JPS6123146A - Preparation of silver halide photographic emulsion - Google Patents

Abstract

PURPOSE:To improve reciprocity law failure characteristics in low illuminance by incorporating a specified amt. of at least one kind of water-soluble iridium compd. CONSTITUTION:A silver halide emulsion is obtained by physically ripening a silver halide emulsion in the presence of ammonia and a water-soluble iridium compd. in an amt. of 10<-3>-10<-5> mol per mol silver halide at a pH of 7-9. A preferable acid added for controlling rise of pH is acetic, sulfuric, nitric, or the like acid, and a concn. of ammonium ions in the soln. is 0.005-1.5mol/l, preferably, in the form of an aq. ammonia, and as the water-soluble iridium compd., a hexahalogeno complex salt, such as hexachloro-Ir(III) acid salt, Ir(III), and (IV) chloride are usable, and it is added, preferably, before the end of growth of silver halide, into a physical ripening reaction vessel.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of the Invention] The present invention relates to a method for producing a silver halide photographic emulsion, and in particular to a silver halide photographic emulsion having high sensitivity and improved low-light reciprocity law failure characteristics by an ammonia method. Relating to a manufacturing method.

[Prior art]

Today's photographic films are used in a wide variety of ways, with exposure times ranging from tens of seconds to flash exposures. However, the sensitivity is usually highest under exposure conditions in the 1/100 to 1/10 second range, but if the exposure time is longer than that, the sensitivity decreases significantly, and a phenomenon commonly called low-light reciprocity law failure occurs. For example, in exposure using an enlarger or printer, or with medical X-ray film, there are many cases in which images are taken with a relatively long light path time, and low-light reciprocity failure is likely to occur.

Furthermore, even in general photography, the level of so-called amateur photographers has increased, and the conditions for photography have become considerably wider.

Regarding the improvement of low-light reciprocity law failure characteristics,
As disclosed in Japanese Patent No. 35810, there is a method of exposing a silver halide emulsion layer to a hydrogen atmosphere under reduced pressure. In this method, during the production of a silver halide photosensitive material,
There is an unfavorable manufacturing process in which the above-mentioned conditions must be created, and the resulting silver halide has a high capri. In addition, as described in JP-A-56-147142, there is a method of adding a water-bathable iridium salt to the surface and vicinity of silver halide grains containing silver iodide, and As described in Japanese Patent No. 57-192942, by the end of physical ripening, silver halide grains produced in the presence of a water-soluble iridium salt and Vr produced in the absence of a water-soluble iridium salt, There are methods such as providing a silver halide emulsion layer containing . Not enough.

[Object of the present invention]

An object of the present invention is to produce a silver halide emulsion with high sensitivity and improved low-light reciprocity failure characteristics.

[Means for achieving the object of the present invention] The present inventors
It has been discovered that a silver halide emulsion that satisfies the above objectives can be obtained as follows. That is, it is a silver halide emulsion that has been physically ripened in the presence of ammonia, at a pH in the range of 7 to 9, and in the presence of at least one water-soluble iridium compound in an amount of 104 to 101 mol per 1 mol of silver halide.

That is, the feature of the method for producing a halogenated emulsion of the present invention is that physical ripening is suppressed to a pH range of 7 to 9, and during ripening, 1 mole of silver halide a! l, 10-
8 to 10-s moles of at least one water-soluble iridium compound is present.

Silver bromide and silver iodobromide emulsions can be used as the silver halide emulsion of the present invention, but silver iodobromide emulsions are particularly preferred.

The inclusion of water-soluble iridium compounds in silver halide emulsions is well known.

However, the specific compound in the present invention, i.e., the specific amount of at least one water-soluble iridium compound, is
There is no known literature regarding silver halide photographic emulsions that are characterized in that silver halide is contained in silver halide emulsions that are physically ripened in the range of 7 to 9.Refreshingly, the low-illuminance reciprocity law failure characteristics of the present invention are remarkable. There is also no literature suggesting a modified silver halide photographic material.

In the present invention, if the pH during silver halide grain growth is
The range is preferably from 7 to 9, particularly preferably from 7.5 to 9.

In order to suppress the significant increase in pH that occurs in the manufacturing process in the conventional ammonia method photographic emulsion manufacturing method, an appropriate amount of acid is added to the reaction vessel in advance, or ammonia During the growth of silver nitrate grains, acid is added to the reaction vessel at an excessive rate.

The enemy is added to the mixed solution via a positive displacement pump with variable speed control, but a portion of it may be mixed into the halide and added.

Preferably, the acid is one that does not adversely affect photographic performance, such as acetic acid, sulfuric acid, and nitric acid.

In addition, in the present invention, when the ammonia source used together with this acid is used in a reaction vessel before silver halide grain growth, it is added to the aqueous solution containing the halide and hydrophilic colloid substance in the reaction vessel.

The concentration of ammonium ions in the solution is arbitrary, but it is preferably 0.005 to 1.5 mol/l, eVC10
', 05 to 0.60 mol/l is preferred. At this time, it is preferable to add a necessary acid in order to adjust the pH of the solution to a range of 7 to 9. The ammonium ions are provided in the form of aqueous ammonia and ammonium salts such as -specialized ammonium, ammonium chloride, ammonium iodide and ammonium nitrate, but preferably in the form of aqueous ammonia.

In the 16 solutions of ammonia-silver nitrate solution used in the present invention, some or all of the silver ions used are used as ammonia silver complex salt, but it is preferable to use all the silver ions as an ammonia silver complex salt.

