JPH04157449A - Silver halide photosensitive material for color photograph - Google Patents

Abstract

PURPOSE:To secure the superior speedy treatment performance and the stable reproducibility of gradation by allowing the silver halide particle having the smaller average particle diameter to adsorb the stabilizing agent having the larger complex body solubility product (pksp) with the silver salt. CONSTITUTION:At least one layer of the silver halide emulsifier layers cotains single dispersion silver halogenide particles each of which has an average particle diameter of 0.05mum or larger and has a silver chloride content of 90 mol% or more, and the stabilizer having the larger complex compound solubility product with the silver salt is adsorbed on the silver halogenide particle having less average particle diameter. When the content of the silver chloride is kept within a range of 99.0-99.9mol%, the speedy treatment performance can be satisfied at the same time. Further, the compound having the larger particle diameter of the pksp value is adsorbed on the blended silver halide particle having less average particle diameter, and when the compound having the larger pksp value is added and adsorbed on the particle having the larger average particle diameter, the reduction of sensitivity and softening of gradation are generated. Accordingly, the superior speedy treatment performance is secured, and the reproducibility of the gradation can be improved drastically.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a silver halide light-sensitive material, and particularly to a silver halide color photographic light-sensitive material for direct viewing.

[Prior art]

The gradations of silver halide photographic light-sensitive materials, particularly light-sensitive materials for direct viewing, are required to have characteristic curves with good continuity from highlight areas to halftone areas and shadow areas. For example, on prints, if the reproduction of the highlights is insufficient, the delicate shadows and textures of a white dress will not appear, and on the other hand, if the reproduction is too high, the reproduction will be muddy or lack sharpness. A delicate design is required.

This also applies to halftone parts and shadow parts, and especially in the case of color prints, Y, M, C3
The balance of layer characteristic curves is important for tone reproduction and color reproduction.

As a technique for arbitrarily controlling gradation, a technique of blending two or more types of emulsions with different average grain sizes is conventionally known.
No. 16, No. 57-150841, No. 57-58137
No. 58-14829, etc. According to this, it is possible to design any characteristic curve by mixing several types of emulsions.

On the other hand, in recent years, rapid processability has been desired for photosensitive materials for color photographic paper in order to finish large quantities of prints in a short delivery time.

As one method, it is known to speed up color development by using a silver chloride emulsion or a silver chlorobromide emulsion with a high silver chloride content as a silver halide emulsion. For example, U.S. Patent Nos. 4,183,756 and 4,225
, No. 666, JP-A-55-26589, JP-A No. 58-91
No. 444, No. 58-95339, No. 58-94340
No. 58-95736, No. 58-106538,
No. 58-107531, No. 58-107532, No. 58-107533, No. 58-108533, No. 5
No. 8-125612 and the like have descriptions regarding the above technology.

However, silver chloride emulsions or silver chlorobromide emulsions with a high silver chloride content have extremely fast development progress, so when the above-mentioned blended emulsion is made, the development progress of each grain is affected by the difference in average grain size. The problem was that there were differences and the gradation was likely to fluctuate.

In particular, it has been found that when the pH of the developer fluctuates, a portion of the shadow collapses or a two-step curve occurs, resulting in a significant deterioration of gradation reproducibility.

[Purpose of the invention]

An object of the present invention is to provide a silver halide color photographic light-sensitive material mainly composed of silver chloride, which has excellent rapid processability and stable gradation reproducibility even when processing conditions such as pH fluctuate. .

[Structure of the invention]

The above object of the present invention is to provide a silver halide color photographic material having at least one silver halide emulsion layer on a support, in which at least one of the silver halide emulsion layers has a silver chloride content of 90 mol% or more. It is silver chlorobromide containing monodisperse silver halide grains each having an average grain size different by 0.05 μI or more, and the silver halide grains have a smaller average grain size, the more the complex with the silver salt. Solubility product (pks
This is achieved by using a silver halide color photographic material to which a stabilizer with a large p value is adsorbed.

The present invention will be explained in detail below.

