JPH01196036A - Production of silver halide photographic emulsion - Google Patents

Abstract

PURPOSE:To retard generation of fog and generation of wet pressure by adding an org. compd. having a predetermined solubility characteristic to a silver halide photographic emulsion during its. CONSTITUTION:At least one org. compd. selected from an org. compd. having 1X10<-11> solubility product (Ksp) with Ag ion in a stage since the particle size attains >=4/5 of the final particle size till the completion of the redispersing stage, is added to a silver halide photographic emulsion in a stage for forming a silver halide particles to be contained in the emulsion. Said silver halide particles may be any of silver chlorobromide, silver chloroiodide, silver chloroiodobromide, or silver chloride. Presence of silver iodide is permitted but its absence is most preferred. By this constitution, a silver halide photographic emulsion having high preparation stability against fog, causing extremely slight generation of sentization fog by the effect of wet pressure, is obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for producing a silver 10-genide photographic emulsion which has excellent production stability and has extremely low occurrence of sensitization fog due to wet pre-pressure.

[Background of the invention]

In recent years, there has been an increasing demand for speeding up color development for various purposes including improving the productivity of photographic prints, and various measures have been taken for this purpose. One method is to use a color development accelerator when developing an exposed silver halide photographic light-sensitive material (hereinafter referred to as light-sensitive material) using an aromatic primary amine color developing agent. Are known.

For example, as such a color development accelerator, US Pat.
, 950.970, 2,515,147, British Patent No. 1,430.998, British Patent No. 1,455.413, JP-A-53-15831, JP-A-55-62450, etc. However, most of these compounds have insufficient development accelerating effects, and even those compounds that exhibit sufficient development accelerating effects often have the disadvantage of forming fog, making them impractical. It wasn't.

In addition, a method using various penetrants (typical example is benzyl alcohol) to promote the penetration of a color developing agent into a photosensitive material, a method of increasing the temperature + pH of a color developing solution, and US Pat. No. 3,719.492 As described in the above issue, methods have been proposed in which a color developing agent is incorporated into a photosensitive material in advance, but the degree of speedup is low, the storage stability of the color developing agent is poor, or Fogging occurred, making it impractical.

On the other hand, it is also known to speed up color development by using a silver chloride emulsion or a chlorobromide emulsion with a high silver chloride content as the silver halide emulsion. For example, U.S. Pat. No. 4,183,756, U.S. Pat.
-95339, 58-94340, 58-95
No. 736, No. 58-106538, No. 58-1075
No. 31, No. 58-107532, No. 58-10753
No. 3, No. 58-108533, No. 58-125612
There is a description of the above technology in the issue. The techniques described in these publications are quite satisfactory from the viewpoint of rapid processability, and in terms of sensitivity, if unstable sulfur compounds and gold compounds are used for chemical sensitization of emulsions containing high silver chloride content, they are practical. It is possible to increase the sensitivity to a level that causes no problems.

However, emulsions containing high silver chloride tend to cause fogging more easily than silver chlorobromide emulsions, silver bromide emulsions, or silver iodobromide emulsions, etc., which have a relatively high silver bromide content, so it is difficult to suppress fogging. This technology is the key to making full use of emulsions containing high silver chloride. For example, in the actual manufacturing process of light-sensitive materials, emulsions that have undergone physical ripening (silver halide grain formation and the subsequent desalting process) are generally stored in a refrigerator and redissolved as necessary. However, emulsions containing high silver chloride may develop fog during storage in a refrigerator, or when the temperature is raised to remelt prior to chemical ripening. may deteriorate.

As a method to avoid such a situation, a physical ripening method is known in which a so-called fog suppressant is added to the silver halide grain formation process and the silver halide grain formation is completed in the presence of the compound. Although the fogging resistance of the physical ripening method material increases significantly, the resistance to pressure of samples coated with chemically sensitized silver halide emulsions in a wet state due to development processing solutions (hereinafter referred to as wet pressure resistance) greatly increases. The inventors of the present invention found out through their studies that it deteriorates.

As a result of extensive studies in order to eliminate the above-mentioned drawbacks, the present inventors have discovered that by adding an organic compound having a specific solubility characteristic value at a specific occasion in the production process of silver halide emulsions, The present invention was made based on the unexpected discovery that it is possible to produce a silver halide photographic emulsion in which the occurrence of fog is effectively suppressed and the occurrence of wet pressure is extremely suppressed.

[Purpose of the invention]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a method for producing a silver halide photographic emulsion which has particularly excellent production stability against fog and in which sensitization fog due to wet pressure is extremely less likely to occur.

[Structure of the invention]

The above-mentioned object of the present invention is to provide a silver halide grain with a final grain size of 4.
From the time when the particle size becomes 15 or more until the end of the redispersion process, the solubility product (KSP) with silver ions is I x 10
This was achieved by a method for producing a silver halide photographic emulsion, which is characterized by adding at least one compound selected from organic compounds having a solubility characteristic of -11 or less.

[Specific structure of the invention]

The silver halide grains contained in the silver halide photographic emulsion of the present invention are high silver chloride grains with a silver chloride content of 90 mol % or more, and from the viewpoint of rapid processability, the preferred silver chloride content is 99. It ranges from 0 mol% to 99.9 mol%.

The silver halide grains according to the present invention may be any of silver chlorobromide, silver iodochloride, silver chloroiodobromide, and silver chloride, and silver iodide may be contained, but the content is , preferably 1
mol% or less, more preferably 0.5 mol% or less,
Most preferably, it does not contain silver iodide. Therefore, preferred silver halide grains for the present invention are silver chlorobromide and silver chloride, and the most preferred grains are silver chlorobromide having the above-mentioned silver chloride content.

The silver halide grains according to the present invention may be used in combination with silver halide grains other than the present invention, but in that case, all the halides in the silver halide emulsion layer containing the silver halide grains according to the present invention The ratio of the projected area occupied by the silver halide grains of the present invention to the projected area occupied by the silver halide grains is preferably 50% or more, more preferably 75% or more.