In the present invention, since the pH of the reaction mixture in the reaction vessel is kept in the range of 7 to 9, the presence of ammonium ions is maintained in the range of 7 to 9.
Growth of silver halide grains occurs quickly.

On the other hand, if p)3 of the reaction mixture is less than 71/m, there is a problem that it takes too much time for the growth of silver halide grains in the manufacturing process, making it unsuitable for practical use.

The production method of the present invention can be widely applied to A production techniques for various photographic emulsions. Typical embodiments thereof are shown below.

(1) Single Jet Method (a) Direct Mixing Method While stirring an aqueous gelatin solution of an alkali halide in a reaction vessel, acetic acid and an aqueous ammonia solution are added thereto, and the pH is adjusted to 7 to 9 with acetic acid. Further, an ammoniacal silver nitrate solution is added during the refilling time. At this time, acetic acid is appropriately added in order to maintain the pH of the reaction mixture in the reaction vessel in the range of 7 to 9. Thereafter, the pH and pAg are adjusted and desalination is carried out according to the method of Kure Rin.

(b) First, heat-processed acetic acid and aqueous gelatin solution of ammonia are poured into the reaction vessel, and ammoniacal silver nitrate solution is added to this while stirring, and then an aqueous gelatin solution of alkali halide is added dropwise within the required time. and mix the emulsion. The pH of the reaction mixture in the reaction vessel is maintained within the range of 7 to 9 in the same manner as described above.

(2) Gurujet method A gelatin bath solution containing an alkali halide, acetic acid, and ammonia is poured into a reaction vessel, and while stirring, an ammoniacal iron nitrate solution and an aqueous gelatin solution of an alkali halide are simultaneously added into a 15-Jj chamber at the same time. to prepare an emulsion. The pH of the reaction mixture in the reaction vessel is maintained within the range of 7 to 9 in the same manner as described above. The subsequent processing is performed in exactly the same manner as described above.

Similarly, as the dispersion medium added to the reaction vessel used in the present invention, there are hydrophilic colloid liquids made of known natural polymer compounds and synthetic polymer compounds including gelatin, and these may be used alone or in combination. can be used.

Furthermore, the halide ions of the alkali halide used in the present invention include bromide ions -ti, iodide ions, etc., and -T:a can be used alone or in combination.

When the silver halide emulsion grains produced according to the present invention have an average grain size of 0.05 μm or more, preferably 0.3 μm or more, the effect l-j of the present invention is significant.

On the other hand, water-soluble iridium compounds used in the practice of the present invention include hexahalogeno complex salts [for example, hexachloroiridate (III), hexabromoiridate (jII), hexachloroiridate (IV),
U salt, hexabromoiridium (■)? N salt, s],
Examples include iridium (III) chloride and (■), iridium bromide (1■) and (■), and the like. It is well known that these water-soluble iridium compounds are used by adding them to silver halide photographic emulsions.

For example, British Special Report No. 602,158 describes the stabilizing effect of silver halide photographic emulsions using ruthenium salts, palladium salts or iridium salts.

The amount of the water-soluble iridium compound used in the ritual of the present invention is particularly effective in the range of 10-8 moles to 10 moles per mole of silver halide, and this rx6
If it is less than this range, the effect of improving the low-light reciprocity law failure characteristic will be weak, and if it is more than this range, the current processing will desensitize, which is undesirable.

In addition, the types of these water-soluble iridium compounds and their optimum conditions are determined by the degree of low-light reciprocity law failure characteristics necessary for silver halide photographic materials, photographic properties such as sensitivity, tone, and capri, and their storage stability. In addition, we take into account the composition of the halide, production and dispersion of silver halide, manufacturing conditions such as physical ripening, water washing, and chemical ripening, and spectral sensitization conditions such as the type and amount of sensitized color. However, the present invention is not limited by these conditions.

The water-bathable iridium compound used in the practice of the present invention is
Although it is effective when added at any stage before the completion of physical ripening, it is particularly preferable to add it to the reaction vessel for physical ripening before the completion of growth of silver halide, or to add it separately at that time. It's good to add it.

The above-mentioned silver halide emulsion C has low-illuminance reciprocity law failure characteristics,
Since it is significantly improved, it is preferably applied to many photosensitive materials.

For example, the photosensitive material using the present invention is not only for the diffusion transfer method, but also for X-ray, black and white general, color, infrared,
This invention can be effectively applied to photosensitive materials for various uses such as micro, silver dye bleaching, and reversal. , but is not limited to these.

In the process of producing silver halide grains according to the present invention, for example, cadmium salt, zinc salt, lead salt, thallium salt, rhodium salt, or a complex salt thereof may be present.

The silver halide emulsion in the present invention can be spectrally sensitized using various dyes.
, cyanine, merocyanine, complex cyanine and complex merocyanine (i.e. tri-, tetra-2 and polynuclear cyanine and merocyanine), oxonol, hemioxonol, styryl, merostyryl and streptocyanine.

Cyanine spectral sensitizing dyes include quinolinium, pyridinium, isoquinolinium, 3H-indolium, benz[e]indolium, oxacillium, oxazolinium, thiazolium, thiazolinium, selenazolium,
Selenacillinium, imidazolium, imidazolinium, benzoxacillinium, benzothiazolium, benzoselenazolium, benzimidazolium, naphthoxazolium, naphthothiazolium, naphthoselenazolium,
Two basic heterocyclic nuclei linked by a methine linkage are included, such as those derived from silihydronaphthothiazolium, pityrium and imidazopyrazinium quaternary salts.

ytoy7=y Spectral sensitizing dyes include barbituric acid, 2
-thiobarbic acid, logenin, hydantoin, 2
-thiohydantoin, 4-thiohydantoin, 2-pyrazolin-5-one, 2-inxacillin-5-one, 'indan-1,3-dione, cyclohexane-1,3-
dione, 1,3-dioxane-4,6-dione, pyrazoline-3,5-dione, pentane-2,4-dione, alkylsulfonylacetonitrile, malonitrile, inquinolin-4-one and chroman-2,4-dione It includes an acidic nucleus derived from a dione and a cyanine dye-type basic heterocyclic nucleus bonded through a methine bond.