In the silver halide photographic light-sensitive material of the present invention, the silver halide grains contained in at least one of the silver halide emulsion layers are high chloride silver halide grains having a silver chloride content of 90 mol% or more, and further, The preferable silver chloride content for the effects of the present invention is in the range of 99.0 to 99.9 mol %, which satisfies the effects of the present invention and rapid processability at the same time.

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 grain is φ 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 particle 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 and sensitivity, it is preferably 0.2 to 1.6 μm1, and more preferably 0.25 to 1.6 μm. The range is 1.2 μm. The particle diameter can be measured by various methods commonly used in the technical field. A typical method is Loveland's "Particle Size Analysis Method J A, S, T, M
, Symposium on Light Microscopy 19
55, pp. 94-122 or "Theory of Photographic Process" co-authored by Mies and James.

It is described in Chapter 2 of the 3rd edition, published by Macmillan (1966). 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.

It is essential that the grain size distribution of the silver halide grains according to the present invention be monodisperse; polydisperse grains do not exhibit the effects of the present invention. Monodisperse refers to silver halide grains having a coefficient of variation of 22% or less, more preferably 15% or less in the grain size distribution. Here, the coefficient of variation is an amount expressed as a percentage of the standard deviation of the particle size distribution divided by the average particle size (arithmetic mean value of particle sizes).

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. be.

The silver halide grains according to the present invention are monodisperse silver halide grains, and a desired gradation can be obtained by blending silver halide grains each having an average grain size different by 0.05 μm or more. If the difference in average grain size is smaller than 0.05 .mu.m, the gradation will be similar to that of a single layer without blending of emulsions, and the effect of the present invention of obtaining the desired gradation will not be achieved.

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 making and growing the seed particles may be the same or different.

Further, the method for reacting the soluble silver salt with the soluble halogen salt may be a forward mixing method, a back mixing method, a simultaneous mixing method, a combination thereof, or preferably one obtained by a simultaneous mixing method. Furthermore, as a form of simultaneous mixing method,
It is also possible to use the I) Ag-controlled double jet method described in No. 48521 and the like.

Furthermore, if necessary, a silver halide solvent such as thioether,
Alternatively, a crystal habit control agent such as a mercapto group-containing compound or a sensitizing dye may be used.

Any shape of the silver halide grains according to the present invention can be used. One preferable example is a cube having a 1001 plane as a crystal surface.

Also, U.S. Patent Nos. 4,183,756 and 4,225,6
No. 66, JP-A-55-26589, JP-A-55-42
No. 737 and The Journal of 7 Otographic Science (J, Photogr, 5ci) 21.
It is also possible to prepare particles having octahedrons, tetradecahedrons, and dodecahedrons by the method described in 39 (1973), etc., and use them. 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,
Adding metal ions using lead salts, thallium salts, iridium salts or complex salts, rhodium salts or complex salts, iron salts or complex salts,
They can be included inside the particles and/or on the particle surfaces, and by placing them in a suitable reducing atmosphere, reduction sensitizing nuclei can be provided inside the particles and/or on the particle surfaces.

In the emulsion of the present invention, unnecessary soluble salts may be removed after the growth of silver halide grains is completed, or they may be left contained. In the case of removing the salts, the method described in Research 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.

The silver halide emulsion according to the present invention can be produced by a reduction sensitization method using a reducing substance, a noble metal sensitization method using a noble metal compound, or the like.

In the present invention, a chalcogen sensitizer can be used. The chalcogen sensitizer is a general term for sulfur sensitizers, selenium sensitizers, and tellurium sensitizers, and sulfur sensitizers and selenium sensitizers are preferred.

Examples of the sulfur sensitizer include thiosulfate, allylthiocarbamide thiourea, allyl isothiacyanate, cystine, p-toluenethiosulfonate, and rhodanine. Other US patents.

574.944, 3,656.955, German Patent No. 1,422,869, Japanese Patent Publication No. 56-24937,
Sulfur sensitizers described in JP-A-55-45016 and the like 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 AgX particle size, but as a guide, 10-
7 to 10-1 mol is preferred.