The silver halide grains of the present invention can be used, for example, in JP-A-59-16
No. 2540, No. 59-48755, No. 60-2228
No. 44, No. 60-222845, No. 60-13673
It can be formed according to the method described in No. 5 and the like.

The grain size of the silver halide grains according to the present invention is not particularly limited, but in consideration of other photographic performance such as rapid processing properties and sensitivity, it is preferably 0.2 to 1.6 μm1, more preferably 0.25 μm. 1.2 μm to 1.2 μm most preferably 0.5
The volume ranges from 0.8 μl to 0.8 μl. The particle diameter can be measured by various methods commonly used in the technical field. Typical methods include Loveland's "Particle Size Analysis Method JA, S, T, M, Symposium on Light Microscopy, 1955, pp. 94-122," or "Theory of Photographic Processes," co-authored by Mies and James, 3rd edition, published by Macmillan (
(1966), Chapter 2. The particle size can be measured using the particle's projected area or diameter approximation.

If the particles are of substantially uniform shape, the particle size distribution can be described fairly accurately as diameter or projected area.

The grain size distribution of the silver halide grains according to the present invention may be polydisperse or monodisperse. Preferably, the silver halide grains are monodisperse silver halide grains having a coefficient of variation of 0.22 or less, more preferably 0.15 or less in the grain size distribution. Here, the coefficient of variation is a coefficient indicating the breadth of the particle size distribution, and is defined by the following equation.

Here, ri represents the particle size on each side of the particle, and ni represents the number thereof.

The grain size here refers to the diameter in the case of spherical silver halide grains, and in the case of grains with shapes other than cubic or spherical, the diameter when the projected image is converted to a circular image of the same area. .

The silver halide grains according to the present invention may be obtained by any of the acid method, neutral method, and ammonia method. The particles may be grown all at once, or may be grown after seed particles are produced. The method of creating and growing the seed particles may be the same or different.

The soluble silver salt and the soluble halide may be reacted by any method such as a forward mixing method, a back mixing method, a simultaneous mixing method, or a combination thereof, but those obtained by a simultaneous mixing method are preferred. Furthermore, as a form of simultaneous mixing method,
4-48521, etc., or the A9-Chondrold double jet method may also be used.

Furthermore, if necessary, a silver halide solvent such as thioether,
Alternatively, a crystal phase control agent such as a sensitizing dye may be used.

Any shape of the silver halide grains according to the present invention can be used. One preferred example is a cube having a (100) plane as a crystal surface.

Also, U.S. Pat. No. 4,183.756 and U.S. Pat. No. 4,225.
No. 666, JP-A-55-26589, JP-A-55-4
2737, etc., and The Journal on Photographic Science (J, Photogr, 5ci) 2
Particles having shapes such as octahedrons, tetradecahedrons, and dodecahedrons can be prepared by the method described in literature such as 1.39 (1973) and used. Furthermore, particles having twin planes or irregularly shaped particles may be used.

The silver halide grains according to the present invention may be of a single shape or may be a mixture of grains of various shapes.

The silver halide grains according to the present invention can be prepared by adding cadmium salt, zinc salt,
Metal ions can be added using lead salts, thallium salts, iridium salts, rhodium salts, iron salts, or complex salts thereof to be included inside the particles and/or on the particle surfaces, and in an appropriate reducing atmosphere. By leaving the particles in place, reduction sensitizing nuclei can be provided inside the particles and/or on the particle surfaces.

In the case of removing unnecessary soluble salts from the emulsion of the present invention after the growth of silver halide grains is completed, the method described in Risch Disclosure No. 17643 can be used.

The silver halide grains according to the present invention may be grains in which a latent image is mainly formed on the surface, or grains in which a latent image is mainly formed inside the grain. Preferably, the particles are particles on which latent images are mainly formed.

In the present invention, the silver halide emulsion containing the silver halide grains according to the present invention has the following properties in the grain forming step:
From the time when the particle size reaches the final particle size of 415 or more until the end of the redispersion process, the solubility product (KSP) with silver ions is
At least one compound selected from organic compounds having solubility characteristics of X 10-■ or less is added.

The desired effect cannot be expected with compounds that have a solubility product with silver ions other than the present invention that exceeds 1 x 10-'', that is, with compounds that have a smaller ability to form salts with silver ions.Measurement of solubility product For calculations, “New Experimental Chemistry Course 1”
Volume 233-250 (published by Maruzen) may be referred to.

In the present invention, the solubility product with the silver ion is I
An organic compound having a solubility characteristic of 10-■ or less (hereinafter referred to as the organic compound of the present invention) preferably has the following general formula [
It is a mercapto compound represented by [S].

(In the formula, Q represents an atomic group necessary to form a 5- or 6-membered heterocycle or a 5- or 6-membered heterocycle condensed with a benzene ring, and M represents a hydrogen atom or a cation.

) The mercapto compound represented by the general formula [31] which is preferably used as the organic compound of the present invention will be described below.

In the general formula [81, Q represents an atomic group necessary to form a 5- or 6-membered heterocycle or a 5- or 6-membered heterocycle fused with benzene rings; Examples include imidazole ring, tetrazole ring, thiazole ring, oxazole ring, selenazole ring, benzimidazole ring, naphthoimidazole ring, benzothiazole ring, naphthothiazole ring, benzoselenazole ring, naphthoselenazole ring, benzoxazole ring, etc. can give.

Examples of the cation represented by M include alkali metals (
Examples include sodium, potassium, etc.), ammonium groups, and the like.

The mercapto compound represented by the general formula [S] is further combined with the following general formulas [SA], [SB], [SO3 and [SD]
The mercapto compounds shown respectively are preferred.