Spectral sensitizing dyes useful for sensitizing silver halide emulsions include British Patent No. 742.112, U.S. Pat. No. 1,846
．． No. 300, No. 1.846, 301, No. 84
6.3o2, 1.846,303, 1.8
No. 46,304, No. 2,078,233, No. 46,304, No. 2,078,233, Same! 2,
No. 089,729, No. 2.165.338, No. 2
．． No. 213,238, No. 2,231,658, @
2.493.747, 2.493.748, 2,526.632, 2.739,964 (
Reissued Patent No. 24,292), $2,778.82
No. 3, No. 2,917,516, No. 3,352.8
No. 57, No. 3, No. 411, No. 916, No. 3, 43
1,111, 2.295.276, 2.4
No. 81.698, P] No. 2.503,776, No. 2
, 688,545, 2,704.714, 2.921.067, 2,945, 763, 3,282.933, J, 397. 0
No. 60, No. 660.102, No. 3.66
No. 0,103, No. 3, No. 335, No. 010, No. 3
, 352.680, 3.384.486, 3,397.981, 3.482.978, 3,623,881, 718,470 Examples of useful dye combinations, including supersensitized color combinations, are described in U.S. Pat. 3.672.898.

British Patent No. .413.826, the use of iodide can be cited by Gilman (
Other compounds can be used, including those described in "Review of the Mechanisms of Supersensitization" by J.D. Gilman).

The above-mentioned sensitizing dye may be added at any time such as at the start of chemical ripening (also called second ripening) of the silver halide emulsion, during ripening, after the end of ripening, or at an appropriate time prior to emulsion coating. .

The method of adding shredded sensitized colored paper to the above photographic emulsion is as follows:
Various methods proposed in the past can be applied.6 For example, as described in U.S. Pat. This may be carried out by dissolving the sensitizing dyes individually in the same or different solvents and adding them to the emulsion before adding them to the emulsion.
These solutions can be mixed or added separately.

In the present invention, when a sensitizing dye is added to a silver halide photographic emulsion, a water-miscible organic solvent such as methyl alcohol, ethyl alcohol, or acetone is preferably used as the dye solvent.

In the present invention, when a sensitizing dye is added to a silver halide emulsion, the amount added is IX per mole of silver halide.
10-' mol to 2.5 X 10-2 mol, preferably 1.0X10'4 mol to 1.OX 10-'
It is s mole. The sensitizing dye can be used in combination with other sensitizing dyes or supersensitizers.

The silver halide grains according to the present invention can be subjected to various commonly used chemical sensitization methods. Namely, activated gelatin; water-soluble gold salt, water-soluble platinum salt, water-soluble palladium salt,
Chemical sensitizers such as noble metal sensitizers such as water-soluble rhodium salts; sulfur sensitizers; selenium sensitizers; chemical sensitizers such as polyamines, reduction sensitizers such as stannous chloride, etc. alone or in combination. You can also feel it.

In the present invention, known sulfur sensitizers can be used as the sulfur sensitizer. Examples include thiosulfate, allylthiocarbamide thiourea, allyl isothiacyanate, cystine, p-toluenethiosulfonate, and rhodanine. Other U.S. Patents No. 1.574.944, U.S. Patent No. 2.410.689, U.S. Patent No. 2,278.947
No. 2,728,668, No. 3.501, 3
No. 13, $3,656,955 + Keisha, German Patent No. 1.42-2.869 Specification, Japanese Patent Publication No. 1983-2
Sulfur sensitizers described in No. 4937, JP-A No. 55-45016, etc. can also be used. The amount of sulfur sensitizer added may be sufficient to effectively increase the sensitivity of the emulsion.

This amount varies over a considerable range under various conditions such as pH, temperature, and the size of the silver particles, but as a guide, it is about 10-7 mol per 1 mol of silver oxide. 1 molar h degree is preferred.

In the present invention, selenium sensitization can be used instead of sulfur sensitization, and the selenium sensitizers include aliphatic isoselenocyanates such as allyl isoselenocyanate, selenoureas, selenoketones, and selenamides. , selenocarboxylic acids and esters, selenophosphates,
Selenides such as diethylselenide and diethylselenide can be used, and specific examples thereof include U.S. Patent Nos. 1.574.944, 1.602.592, and 1,623.499. It is stated in the specification.

As with sulfur sensitizers, the amount added varies over a wide range, but as a guide, approximately 1 mol of silver chloride is added.
The amount is preferably about 10-' moles.

In the present invention, as the gold sensitizer, various gold compounds can be used, whether the gold oxidation number is +1 or +3. Typical examples include chloraurate, potassium chloroaurate, auric trichloride, Potassium auric thiocyanate, potassium iodoaurate, tetracyanooli thiocyanate, ammonium aurothiocyanate, pyridyl trichlorogold, and the like.

The amount of gold sensitizer added varies depending on various conditions, but as a guide, it is about 10-' moles to 10 moles per mole of silver chloride.
A range of up to 1 mole is preferred.