In the present invention, it is preferable to use a compound containing gold in combination with a sulfur sensitizer.

The gold sensitizer (gold-containing compound) for the gold sensitization described above may have an oxidation number of +1 or +3, and gold compounds commonly used as gold sensitizers can be used. Typical examples include chlorauric acid salt, potassium chloroaurate, auric trichloride, potassium auric thiocyanate, potassium iodoaurate, tetracyanoauric acid, ammonium aurothiocyanate, pyridyl trichlorogold, and the like.

The amount of gold sensitizer added varies depending on various conditions, but the amount of gold compound added is 5% per mole of silver halide.
X 10-' to 5 X 10-'' moles are preferred, and 2
More preferably, X 10-6 to l X 10-', 2
．． More preferred is 6X 10-' to 4X 10-' moles.

In the preparation method of the present invention, the temperature for chemical ripening is arbitrary as long as the desired sensitization is achieved, but it is preferably 90°C to 20°C, more preferably 80°C to 30°C.
C, particularly preferably 70°C to 35°C.

The silver halide grains according to the present invention have a complex solubility product (
Compounds (stabilizers) with different pksp values are added and adsorbed, and the silver halide grains to be blended are characterized in that the smaller the average particle diameter, the more compounds with larger pksp values are adsorbed. When a compound with a large pksp value is added and adsorbed to particles with a large average particle size, the development progress of particles with a large average particle size tends to be slow, so a decrease in sensitivity or a softening of the gradation may occur. I don't like it.

“New Experimental Chemistry Course Volume 1” for measuring and calculating complex solubility products
(published by Maruzen), pages 233-250, the pH at the time of complex formation where the stabilizer reacts with silver ions can be adjusted to either an acidic range (equivalent to emulsion rjH) or an alkaline range (developing solution pH).
It can be determined by adjusting the potential difference for a region close to .

In the present invention, any stabilizer can be used, but preferably a mercapto compound represented by the following general formula C3).

General formula [S] ,Q,.

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

The mercapto compound represented by the general formula C3) which is preferably used as the organic compound of the present invention will be described below.

In the general formula (S), 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 of the ring include an imidazole ring, a tetrazole ring, a thiazole ring, an oxazole ring, a selenazole ring, a benzimidazole ring, a naphthothiazole ring, a benzothiazole ring, a naphthothiazole ring, a benzoselenazole ring, a naphthoselenazole ring, and a benzoxazole ring. Examples include.

Examples of the cation represented by M include alkali metal ions (e.g., sodium ions, potassium ions, etc.),
Examples include ammonium groups.

The mercapto compound represented by the general formula (S) can further include the following general formula (SA), C3BI, C5C, ] and [SD'l
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 carpoquine group or its salt, a sulfo group or its salt, or an amine group, and Z
represents -NH-, -0- or -3-, M is the general formula C5
) is synonymous with M in ).

General formula C5B) Ar 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 amine group, an acylamino group, a carbamoyl group, or a sulfonamide group. .

n represents an integer of 0 to 2. M is a general formula [M in SD
is synonymous with

In the general formula (SA:] and CSB:l, 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 chloride. Examples include salts, ammonium salts, and the like.

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.

Examples of the anrulamino group represented by RB in the general formula (SB) include methylcarbonylamino group and benzoylamino group, examples of carbamoyl group include ethylcarbamoyl group and phenylcarbamoyl group, and examples of sulfonamide group include Examples include methylsulfonamide group and phenylsulfonamide group.

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

General formula (SC) -N. RAlt represents a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, a cycloalkyl group, -5RA, a group,
RAl is a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, -coRA4 or -302R
RA2 and RA each represent a hydrogen atom, an alkyl group or an aryl group, and RA4 and RAS each represent an alkyl group or an aryl group.

M has the same meaning as M in general formula [s].

General formula [sc] RAI RAII RAII
The alkyl groups represented by RA31RA4 and RAM are:
Examples of the aryl group include a methyl group, a benzyl group, an ethyl group, a propyl group, and the like, and examples of the aryl group include a phenyl group and a naphthyl group.