In the formula, %RA is a hydrogen atom, an alkyl group, an alkoxy group,
represents an aryl group, a halogen atom, a carboxyl group or a salt thereof, a sulfo group or a salt thereof, or an amino group, 2 represents -NB+, -o-, or -S-, and M represents M in the general formula [5] are synonymous.

General formula [SB] +r In the formula, Ar represents an alkyl group, an alkoxy group, a carboxyl group or a salt thereof, a sulfo group or a salt thereof, a hydroxyl group, an amino group, an acylamino group, a carbamoyl group or a sulfonamide group. represent. n represents an integer of 0 to 2. M has the same meaning as M in general formula [S].

In general formulas [SA] and [SB], RA and R
Examples of the alkyl group represented by 11 include methyl group, ethyl group, butyl group, etc., examples of alkoxy groups include methoxy group, ethoxy group, etc., and examples of salts of carboxyl group or sulfo group include sodium salt,
Examples include ammonium salts.

In the general formula [SA], examples of the aryl group represented by RA include a phenyl group and a naphthyl group, and examples of the halogen atom include a chlorine atom and a bromine atom.

In the general formula [SB], examples of the acylamino group represented by R1 include methylcarbonylamino group, benzoylamino group, etc., examples of the carbamoyl group include ethylcarbamoyl group, phenylcarbamoyl group, etc., and examples of the sulfonamide group include Examples include methylsulfonamide group and phenylsulfonamide group.

The above-mentioned alkyl groups, alkoxy groups, aryl groups, amino groups, acylamino groups, carbamoyl groups, sulfonamide groups, etc. further include those having substituents.

General formula [SC] Represents. RA represents a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, a cycloalkyl group, -S RAI%, or a heterocyclic group, and RAl represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, - C.O.R.
A, , or -So, RA, RAl and R
A3 represents a hydrogen atom, an alkyl group, or an aryl group, and RA4 and RAS represent an alkyl group or an aryl group. M has the same meaning as M in general formula [S].

RA in general formula [SC], RA,, RA2.
Examples of the alkyl group represented by RA3°RA4 and RAS include methyl group, benzyl group, ethyl group, and propyl group e, and examples of the aryl group include phenyl group and naphthyl group.

Examples of the alkenyl group represented by RA and RA include a propenyl group, and examples of the cycloalkyl group include a cyclohexyl group.

Examples of the heterocyclic group represented by RA include furyl group and pyridinyl group.

Above RA, R□, RA! , RAS, RA, and RAS
Alkyl and aryl groups, RA and R
An alkenyl group and a cycloalkyl group represented by A,
The heterocyclic group represented by RA also includes those having a further substituent.

General formula '[SD] (1) In the formula, RA and M each represent the same groups as RA and M in the general formula [SC].

Further, R11 and Ro each represent a group having the same meaning as RAI and RAl in the general formula [SC].

Specific examples of the compound represented by the general formula [3] are shown below, but the present invention is not limited thereto.

SA-1sA-2 SA-3SA-4 SA-5SA-6 SA-7SA-8 SB-ISB-2 SR-3SB-4 SB-5SB-6 The compound represented by the maximum [S] above is, for example, 4
No. 0.28496, JP-A-50-89034, Journal of the Chemical Society (J, Chem, So
c, ) 49.1748 (1927), 4237 (19
52), Journal of Organic Chemistry
Story (J, Org, Chem,) 39.246
9 (1965), U.S. Patent No. 2,824,001,
Journal of Chemical Society, 1723
(1951), JP-A-56-111846, British Patent No. 1,275.701, U.S. Patent No. 3,266.897, U.S. Patent No. 2.403,927, etc.
The synthesis method can also be carried out in accordance with the methods described in these documents.

In order to incorporate the compound represented by the general formula [S] according to the present invention (hereinafter referred to as compound [31]) into a silver halide emulsion containing silver halide grains according to the present invention, water or water and optionally organic solvents (e.g. methanol,
It can be added after being dissolved in ethanol, etc.). Compound [S] may be used alone, - in combination with two or more compounds represented by maximum [S], or - in combination with other stabilizers or fog suppressants other than the compound represented by maximum [5] It may also be used.

Compound [S] may be added at any time in the silver halide grain formation process from when the final grain size reaches 415 or more until the end of the redispersion process. This process will be described in detail below.

In a preferred embodiment of the present invention, the silver halide forming step is a pAg-chondrald double jet method, in which a silver ion-containing solution and a halogen-containing solution are injected until grain formation is completed.

Since the silver halide emulsion containing silver halide grains formed in this way usually contains unnecessary soluble salts, the salts must be removed to prevent them from causing failure in subsequent processes and after the product is made. Perform the operation. This is called the desalination process.

In the desalting process, a suitable precipitating agent is added to the silver halide emulsion to coagulate gelatin, thereby settling the silver halide grains, draining the supernatant, and adding washing water to dilute the soluble salts. do.

Next, by adding a suitable precipitant and repeating the above operation, it becomes possible to significantly reduce the concentration of soluble salts that was initially present.

However, due to the operation of the desalting step, not only soluble salts but also gelatin flow out at the same time, so that the gelatin concentration in the silver halide emulsion ultimately decreases. The process of adding additional gelatin to compensate for this and mixing it with the silver halide emulsion coagulated in the desalting process is called a redispersion process.

By performing this operation, silver halide grains are dispersed in gelatin at an appropriate concentration, making it possible to prepare a uniform silver halide emulsion without grain agglomeration or grain imbalance. Become.

If the compound [S] is added to the reaction vessel before silver halide formation, or added from the initial stage of grain formation to before the grain size reaches the final grain size of 415, fogging can be suppressed, but wet pressure will be generated. However, unlike the present invention, it is not possible to achieve both the effects of suppressing fog and preventing the generation of wet pressure. That is, the unique effects of the present invention can be obtained by not participating in the formation of silver halide grains and existing on the silver halide grain surface or subsurface (a site extremely close to the surface inside the silver halide grain). become.