In the present invention, it is also possible to further use reduction sensitization. Reducing agents include, but are not particularly limited to, known stannous chloride, thiourea dioxide, hydrazide derivatives,
Examples include silane compounds.

It is preferable to perform reduction sensitization during the growth of silver halide grains or after completion of sulfur sensitization and gold sensitization.

Various compounds are added to the silver halide grains of the present invention at the end of chemical ripening for the purpose of preventing capri formation during the manufacturing process, storage or processing, or stabilizing photographic performance. It may be included.

Azoles, such as benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzimidazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles , mercaptotetrazoles (
1cI-phenyl-5-mercaptotetrazole), matamercagutopyrimidines, mercaptotriazines, thioketo compounds such as oxazolinthione, and further benzenethiosulfinic acid, benzenesulfinic acid, benzenesulfonic acid amide, hydroquinone derivatives, Many compounds known as antifoggants or stabilizers can be added, such as amine phenol derivatives, gallic acid derivatives, ascorbic acid derivatives, etc.

These chemicals are preferably added during chemical ripening or before coating.

Various hydrophilic colloids including gelatin are used as binders for the silver halide emulsion of the present invention. Gelatin includes not only gelatin but also derivative gelatin, and derivative gelatin includes a reaction product of gelatin and an acid anhydride, a reaction product of gelatin and isocyanate, or a reaction product of gelatin and a compound having an active halogen atom. Products, etc. are included. Examples of the acid anhydride used in the reaction with gelatin include maleic anhydride, phthalic anhydride, benzoic anhydride, acetic anhydride, isatoic anhydride, and succinic anhydride, and examples of the isocyanate compound include, for example, phenyl anhydride. Examples include isocyanate, p-bromophenyl isocyanate, p-chlorophenylisocyanate, p-tolyl isocyanate, p-nitrophenyl isocyanate, naphthylisocyanate, and the like.

Examples of compounds having active halogen atoms include evabenzenesulfonyl chloride, p-methoxybenzenesulfonyl chloride, p-phenoxybenzenesulfonyl chloride, p-bromobenzenesulfonyl chloride, p-toluenesulfonyl chloride, m-nitrobenzenesulfonyl chloride, m- Sulfobenzoyl dichloride, naphthalene-β-sulfonyl chloride,
p-chlorobenzenesulfonyl chloride, 3-nitro-4-aminebenzenesulfonyl chloride, 2-carboxy-4-bromobenzenesulfonyl chloride, m
-carboxybenzenesulfonyl chloride, 2-amino-5-methylbenzenesulfonyl chloride, phthalyl chloride, p-nitrobenzoyl chloride, benzoyl chloride, ethyl chlorocarbonate, furoyl chloride, and the like.

-i) In addition to the above-mentioned derivative gelatin and ordinary photographic gelatin, colloidal albumin is used as a hydrophilic colloid to prepare a silver halide emulsion.
Agar, gum arabic, texturan, alginic acid, cellulose derivatives such as cellulose acetate hydrolyzed to an acetyl content of 19-26%, polyacrylamide, imidized polyacrylamide, casein, such as vinyl alcohol-vinyl cyanacetate copolymer. Vinyl alcohol polymers containing urethane carboxyl groups and hacyanoacetyl groups, polyvinyl alcohol-polyvinyl pyrrolidone, hydrolyzed S polyvinyl acetate, obtained by polymerization of protein fragments or saturated acylated proteins and monomers having vinyl groups. It is also possible to use polymers such as polyvinylpyridine, polyvinylamine, polyaminoethyl methacrylate, polyethyleneimine, and the like.

The silver halide emulsion of the present invention contains a coating aid, an antistatic agent,
Improved slipperiness, emulsification and dispersion, prevention of adhesion and improved photographic properties (
For example, various known surfactants may be included for various purposes such as enhancement of color density, contrast enhancement, and sensitization.

That is, U.S. Patent No. 2.240,472;
No. 831,766, same article: No. 1158.484, same article No. 3
．． 210.191, 4@3.294.540, 3.507.660, British Patent No. 1,012,495
No., @1. o22. s7s No. 1,179.29
No. 0, No. 1,198.450, U.S. Patent No. 2,73
9.891, 2.823.123, 1.1
No. 79,290, No. 1.198,450, No. 2.
No. 739,891, No. 2,823,123, No. 3
．． No. 068.101, No. 3, 415, 649
No. 3,666.478, No. 3,756,82
8, British Patent No.], 397,218, British Patent No. 3,
113, 816, 3.411.413, 473.174, 345, 974
No. 3,726.683, No. 3.843.36
No. 8, Belgian Patent No. 731.126, British Patent No. 1
, No. 138.514, No. 1.159,825, No. 1,374.780, United States, t# Grant No. 2,271.
No. 623, No. 2.288.226, No. 2.944
, No. 900, No. 3,235,919, No. 3,67
No. 1.247, No. 3,772,021, No. 3,
589, No. 906, No. 3,666.478, No. 3.754.924, West German Patent Application Publication (Dj
JO8) No. 1.961,683, Japanese Unexamined Patent Publication No. 50-117
No. 414, No. 50-59025, Special Publication No. 40-378
No. 40-379 and No. 43-13822. For example, saponins (steroids), alkylene oxide derivatives (e.g. polyethylene glycol, polyethylene glycol/polypropylene glycol condensates, polyethylene glycol alkyl or alkylaryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkyl amines or amides) (classes, polyethylene oxide adducts of silicone)
, glycidol derivatives (e.g., alkenylsuccinic polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyalcohols, alkyl esters of sugars, nonionic surfactants such as urethanes or ethers, triterpenoids. saponin,
Alkylcarbo 7M salt, alkylbenzene sulfonate, alkylnaphthalene sulfone rn, salt, alkyl sulfate, alkyl phosphate, N-acyl-
Carboxy groups, sulfo groups, phosphor groups such as N-alkyltaurines, sulfosuccinic acid esters, sulfoalkyl polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl phosphates, etc.
Anionic surfactants containing acidic groups such as sulfate ester groups and phosphate ester groups, amino acids, aminoalkylsulfonic acids, aminoalkyl sulfates or phosphates,
Ampholytic surfactants such as alkyl betaines, J-mine imide systems, amine oxides, alkyl amine salts, aliphatic or aromatic quaternary ammonium salts, heterocyclic quaternary ammonium salts such as pyridium and imidazolium, and aliphatic salts. Alternatively, a cationic surfactant such as a sulfonium or sulfonium salt containing a heterocyclic ring can be used.

