halide photographic element comprising at least one silver bromoiodide emulsion layer, wherein the silver bromoiodide emulsion has an average iodide content of 4 mol% or more, and has the following formula :

Embedded image Wherein X is sulfur and R ₁ , R ₂ , R ₃ and R ₄
Each independently represents an alkylene group having 1 to 6 carbon atoms, and A ₁ , A ₂ , A ₃ and A ₄ are each independently hydrogen or a carboxyl, sulfine, sulfone or hydroxam Represents a nucleophilic group,
However, at least one of A ₁ R _{1 to} A ₄ R ₄ is 2
Containing a nucleophilic group bonded to the nitrogen atom of urea via a three- or three-membered chain). (Aspect 15) A silver halide emulsion represented by the following formula:

Embedded image Wherein R ⁷ is a substituent and Z contains the carbon atoms necessary to form a 5- or 5-membered substituted or unsubstituted non-aromatic ring. 15. The silver halide element according to aspect 14, which has been chemically sensitized. (Aspect 16) R ⁷ is a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, or a substituted or unsubstituted group A silver halide photographic element according to embodiment 15, which is a 5- or 6-membered heterocyclic ring. (Aspect 17) A method for producing a silver halide emulsion, wherein a silver bromoiodide emulsion having an average iodide content of 4 mol% or more is used, and this emulsion is represented by the following formula:

Embedded image Wherein X is sulfur, selenium or tellurium, and R ₁ ,
R ₂ , R ₃ and R ₄ are each independently an alkylene group, a cycloalkylene group, a carbocyclic arylene group, a heterocyclic arylene group, an alkarylene group or an aralkylene group, or With the nitrogen atom being present, R ₁ and R ₂ or R ₃ and R ₄ may complete a 5- to 7-membered heterocycle, and A ₁ , A ₂ , A ₃ and A ₄ are each independently hydrogen Or a carboxyl, sulfin, sulfone, hydroxam, mercapto, sulfonamide or primary or secondary amino nucleophile, provided that at least one of A ₁ R _{1 to} A ₄ R ₄ is Containing a nucleophilic group bonded to the nitrogen atom of urea through a two- or three-membered chain). (Aspect 18) X is sulfur, the nucleophilic group is carboxyl,
A group of sulfin, sulfone or hydroxam,
And R ₁ , R ₂ , R ₃ and R ₄ are each independently 1 to 1
Embodiment 18. The method of embodiment 17, wherein the method represents an alkylene group having 6 carbon atoms. (Aspect 19) The method according to Aspect 18, wherein the nucleophilic group is a carboxyl group. (Aspect 20) A silver halide emulsion represented by the following formula:

Embedded image Wherein R ⁷ is a substituent and Z contains the carbon atoms necessary to form a 5-membered substituted or unsubstituted non-aromatic ring. 18. The method according to aspect 17, wherein the chemical sensitization is performed. (Aspect 21) A silver halide emulsion represented by the following formula:

Embedded image Wherein R ⁷ is a substituent and Z has the carbon atoms necessary to form a 5-membered substituted or unsubstituted non-aromatic ring. 20. The method according to aspect 19, which is chemically sensitized with

Claims (1)

[Claims] 1. A silver halide photographic element comprising at least one silver bromoiodide emulsion layer, wherein the silver bromoiodide emulsion has an average iodide content of 4 mol% or more, and Formula: (Wherein X is sulfur, selenium or tellurium, and R ₁ , R ₂ , R ₃ and R ₄ are each independently an alkylene group, cycloalkylene group, carbocyclic arylene group, heterocyclic arylene group, R ₁ and R ₂ or R ₃ and R ₄ together with the nitrogen atom to which they represent a arylene or aralkylene group may form a 5- to 7-membered heterocycle, and A ₁ , A ₂ , A ₃ and A ₄ are each independently hydrogen or represent a carboxyl, sulfine, sulfone, hydroxam, mercapto, sulfonamide or primary or secondary amino nucleophilic group, At least one of A ₁ R _{1 to} A ₄ R ₄ is 2
Containing a nucleophilic group attached to the nitrogen atom of urea via a three- or three-membered chain).