Therefore, the compound [S] can be added in multiple doses even if the entire amount is added at once, as long as the particle size reaches the final particle size of 415 or more in the above-mentioned particle formation process and until the end of the redispersion process. It may also be added continuously. After the redispersion step is completed, the effects of the present invention cannot be obtained, or even if they are obtained, they are only minimal, which is not preferable.

The most suitable addition time for exhibiting the effects of the present invention is after the silver halide grains have been formed into a predetermined shape before proceeding to the desalting step, preferably during the grain forming step.

There is no particular restriction on the amount added, but it is usually I x 10-' mol to I x 10-' mol per mol of silver halide.
'mol, preferably l x 10-' moles to I x
It is added in a 10-" mole range.

The silver halide emulsion according to the present invention can be subjected to conventional chemical sensitization, that is, sulfur sensitization, gold sensitization, reduction sensitization, and noble metal sensitization, but preferably, the presence of unstable sulfur compounds and gold compounds can be applied. Chemically sensitized below.

The unstable sulfur compound and gold compound preferably used in the present invention will be explained below.

The unstable sulfur compound used in the present invention is a fused metal compound having the property of forming a silver salt when reacting with silver halide, and further forming silver sulfide under strong alkaline conditions, for example. Mention may be made of sulfur sensitizers such as thiosulfate, allylthiocarbamide, thiourea, allylisothiocyanate, cystine, and the like.

The amount of the sulfur sensitizer, which is an unstable sulfur compound, used in the present invention varies depending on various conditions, but is 1.5% per mole of silver halide. I x 10-' mole to 1 x 10-
It is preferably used in the range of 1 x 10-' mol, more preferably from 1 x 10-' mol to 1 x 10-' mol, particularly preferably from 2 x 10-' mol to 8 x 10-' mol. Further, when the above-mentioned sulfur sensitizer is added to an emulsion, it may be added after being dissolved in water or an alcohol such as methanol or ethanol.

Examples of the gold compound used in the silver halide emulsion layer of the present invention include chloroauric acid, sodium chloroaurate, and gold potassium thiosulfate.

However, it is not limited to these.

The amount of the gold compound according to the present invention added is preferably 1 x 10-' to 5 x 10-3 mol, more preferably 2 x 10-' to I x 10-' per 1 mol of silver halide.
It is a molar concentration, which is more preferable.
0-' to 4 x 10-'.

Most preferably 2.6X 10-@~9X10-'
It is.

The gold compound according to the present invention may be added from the time when the silver halide grains according to the present invention are formed until the chemical sensitization is completed.

The unstable sulfur compound and gold compound according to the present invention need only be present during chemical sensitization of the high silver chloride grains according to the present invention, and specifically, from the end of the formation of the grains to the end of chemical sensitization. be added to and present.

On the other hand, the organic compound according to the present invention is used at the end of chemical sensitization of a silver halide emulsion or at a later stage for the purpose of preventing fogging and improving the stability over time or storage stability of a light-sensitive material.
Although it may be added to the emulsion, other general so-called antifoggants may be used alone or in combination. Preferably, organic compounds according to the invention are used.

The emulsion according to the present invention can be spectrally sensitized to a desired wavelength range using dyes known as sensitizing dyes in the photographic industry. The sensitizing dyes may be used alone or in combination of two or more. Along with the sensitizing dye, the emulsion contains a dye that itself does not have a spectral sensitizing effect, or a supersensitizer, which is a compound that does not substantially absorb visible light and enhances the sensitizing effect of the sensitizing dye. Good too.

When the silver halide emulsion according to the present invention is used as a blue-sensitive emulsion, it is preferable to perform spectral sensitization with a sensitizing dye represented by the maximum [A] below.

- Maximum [A] In the general formula [A], % Z11 and Z12 are respectively a benzoxazole nucleus, a naphthoxazole nucleus, a benzoselenazole nucleus, a naphthoselenazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a benzimidazole nucleus,
It represents a group of atoms necessary to form a naphthoimidazole nucleus, a pyridine nucleus, or a quinoline nucleus, and these heterocycles include those having substituents.

Substituents for the heterocycle formed by z1□ and z1□ include a halogen atom, a cyano group, a methyl group, an ethyl group,
It is a methoxy group or an ethoxy group.

R31 and R1* each represent an alkyl group, an alkenyl group, or an aryl group, preferably an alkyl group, more preferably an alkyl group substituted with a carboxyl group or a sulfo group, and most preferably an alkyl group substituted with a carboxyl group or a sulfo group. 1 to 4 sulfoalkyl groups.

Further, RSS is selected from a hydrogen atom, a methyl group, and an ethyl group.

xe represents an anion, and a represents 0 or l.

-Among the sensitizing dyes represented by maximum [A], particularly useful dyes are the following sensitizing dyes represented by maximum [A'].

General Formula [A'] Here, YI and Y each represent an atomic group necessary to complete a benzene ring or a naphthalene ring which may be substituted.

Y, and Y! The benzene ring and naphthalene ring formed by the above may have a substituent, and the substituent is preferably a halogen atom, a cyano group, a methyl group, an ethyl group, a methoxy group or an ethoxy group.

Rx+, Rz2. Rzs, Xe, and 12 are 111
It is the same as that shown in formula [A].

Specific examples of the sensitizing dye represented by the general formula [A] used in the present invention are shown below.

1. -f) ((H2)5sOi' (L:th), SO,
NaA-6 (CHz)ssOs CHzCOOH When the silver halide emulsion according to the present invention is used as a green-sensitive emulsion, it is preferable to perform spectral sensitization with a sensitizing dye represented by the maximum [B] below.

-Maximum [B] In the formula, zll and Z1□ each represent an atomic group necessary to form a benzene ring or a naphthalene ring fused to an oxazole.