In the silver halide emulsion of the present invention, as a current monomer promoter,
In addition to the above-mentioned surfactants, West German patent application publication (DBO8)
No. 2,002,871, No. 2, '445,611, No. 2,360.878, British Patent No. 1.35
It may contain imidazoles, thioethers, cere, phethers, etc. described in 2.196 specification and the like.

The light-sensitive materials produced using the present invention may contain hydroquinone derivatives, aminophenol derivatives, gallic acid salt conductors, ascorbic acid derivatives, etc. as color anticaprilants, specific examples of which are disclosed in U.S. Pat. issue,
2.336.327, 2.403.721, 2.418.613, 2.675,314
No. 2,701.197, No. 2,704.71
No. 3, No. 2.728.659, No. 2.732.3
No. 00, Specification No. 2,735,765, Japanese Patent Application Laid-open No. 1973
-92988, 50-92989, 50-93
No. 928, No. 50-110337, Special Publication No. 50-23
It is described in Publication No. 813, etc.

Effective anti-borrow agents include diacetyl cellulose, styrene-perfluoroalkyl sodium ma-Vate copolymer, and alkali salts of the reaction product of styrene-7X maleic acid-free copolymer and p-aminebenzenesulfonic acid. be.

Examples of matting agents include polymethyl methacrylate, polystyrene, and alkali-soluble polymers.

Furthermore, it is also possible to use colloidal silicon oxide.7 Also, examples of the latex added to improve the physical properties of the film include copolymers of acrylic esters, vinyl esters, etc. and other monomers having ethylene groups. be able to. Examples of gelatin plasticizers include glycerin and glycol compounds, and examples of thickeners include styrene-sodium maleate copolymers, alkyl vinyl ether-maleic acid copolymers, and the like.

Supports for light-sensitive materials made using the silver halide emulsion prepared as described above include, for example, baryta paper, polyethylene-coated paper, polyprocellulose nitrate, polyvinyl acetal, polypropylene, polyethylene terephthalate, etc. There are polyester films, polystyrene, etc., which are appropriately selected depending on the type of support and the intended use of the photosensitive material.

These supports are subjected to undercoat processing, if necessary.

The silver halide emulsion of the present invention can be applied to many photosensitive materials, but it is particularly useful to apply it to color diffusion transfer photosensitive materials, which are widely known. 6 For example, U.S. Patent No. 2.983,606, U.S. Patent No. 3.345.163, U.S. Pat.
3.594.1fi4 and 3.594.1
It is disclosed in many specifications such as No. 65. As shown in these specifications, color diffusion transfer photosensitive materials are:
a photographic element containing a dye image-providing material in combination with a silver halide emulsion, a receiving element that receives the dye generated by the image and performs the image formation, and an alkaline processing composition necessary to cause its development. It consists of

When the silver halide emulsion prepared according to the present invention is applied to a color diffusion transfer light-sensitive material, the dye image-providing substance is useful in that it acts on a positive or negative and is initially mobile or immobile during processing with an alkaline composition. The initially mobile, positive-working dye image-providing material useful in the preferred embodiment of the present invention is described in U.S. Pat.
, No. 983.606, No. 3, 53 fi, 73
No. 9, No. 2.756.142, No. 9! 3,705,1
No. 84, No. 3,482,972, No. 3,880.
No. 658 and No. 3,854,985. Examples of negative-working dye image-providing materials useful in the preferred practice of the invention include common couplers that react with oxidized aromatic primary amine color developing agents to form or release dyes, such as U.S. Patent No. 3.
No. 227,550 and Canadian Patent No. 602,607
This is what is written in the name and regulations.

In a preferred embodiment of the invention, the dye image-providing material is a dye-releasing redox compound (DRR).

Such compounds are well known in the art and react with oxidized or non-oxidized developer or electron transfer agents to release dyes. Examples of such non-diffusible 1) RRs include compounds that work on negatives, such as U.S. Pat. No. 3,728,113;
No. 25.062, No. 3.698.897, No. 3
．． No. 628.952, No. 3.443,939, No. 3.443.940, No. 4.053,312, No. 4,076.529, and JP-A No. 1983-10
No. 4343, No. 53-46739, No. 53-5073
No. 6, No. 51-113624, No. 53-3819,
No. 54-54021, No. 56-16131, No. 57
-85055 Publication and Research Disclosure 1
5157 (1976), 15654 (] 977)
This is what is described in .

In a preferred embodiment of the present invention, the above-mentioned Japanese Unexamined Patent Publication No. 51
Dye-releasing agents such as those described in Japanese Patent No. 104343 and No. 57-85055 are used. Such compounds are stabilized sulfonamide compounds that can undergo alkaline cleavage upon oxidation to release a diffusible dye.