The heterocyclic nucleus formed may be substituted with various substituents, and these preferred substituents are halogen atoms, aryl groups, alkyl groups, or alkoxy groups. More preferred substituents are a halogen atom, a phenyl group, and a methoxy group, and the most preferred substituent is a phenyl group.

According to a preferred embodiment of the invention, Zll and 212
both represent a benzene ring fused to an oxazole ring, and at least one of these benzene rings has a
The 5-position of one benzene ring is substituted with a phenyl group, or the 5-position of one benzene ring is substituted with a phenyl group, and the 5-position of the other benzene ring is substituted with a halogen atom.

R21 and R22 each represent an alkyl group, an alkenyl group, or an aryl group, preferably an alkyl group.

More preferably, R21 and R22 are each an alkyl group substituted with a carboxyl group or a sulfo group, and most preferably a sulfoalkyl group having 1 to 4 carbon atoms. Most preferred is a sulfoethyl group.

R23 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, preferably a hydrogen atom or an ethyl group.

X and e represent anions, such as chlorine, bromine, CH3
Examples include anions such as SO4 and CH3SO4.

n represents 1 or O. However, when the compound forms an inner salt, n represents 0.

Specific examples of the sensitizing dye represented by the general formula [B] that are preferably used in the present invention are shown below.

-I (CHz)4SOsNa When the silver halide emulsion according to the present invention is used as a red-sensitive emulsion, a sensitizing dye represented by the maximum [C] below or a sensitizing dye represented by the maximum [D] below is used. Spectral sensitization is preferred.

-Maximum [C] ■ Rr Rz c
, z x, Z a and 2. represents an atomic group necessary to form a benzene ring or naphthalene ring condensed to a thiazole ring or selenazole ring, respectively, Z3 represents a hydrocarbon atomic group necessary to form a 6-membered ring, and α represents 1 or 2. 2 represents a sulfur atom or a selenium atom, and xe represents an anion.

In the above-mentioned maximum, the alkyl group represented by R includes a methyl group, an ethyl group, and a probyl group, and R is preferably a hydrogen atom, a methyl group, or an ethyl group. Particularly preferred are a hydrogen atom and an ethyl group.

R I+R again! , Rs and R6 are each a linear or branched alkyl group (this alkyl group may have a substituent. For example, methyl, ethyl, propyl, chloroethyl, hydroxyethyl, methoxyethyl, acetoxyethyl, carboxymethyl, carboxy Ethyl, ethoxycarbonylmethyl, sulfoethyl, sulfopropyl,
Sulfobutyl, β-hydroxy-γ-sulfopropyl,
sulfate propyl, allyl, benzyl, etc.) or an aryl group (this aryl group may have a substituent, for example, phenyl, carboxyphenyl, sulfophenyl, etc.), and represents a group selected from Z , , z 2+2, and 2. The heterocyclic nucleus formed by may have a substituent, and preferred substituents are a halogen atom, an aryl group, an alkyl group, or an alkoxy group, and further a halogen atom (for example, a chlorine atom), a phenyl group, , methoxy group is preferred.

CHsSOt, C2H55Oa, etc.), and a represents 1 or 2.

However, when the compound forms an inner salt, a represents l.

Typical specific examples of the sensitizing dyes represented by the general formulas [C] and [D] that are preferably used in the present invention are shown below.

C2Hs L; zHs , 6r C-8 -I The above-maximum amount of the sensitizing dye represented by [A], [B], [C] or [D] is not particularly limited, but is approximately 1 mol of silver halide. per I x 10-'~l x
It is preferably used in a range of 10-3 mol, more preferably 5 x 10-' to 5 x 10-' mol.

As a method for adding the sensitizing dye, a method well known in the art can be used.

For example, these sensitizing dyes can be dissolved in water-soluble solvents such as pyridine, methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, etc. (or mixtures of such solvents), in some cases diluted with water, and If necessary, they can be dissolved in water and added in the form of these solutions.

It is also advantageous to use ultrasonic vibrations for this dissolution. Furthermore, the sensitizing dye used in the present invention is described in U.S. Pat.
69,987, in which a dye is dissolved in a volatile organic solvent, the solution is dispersed in a hydrophilic colloid, and this dispersion is added, as described in Japanese Patent Publication No. 46-24185, etc. A method may also be used in which a water-insoluble dye is dispersed in a water-soluble solvent without being dissolved, and this dispersion is added. Further, the sensitizing dye used in the present invention can be added to the emulsion in the form of a dispersion by an acid dissolution and dispersion method, and the addition method is described in U.S. Pat.
342.605, 2,996,287, 3,4
25,835 and the like can also be used.

The sensitizing dyes to be contained in the silver halide emulsion of the present invention can be dissolved in the same or different solvents, and these solutions can be mixed or added separately before being added to the silver halide emulsion. Good too. When adding them separately, the order, time, and interval can be arbitrarily determined depending on the purpose. The sensitizing dye used in the present invention may be added to the emulsion at any time during the emulsion manufacturing process, but it is preferably added during or after chemical ripening, and more preferably during chemical ripening.

The photosensitive material of the present invention having the above structure can be, for example, color negative and positive films, color photographic paper, etc., but especially when used in color photographic paper for direct viewing, the method of the present invention may be used. The effects of this will be effectively demonstrated.

The photosensitive materials of the present invention, including this color photographic paper,
It may be for single color or multicolor.

In the case of multicolor light-sensitive materials, in order to perform subtractive color reproduction, a silver halide emulsion layer containing magenta, yellow, and cyan couplers as photographic couplers and a non-light-sensitive layer are usually used as photographic couplers. Although it has a structure in which layers are laminated on top in an appropriate number and order of layers, the number and order of layers may be changed as appropriate depending on the important performance and purpose of use.

When the photosensitive material used in the present invention is a multicolor photosensitive material, the specific layer structure includes a yellow dye image forming layer, an intermediate layer, a magenta dye image forming layer, Particularly preferred is an arrangement of an interlayer, a cyan dye image-forming layer, an interlayer, and a protective layer.

The dye image-forming coupler used in the present invention is not particularly limited, and various couplers can be used, but the compounds described in the following patents are included as representative examples.

Yellow dye image-forming couplers include acylacetamide deaf, benzoylmethane 4-equivalent or 2-equivalent couplers, such as those described in U.S. Pat.
No. 2,875,057, No. 2,908,573, No. 2,908.513, No. 3,227.155,
3,227.550, 3,253.924, 3,265,506, 3,277.155, 3
, No. 341.331, No. 3,369,895, No. 3,
No. 384,657, No. 3,408.194, No. 3,4
No. 15,652, No. 3,447,928, No. 3,55
1.155, 3,582,322, 3,725
, No. 072, German Patent No. 1,547.868, No. 2,
No. 057,941, No. 2,162.899, No. 2,1
No. 63.812, No. 2,213.461, No. 2,21
No. 9.917, No. 2,261.361, No. 2,263
．． No. 875, Japanese Patent Publication No. 13576 (1977), Japanese Patent Publication No. 1977 (1977)
No. 29432, No. 48-66834, No. 49-107
No. 36, No. 49-122335, No. 50-28834
No. 50-132926, No. 55-144240, and No. 56-87041.

Examples of magenta dye image-forming couplers include 4-equivalent or 2-equivalent magenta dye image-forming couplers such as 5-pyrazolone, pyrazolotriazole, pyrazolinopenzimidazole, indasilone, and cyanoacetyl. U.S. Patent No. 2,600.788, 3,
No. 061,432, No. 3,062,653, No. 3,1
27.269, 3,311.476, 3,15
No. 2.896, No. 3,419,391, No. 3,519
．． No. 429, No. 3,555.318, No. 3,684.
No. 514, No. 3,705.896, No. 3,888゜6
No. 80, No. 3,907,571, No. 3,928.04
No. 4, No. 3,930゜861, No. 3,930,816
No. 3,933,500, JP-A-49-29639
No. 49-111631, No. 49-129538, No. 51-112341, No. 52-58922, No. 55-62454, No. 55-118034, No. 56
-38643, No. 56-135841, Special Publication No. 1977
-60479, 52-34937, 55.29
No. 421, No. 55-35696, British Patent No. 1,247
．． No. 493, Belgian Patent No. 769.116, West German Patent No. 2,156,111, and Japanese Patent Publication No. 46-60479.
No., JP-A-59-125732, JP-A No. 59-22825
No. 2, No. 59-162548, No. 59-171956
No. 60-33552, No. 60-43659, West German Patent No. 1,070.030, and U.S. Patent No. 3,725.
It is described in each issue of No. 067.

Typical cyan dye image-forming couplers include phenolic and naphthol-based 4-equivalent or 2-equivalent cyan dye image-forming couplers, and are disclosed in U.S. Pat. No. 362,598,
2,367.531, 2,369.929, 2,423,730, 2,474.293, 2
, 476.008, 2,498.466, 2,
No. 545.687, No. 2,728.660, No. 2,7
72.162, 2,895.826, 2. j7
s, +46 No. 3,002.836, No. 3,419
, No. 390, No. 3,446.622, No. 3,476.
No. 563, No. 3,737.316, No. 3,758,3
No. 08, No. 3,839.044, British Patent No. 478.9
Old name, No. 945.542, No. 1,084.480,
1,377.233, 1,388.024 and 1,543゜040, and JP-A-47-3
No. 7425, No. 50-10135, No. 50-2522
No. 8, No. 50-112038, No. 50-117422
No. 50-130441, No. 51-6551, No. 51-37647, No. 51-52828, No. 51-
No. 108841, No. 53-109630, No. 54-4
No. 8237, No. 54-66129, No. 54-1319
No. 31, No. 55-32071, No. 59-146050
No. 59-31953 and No. 60-117249.

These dye-forming couplers preferably have a group called a ballast group in the molecule, which makes the coupler non-diffusive and has a carbon number of 8 or more. Furthermore, even if these dye-forming couplers are 4-equivalent, in which 4 silver ions need to be reduced in order to form one molecule of dye, only 2 silver ions need to be reduced. It may be either 2-equivalent.

It is advantageous to use gelatin as the binder (or protective colloid) used in the photosensitive material of the present invention, but
In addition, hydrophilic colloids such as gelatin derivatives, graft polymers of gelatin and other polymers, proteins, sugar derivatives, cellulose derivatives, and synthetic hydrophilic polymer substances such as single or copolymers can also be used. .

The photosensitive material of the present invention further includes a hardening agent, a color clouding preventive agent,
Additives such as image stabilizers, ultraviolet absorbers, plasticizers, latex, surfactants, matting agents, lubricants, and antistatic agents can be used as desired.

An image can be formed on the photosensitive material of the present invention by subjecting it to a color development process known in the art.

The color developing agents used in the color developing solution of the present invention include aminophenol and p-phenylenediamine derivatives that are widely used in various color photographic processes.

The color developing solution applied to the processing of the light-sensitive material of the present invention includes:
In addition to the above-mentioned primary aromatic amine color developing agent, known developer component compounds can be added.

The pH value of the color developer is usually above 7, most commonly about 10-13.

The color development temperature is usually 15°C or higher, and -2 for boat fishing.
It is in the range of 0 to 50°C. For rapid development, it is preferable to carry out the process at 30°C or higher. In addition, conventional processing takes 3 minutes or more.
4 minutes, but the color development time of the present invention aimed at rapid processing is generally preferably carried out in the range of 20 seconds to 60 seconds, more preferably in the range of 30 seconds to 50 seconds. .

After color development, the photosensitive material of the present invention is subjected to a bleaching process and a fixing process. Bleaching treatment may be performed simultaneously with fixing treatment.