In other preferred embodiments of the present invention, positive compounds such as U.S. Pat. No. 3,980,479,
4,139,379, 4.139,389, 4.199.354 and 4.199.
Non-diffusible DRR compounds of the type disclosed in No. 355 can be used.

Photographic elements in preferred embodiments of the invention are used to form star or polychromatic color images. The silver halide emulsion layer of the photographic element is combined with a dye image-providing material. The six-dye image-providing material has a major spectral absorption within the region of the visible spectrum to which the silver halide emulsion is sensitive. That is, the blue-sensitive silver halide emulsion layer is combined with a yellow dye image-providing substance, the green-sensitive silver halide emulsion layer is combined with a magenta dye image-providing substance, and the red-sensitive silver halide emulsion layer is combined with a cyan dye image-providing substance. ing. The dye image-providing material associated with each silver halide emulsion layer is contained either in the emulsion layer itself or in a colorant layer adjacent to the emulsion layer. Usually, the colorant layer containing the dye-1 obscene substance is coated as a separate layer below the emulsion layer with respect to the exposure direction.

The various silver halide emulsion layers of the photographic base used in a preferred embodiment of the invention are arranged in the usual order, ie, from the exposed side, first the blue-sensitive silver halide emulsion 1-1, then the green-sensitive silver halide emulsion layer. and a red-sensitive silver halide emulsion layer, but this can be changed arbitrarily depending on the purpose.A single yellow filter layer can be arranged between the blue-sensitive silver halide emulsion layer and the green-sensitive silver halide emulsion layer. .

In a preferred embodiment of the invention, the treated addition elements include:
A variety of silver halide developing agents are useful in the present invention. Combinations of different developers can also be used, for example as disclosed in US Pat. No. 3,039,869. Although such developing agents may be used in liquid processing compositions, they may be used in producing elements to be activated by alkaline processing compositions or in one or more layers in receiving elements, e.g. emulsions. Good results are obtained when the developer is mixed in the layer, in the hue, in the intermediate layer or in the slag-receiving layer.

The N of the developing agent that can be used in the present invention is as follows.

Hydroquinone, amine phenols such as N-methylaminophenol, 1-phenyl-3-pyrazolidinone, 1-phenyl-4,4-dimethyl-3-pyrazolidinone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidinone , 1-p-tolyl-3-pyrazolidinone, 1~p-)')-4-methyl-4-hydroxydimethyl-:3-pyrazolidinone, N,N-diethyl-p-7enincyamine,:3-mef- N, N-
D-c-p-phenylenediamine, 3-methoxy~
N-x) xy-p-phenymphodiaminenato.

Among those mentioned herein, black and white color developing agents are particularly preferred, as they generally have the property of reducing stain formation. A conventional aqueous solution of a substance such as an alkali metal hydroxide or carbonate, in particular sodium hydroxide or carbonate, or an amine such as diethylamine, which aqueous solution preferably contains 13
It has a pH value exceeding .

The treatment composition contains antioxidants such as sodium sulfite, ascorbate, piperidinohexose reductone, and may contain silver ion concentration regulators such as potassium bromide. It may also contain a viscosity-increasing compound such as phthalate, hydroxyethylcellulose, or sodium carboxymethylcellulose.

In addition, the present alkaline treatment composition may contain a compound that promotes the phenomenon, such as benzyl alcohol or aliphatic @ primary amino acid (for example, 11-aminoundecanoic acid), or that promotes the diffusion of the dye. Also good.

In addition, the processing composition also contains light-absorbing substances such as titanium chloride, carbon black, and a pH indicator to prevent the silver halide emulsion from fogging due to external light during processing, and U.S. Pat. It may be advantageous in some cases to contain desensitizers such as those described in US Pat. No. 5,579,333. Furthermore, in the treatment composition [is benzo] I
Elephant suppressants such as J azoles can be added.

The use of a neutralizing layer in the photographic stabilizers of this invention increases the stability of the transferred gap.

The neutralizing layer used in the present invention lowers the pH of the slag-receiving layer to about 13.
Preferred are polymeric acids containing sufficient acid groups to reduce the size from 14 to at least 11, and preferably from about 5 to 8 within a short period of time after cessation of the reaction. These polymer acids are disclosed in JP-A-52-153739,
No. 53-4541, No. 53-1023, No. 54-1
Publication No. 39523, Research Disclosure (
Research Disclosure) 123
31 (1974) and 13525 (1975).

One or more timing layers or inert spacer layers may be used which are placed in superposition (directly or indirectly) above or below the above-mentioned intermediate layers. This layer has the function of controlling the timing of the pH drop as a function of the rate at which the alkaline treatment composition diffuses through the inert spacer layer. Examples of such timing layers and their functionality are given in JP-A-5
No. 6-69629, No. 57-6842, No. 57-68
No. 43, No. 52-145217, No. 55-54341
No. 57-60332.

The pigeon used in the present invention is a mordant for fixing the diffusion transfer dye, and various known mordants can be used.

As specific examples of mordants, nitrogen-containing secondary and tertiary amines, nitrogen-containing heterocyclic compounds, and quaternary cationic compounds thereof are widely known.

U.S. Patent No. 2,548,564, U.S. Patent No. 2,484
, No. 43Q, No. 3.148.061, No. 3.75
No. 6.814 vcFi, vinylpyridine polymers and vinylpyridinium cationic polymers are disclosed.

U.S. Pat. No. 2,675,316 discloses the use of polymers containing dialkylamino groups as mordants.

Aminoguanidine derivatives are disclosed in US Pat. No. 2,882,156.