After the fixing process, a washing process is usually performed.

Further, as an alternative to the water washing treatment, a stabilization treatment may be performed, or both may be used in combination.

[Specific effects of the invention]

As explained above, the silver halide photographic emulsion of the present invention was an excellent emulsion with excellent production stability and extremely suppressed generation of wet pressure. Moreover, it was also excellent in rapid processing properties.

〔Example〕

EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the embodiments are not limited thereto.

(Example-1) 20% gelatin aqueous solution 1010 with temperature raised to 40°C
00, according to the method described in JP-A-50-45437, 4M (molar concentration)-AgNO3 aqueous solution 5 parts 0
3M-NaCff aqueous solution containing 0.5 mff 500!1 (
2 to pAg 6 by Chondrold double jet method.
．． 6. Added over 35 minutes while controlling pH to 2.0.

The aqueous gelatin solution containing AgX particles thus obtained is
After adjusting the pH to 5.5 with an aqueous potassium carbonate solution, a 5% aqueous solution of Demol N 7301 manufactured by Kao Atlas Co., Ltd. was added as a precipitant.
1I2 and 500 I of a 20% aqueous solution of magnesium sulfate as a polyvalent ion were added to cause coagulation, and the mixture was allowed to settle by standing. After decanting the supernatant, 2000 μa of distilled water was added to disperse it again. Next, add 80% magnesium sulfate aqueous solution.
mQ was added, coagulated again, the precipitated supernatant was decanted, and the total volume was reduced to 15% with an aqueous solution containing ossein gelatin 809.
An AgX emulsion was prepared by dispersing at 40°C for 40 minutes at 00 mQ.

As a result of electron microscopic observation, this emulsion has an average grain size of 0.13.
The emulsion was a monodisperse emulsion consisting of cubic grains of μm in size.

The following silver halide emulsions were prepared using the above emulsions as seed emulsions. A 2.2% gelatin aqueous solution 400II112 emulsion with the temperature raised to 40°C was dispersed at 24.3yaQ,
M-AgNOs 322mff and 0-1+*oQ% of KBr and exemplified compound 5B-5 (solubility product with silver ion (
0.3% methanol solution of pksp) 14.0) 9.3
322 mff of a 3 M-NaCI2 aqueous solution containing s(1) was purified with a pAg of 7-3
, while controlling the pH to 5.8.

In addition, at the addition point corresponding to addition of 55% of the total Ag amount.
An aqueous solution containing 0.5 μl of IrCff was added.

This silver halide emulsion was desalted using a precipitant in the same manner as the seed emulsion, and additional ossein gelatin was added for redispersion. This AgBrCff emulsion containing 0.1 mol % of AgBr was found to be a monodisperse emulsion consisting of cubic grains with an average grain size of 0.5 .mu.m and a coefficient of variation of 8% in grain size distribution as a result of electron microscopic observation.

This emulsion is designated as EM-1.

As shown in the table below, emulsions EM-2 to EM-6 were prepared in which the addition position of compound 5B-5 was changed.

Table-1 Next, a photosensitive material was prepared using the emulsion prepared above.

Emulsions EM-1 to EM-6 were each sampled in an amount containing 0.5 mol of silver, heated to 50 DEG C., and left to stand for 4 hours with stirring.

Next, sodium thiosulfate and chloroauric acid were added to this to perform optimal chemical ripening. Furthermore, an emulsion of EM-6 which was not subjected to heat treatment was also chemically ripened to form EM-6'. Before the end of the chemical ripening, 3.0% of the sensitizing dye A-7 was added per mole of AgX. 10-' mol of OX was added, compound 5B-5 was
Chemical ripening was completed by adding 1-5X 10-3% Ay per X 1-f nitrogen.

Next, 0.4 mol of the following yellow coupler (Y-1) per 1 mol of AgX and 0.15 mol of the following color stain inhibitor per 1 mol of the coupler, which were simultaneously dispersed with dioctyl phthalate, were added to the above emulsion. A coating solution was prepared.

On a paper support laminated with polyethylene, the coating solution was coated at a coating amount of 0.409/ml as metallic silver and 3.089/ml of gelatin as a protective layer of gelatin. After coating, sample No. 1~
6 was created.

The protective layer contains a hardening agent of 2,4-dichloro-6-hydroxy-S-sodium triazine at 0.00% per gram of gelatin.
Contains 179.

Yellow Coupler Y-1 Color Stain Inhibitor I H Using the prepared samples, fog development and pressure resistance were evaluated.

The test method is to immerse the sample in pure water and lubricate it, then use a needle with a diameter of 0.
．． The surface of the sample was continuously scratched by applying a load to a 5 mm needle, and then the sample was subjected to the color development treatment shown below, and the minimum load at which fogging occurred was measured. Fogging development was carried out by extending the color development process of an unexposed sample piece to twice the time (90 seconds).

[Processing process] Temperature Time Color development 34.7±0.3℃ 45 seconds Bleach fixing 34.7±0.5℃ 45 seconds stabilization
Dry for 90 seconds at 30-34℃ 60-80℃
60 seconds [Color developer] Pure water
800mQ ethylene glycol
lOa+ffN, N-diethylhydroxylamine
109 Potassium chloride 2g
N-Ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 5g Sodium tetrapolyphosphate 2g Potassium carbonate
309 Fluorescent bleach (4,4'-diaminostilbendisulfonic acid derivative) 19 Add water to bring the total volume to IQ, and adjust to pH 10.08.

(Bleach-fix solution) Ethylenediaminetetraacetic acid ferric ammonium dihydrate 609 Ethylenediaminetetraacetic acid 3g ammonium thiosulfate (70% solution) lOOI! IQ ammonium sulfite (4
0% fm liquid) Adjust the pH to 7.1 with 27.5 mff potassium carbonate or glacial acetic acid, and add water to bring the total volume to 1a.

(Stabilizing liquid) 5-chloro-2-methyl4-inthiazolin-3-one 191-hydroxyethylidene-1, todisulfonic acid Add 2 g of water to make 1a, and adjust the pH to 7.0 with sulfuric acid or potassium hydroxide. Adjust to.

The obtained sample was measured using a densitometer PDA・65 (Konica (
Reflection density was measured using a method (manufactured by Co., Ltd.).

The results are shown in Table-2.

Table 2 Comparative samples No. 1 and No. 2 show how the physical ripening emulsion is affected by heating, that is, the fog value (accelerated test of the effect of heating during the manufacturing process and the effect of aging)
is small, but the generation of wet pressure is large.

Comparative samples No. 5 have strong resistance to the generation of wet pressure, but compared to No. J' which was not subjected to heat treatment, the fog increased significantly due to heating, which is not preferable.

In contrast, Sample No. 3.4.5 of the present invention had a low fogging value despite being heat treated, and also had excellent wet pressure resistance, achieving improvements in manufacturing stability and pressure resistance at the same time. It can be seen that it has been done.

In particular, sample No. 4 of the present invention was found to have low bulge and extremely excellent wet pressure resistance.

(Example-2) A silver halide emulsion was prepared by the same operation as EM-4 used in Example-1, but as shown in the table below, various organic compounds were added to Compound 5B used in Example-1. -5 was added in an equimolar amount.

The obtained silver halide emulsion was heated and gold/sulfur sensitized in the same manner as in Example 1 to obtain sensitizing dye A-7 and compound 5B-5.
The chemical ripening was completed by adding 1.5X 10-'' of AgX 10-'' per L-L.

Coated samples were prepared from these emulsions, and fog development and wet pressure tests were conducted.

Table 3 From the above table, samples Nos. 7 to 10 containing organic compounds having a large solubility product with silver ions other than those of the present invention are less than satisfactory in terms of fog and wet pressure #. On the other hand, Sample No. 11-19 of the present invention had sufficient fogging resistance and was also extremely excellent in wet pressure resistance, and was found to have achieved the object of the present invention.

(Example-3) 2.2% gelatin aqueous solution 400 with temperature set at 40°C
18.5 mQ of the seed emulsion used in Example-1 was dispersed in the ran, and 334 mA of 3 M-AgNOs and 0.3 mQ of the seed emulsion used in Example-1 were dispersed.
3M-NaCff aqueous solution containing ff% KBr 3341
pAg7.0 by Chondrold double jet method
, while controlling the pH to 5.85.

Immediately after the addition was completed, Exemplary Compound 5B-5 (solubility product with silver ion (pksp) 14.0) was added in an amount shown in Table 4, and stirred for 5 minutes. The obtained silver halide emulsion was
Desalting was performed using a precipitant, and additional ossein gelatin was added for redispersion.

As a result of electron microscopy, the average grain size of this emulsion was 0.7 μm.
The particle size distribution consisting of m cubic grains was a monodisperse emulsion with a coefficient of variation of 9.5%.

Next, amounts containing 0.5 mol of silver each were sampled from these emulsions, heated to 50° C., and left for 4 hours with stirring.

Next, the above emulsions, including those not subjected to heat treatment, were optimally chemically ripened by adding sodium thiosulfate and chloroauric acid.
12 and the following sensitizing dye RB-1 was added at 2.6X 10-' mol per 1 mol of Agx, and compound 5B-1 was added to Ag
The chemical ripening was completed by adding 1.3×10 −3 mol per 1 mol.

The rest of the experiment was conducted in the same manner as in Example-1.

Table 4 Sensitizing Dye RB-1 From Table 4, regarding the addition amount of the compound 5B-5 of the present invention, sample No. 20.21.26.27, which had a small amount, had poor fog suppression properties and wet pressure resistance. However, the preferred addition amount is sample No. 22°23.
It can be seen that samples No. 24, 25.28, and 29.30 have good levels of antifogging properties and wet pressure resistance, and fully exhibit the effects of the present invention.

Regarding the sensitizing dyes, both A-12 and RB-1 are equivalent in terms of exerting the characteristic effects of the present invention, but A-1 is superior in terms of fogging value and wet pressure resistance level.
It was found that No. 2 is a more preferable sensitizing dye.

(Example 4) A silver chlorobromide emulsion having a silver chloride content of 99.7 mol % was prepared according to Example 3 by changing the amount of the seed emulsion used in Example 1. Each has an average particle size of 0.7 μm.

They were 0.4 μm and 0.35 μm.

After adding the AgNOS solution and the KBr/NaCQ solution, this emulsion was mixed with exemplified compound 5 as shown in the table below after 3 minutes.
B-5 was added to each, stirred for 5 minutes, and then redispersed.

The obtained emulsion was subjected to heat treatment, with heat treatment (50℃
A blue-sensitive emulsion, a green-sensitive emulsion, and a red-sensitive emulsion were prepared by changing the sensitizing dye as shown in the table below.

Table 5 Using these emulsions, multilayer coating samples corresponding to color vapor were prepared with the configuration shown in Table 6. The obtained sample was subjected to the same test as in Example-3.

Table-6 The results obtained are shown in Table-7.

Table 7 Blue-sensitive emulsions, green-sensitive emulsions, and red-sensitive emulsions prepared according to the structure of the present invention show almost no fogging even under forced deterioration conditions due to heating, and have extremely excellent resistance to wet pressure. It is clear from Table 7 that this is an excellent color paper.

Claims (1)

[Claims] The solubility product (K_S_P) with silver ions during the formation process of silver halide grains contained in a silver halide photographic emulsion, from when the grain size reaches 4/5 or more of the final grain size until the end of the redispersion process. 1. A method for producing a silver halide photographic emulsion, which comprises adding at least one compound selected from organic compounds having a solubility characteristic of 1×10^-^1^1 or less.