U.S. Patent No. 3.625,694, U.S. Patent No. 3.859.0
96, British Patent No. 1,277.453, British Patent No. 2.0
No. 11,012 discloses gelatin and a crosslinkable mordant.

U.S. Patent No. 3,958,995, U.S. Patent No. 2,721.8
No. 52, No. 2,798.063 discloses an aqueous sol type mordant.

JP-A-50-61228 discloses a water-insoluble mordant.

Other U.S. Patent No. 3,709.690, U.S. Patent No. 3.78
No. 8,855, West German Patent Application Publication (DEO8) No. 2.8
43,320 specification, JP 53-30328, JP 52-155528, JP 53-125, JP 53-1
No. 024, No. 54-74430M, No. 54-12472
No. 6, No. 55-22766, U.S. Patent No. 3,64
No. 2,482 No. 3.488.706, No. 1 No. 3, 5
No. 57,066, No. 3.271.147, No. 3.
Specification No. 271,148, Japanese Patent Publication No. 55-29418,
Various mordants are disclosed in Publications No. 56-36414, No. 57-12139, and Research Disclosure 12045 (1974).

Example 1 An emulsion sample of the present invention [hereinafter referred to as emulsion (1)] was prepared as follows.

One minute after adding 3.5 x 10-' mol of potassium hexachloroiridate(III) into the solution (5) kept at 40°C, the solution (Bl and (C1) was added simultaneously during particle growth. was added in proportion to the surface area of the reaction vessel.At this time, the pH of the reaction vessel was controlled to 8 with a 50% aqueous acetic acid solution.
I did it. Next, a Demolgy aqueous solution and a magnesium sulfate aqueous solution manufactured by Kao Atlas Co., Ltd. were added to perform precipitation desalination.
Gelatin was added to obtain an emulsion with pAg 7.8 and pH 6.0. Furthermore, sodium thiosulfate, chloroauric acid, and rhodan ammonium were added, and chemical ripening was performed to produce 4-hydroxy-
6-Methyl-113138,7-chitrazaindene was added, and gelatin was further added to obtain a silver iodobromide emulsion. Here, the seeds of silver iodobromide in solution (A) Ic were added to a reaction vessel by adding an aqueous gelatin solution to the pAg and pH values in the reaction vessel.
While controlling [7], a silver nitrate aqueous solution and an incorporated potassium aqueous solution were added in proportion to the surface area increase VC during particle growth, and then precipitated and removed as described above. The resulting emulsion has an average grain size of 0.6μ
The particles were m.

By changing the emulsion sample (2
), (:+), (4), (5), (6
), (7), (s).

Prepare (9), (10), and (11).

Table 1, Example Row 2 Photosensitive ammonium (photosensitive sheet) samples were prepared as follows.

180μ thick transparent poly(ethylene terephthalate)
The following layers were applied in sequence onto the film support.

No (1) Neutralization layer poly(n-butyl acrylate-←acrylic acid) (30
A methanol solution containing 100 parts of an acid polymer (770% by weight), 6 parts of carbon black (Mitsubishi Kasei Corporation MMA-100") and 2 parts of a silane coupling agent (manufactured by Toshi Silicone) as a hardening agent was added to the acid polymer. Neutralizing layer layered so that the coating amount is 20 g7'i.

Layer (2) Timing Layer 1 part poly(acrylonitrile-vinylidene chloride-acrylic acid) latex (weight ratio 14/79/7) and allyl acetate-maleic anhydride copolymer were hydrolyzed, lactonized, and 1-butanol. Mixture 2-6 with 1 part of the lactone polymer described in Japanese Patent Application No. 56-65445 with a #/butyl ester ratio of 15/85 prepared by partial esterification with
A timing layer consisting of 11/rrl.

Layer (3) Climer layer A coating solution with the following composition was coated with gelatin in an amount of 0.2°1/
/rrt and immediately dried at 100'C for 3 minutes without setting.

Alkali-treated gelatin 5.011 Aqueous solution of surfactant (S-1) 5.0 Aqueous solution of surfactant (S-2) 5.0; 71 Nocolloidal silicon oxide (matting agent) 35Ln9N, N/
, N//-triacryloyl-hexahydro-8-)
to riazine 607n9, N'-bis(l-
aziridine-carbonyl)hexamethylenediamine 2001 was made up to 1000 m with water.

The structural formula of the activator used here is shown below.

Activator S-2 Layer (4) Cyan colorant layer The following cyan image-providing substance (0, (i4g/rrt)
, tricresyl phosphate (0,32,9/rrt
) and gelatin (1,69/mj).

H 1m (51 Red-sensitive negative-working silver halide emulsion layer - (negative-working) silver iodobromide emulsion obtained by color-sensitizing the emulsion sample (1) shown in Table 1 to red sensitivity (silver coating amount: 35 g/m) , 275
Emulsion layer containing potassium ec-octadecylhydroquinone-5-sulfonate (0,171/rrt) and gelatin (1,5g/7f).

Layer (6) Protective gelatin (1 g/g), 2-acetyl-5-octadecylhydroquinone (0,29/i), particle size 2-4 μ°
A protective layer containing silicon oxide (o, ox5.9/m) and glyoxal <o, 2y/rrt).

Then, in exactly the same manner as Sample A obtained above, the emulsion used in layer (5) above was changed to emulsion samples (2) to (11) in Table F. Accordingly, sample H- was selected, and a total of 11 types of photosensitive elements (photosensitive sheets) were prepared.
It was created.

A receptor ammonium (image-receiving sheet) was then prepared by coating the following layers in the order listed onto an opaque paper support.

No tension v (1) Uke 16ρ layer styrene and N, N-Schiff 1 Chill-N-Hair Sil-N
-consisting of p-(methacroylaminophenyl)methylgelatin (2,7,!i'/n?) and 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidinone (0,33N/m") Slag receiving layer.

Layer (2) Intermediate layer Ceratin C1,2gi77L'), UV absorber (0,
81/ml) and glyoxal (0-0611
/rtt) middle layer.

Layer (3) Protective layer Protective layer of gelatin (0,651/I).

Layer (4) Overcoat layer Gelatin (0,271/rrt) and silica (
], 4g as a light source, 0.5 second exposure (exposure method I), and 16 second exposure (exposure method 2) with red light through a wedge. Here, the exposure amounts in the exposure methods (1) and (2) are the same. Thereafter, it was immersed for a few seconds in an activator bath having the composition shown below in a shallow tray-type processing device at a temperature of 23'C, and then passed between a pair of pressure rollers and superimposed on the above-described image-receiving sheet.

Composition of activator solution After 10 minutes, the photosensitive sheet and the photosensitive sheet were peeled off.

For the color images obtained on the reception sheet through the above process, the relative sensitivity was adjusted to 61 using red light.
There were 1j tails. The measurement results are shown in Table 2 below.

The above relative sensitivity is expressed as the relative value of the reciprocal of the exposure amount that gives a density of 0.8, and E2/El is the relative sensitivity of the sample for exposure method Ⅰ, and the relative sensitivity for exposure method I is shown in Table 2. As is clear from the samples A and H of the present invention.

(2) and J. In addition to improving the low-illuminance reciprocity law failure characteristics, the sensitivity is high, and the decrease in sensitivity due to the inclusion of the water-soluble iridium compound is small in the exposure method (2). Furthermore, the amount of the water-soluble iridium compound is effective in the range from 10" mole to 10-5 mole per mole of silver halide. If it is less than that, there will be no effect of improving the low-illuminance reciprocity law failure characteristic, and if it is more This results in a decrease in sensitivity.

Example-3 Transparent poly(ethylene terephthalate) with a thickness of 180μ
A sample was prepared by sequentially coating the following layers on a film support.

Layer 1...Layer 1 described in Example 2 〃2... 2〃3...
314 yen 4 〃5... 5 Han 6 Medium
1' + penalty layer gelatin < 0.63 i 7m) and 2-acetyl-5-5ec-octadecylhydroquinone (o, 4s
I/rr? ).

Layer 7 Magenta color material layer A magenta image desecration substance represented by the following structural formula (0-8
1/rl), ethyl lauramite (o, 4 g/d) and gelatin (1,5y/rrt) + magenta hue layer.

Layer (8) Green-sensitive negative-working silver halide emulsion layer $1 A (negative-working) silver iodobromide emulsion obtained by color-sensitizing the emulsion sample (1) shown in the table to green sensitivity (Gin Coating Co., Ltd. 0.5 fl/m) ), potassium 2-octadecylhydroquinone-5-sulfonate (0,17i/rrt > and gelatin (1
, 3&/m).

Layer (9) Intermediate layer gelatin (0,63,!i'/trt) and 2
Interlayer consisting of -acetyl-5-5ec-octadecylhydroquinone (0,45117m).

layer (1ω yellow coloring material layer yellow double-opening donor material of the following structural formula (0,56jj/r
rl), tricresyl phosphate (0,25,!?
/rrl') and gelatin (0,12 g/m")
A yellow color material layer consisting of.

1m (11)! Sensitive negative silver halide emulsion layer 1
Silver iodobromide emulsion (negative type) in which the emulsion sample (1) shown in the table was color-sensitized to blue sensitivity (silver coating amount o, ss i / m), 2
-octadecylhydroquinone-5-potassium sulfonate (0,179/m) and gelatin (1,3
A blue-sensitive silver halide emulsion layer consisting of g/m').

Noso (12) Tamotsu! f1j gelatin (0.8F/m), methacrylate beads (
2~4μrrLO, 15g/n? ) Particle size 0-2pr
n silica (0,4597m) and tetrakis(vinylsulfonylmethyl)methane (0,2,!?/i,)
J: Reen.

protective layer.

Layer (5) as described above.

Emulsion samples contained in layer (8) and r* (11) (
1) in the emulsion samples (21, (4) and (21) shown in Table 1).
5) for samples M, N and O, respectively.
was created.

The obtained samples L, M, N, and O were each exposed for 0.5 seconds using a tungsten lung as a light source (lip plate L).
Method ①) and 16 second exposure (exposure method ①) were carried out through a wedge, and the process was carried out in the same manner as in Example ψ112 to obtain colored iron on the slag receiving sheet. Next, the relative sensitivity of each of the above samples was measured in the same manner as in Example 2, and as can be seen from the table, the sample sample according to the present invention had a blue sensitivity in the multi-IiiiIi type color diffusion transfer sensitive material. It is clear that both the green-sensitive and red-sensitive layers have improved low-illuminance reciprocity law failure characteristics, high sensitivity, and little decrease in sensitivity due to the inclusion of the water-soluble iridium compound.

Claims (2)

[Claims] (1) A step of physically ripening by an ammonia method in the pH range of 7 to 9 and in the presence of at least one water-soluble iridium compound in an amount of 10^-^8 to 10^-^5 mol per mol of silver halide. 1. A method for producing a silver halide photographic emulsion comprising: (2) The method for producing a silver halide photographic emulsion according to claim 1, wherein the silver halide constituting the silver halide photographic emulsion is silver iodobromide.