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

Further, the heterocyclic group represented by RA includes, for example, a furyl group and a hyridinyl group.

The above RA1RA1+RA2. RA3. RA4 and RAS
Alkyl groups and aryl groups represented by RA and RAl
The alkenyl group and cycloalkyl group represented by these, and the heterocyclic group represented by RA further include those having a substituent.

General Formula (SD) In the formula, RA and M represent the same groups as RA and M in the general formula (SC), respectively. In addition, R8□ and RB2 are RAl and RA2 in the general formula CSC), respectively.
represents a group synonymous with

Furthermore, RBI and R8□ may be bonded to each other to form a ring.

Table 8 shows specific examples of compounds represented by the general formula [SD, but the present invention is not limited thereto.

The compound represented by the above general formula [S] is, for example,
No. 0-28496, JP 50-89034, Journal of Chemical Society (J, Chem, So
c, ) 49, 1748 (1927), 42378
(1952), Journal of Organic Chemistry (J, Org, Chem,) 39, 2469 (
1965), U.S. Patent No. 2,824,001, Journal of the Chemical Society, 1723 (195
1), Japanese Patent Application Publication No. 56-111846, British Patent No. 1,27
No. 5,701, U.S. Patent No. 3,266.897, No. 2,
403,927, etc., and can be synthesized according to the methods described in these documents.

A compound represented by the general formula [S] according to the present invention (hereinafter referred to as compound C3) is incorporated into a silver halide emulsion layer containing silver halide grains according to the present invention. teeth,
It may be added after being dissolved in water or an organic solvent optionally miscible with water (for example, methanol, ethanol, etc.). Compound (S) may be used alone or may be represented by general formula C3)
A combination of two or more compounds represented by, or general formula [S]
It may be used in combination with other stabilizers or antifoggants other than those shown.

Compound C5) may be added at any time from the time of silver halide grain formation to the time of coating, but preferably from after the grain formation to the end of chemical sensitization.

Compound [S] may be added in its entirety at one time, or
It may be added in multiple portions.

There is no particular restriction on the amount added, but it is usually 1 x 10-' to 1X10-' mol per 1 mol of silver halide,
It is preferably added in a range of 1xio-' to 1X10-2 mol.

The type of compound [S] is changed in emulsions having different average grain sizes, and the amount of each addition may be optimally adjusted within the range of the amount added above.

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, a super sensitizer, which is a dye that itself does not have a spectral sensitizing effect, or a compound that does not substantially absorb visible light, and which enhances the sensitizing effect of the sensitizing dye, is contained in the emulsion. You can.

When the silver halide emulsion according to the present invention is used as a blue-sensitive emulsion, it is preferably spectrally sensitized with a sensitizing dye represented by the following general formula [A].

General formula [A] In general formula [A], Zl and z2 each represent a benzoxazole nucleus, a naphthoxazole nucleus, a benzoselenazole nucleus, a naphthoselenazole nucleus, a benzothiazole nucleus,
Represents an atomic group necessary to form a naphthothiazole nucleus, benzimidazole nucleus, naphthoimidazole nucleus, pyridine nucleus, or quinoline nucleus, and these heterocycles include those having substituents. The substituent of the heterocycle formed by Zl and Z2 is a halogen atom, a cyano group, a methyl group, an ethyl group, a methoxy group, or an ethoxy group.

R1 and R2 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. 4 sulfoalkyl. Further, R is selected from a hydrogen atom, a methyl group, and an ethyl group. Xθ represents an anion, and Q represents O or l.

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

General Formula [A'] Here, Yl and Y2 each represent an atomic group which may be substituted and is necessary to complete a benzene ring or a naphthalene ring. The benzene ring and the 7-talene ring include those having a substituent, and the substituent is preferably a halogen atom,
An ano group, a methyl group, an ethyl group, a methoxy group, or an ethoxy group.

R,, R2, R,, X'' and Q are the same as those shown in general formula [A].

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 following general formula CB.

General Formula [B] In General Formula CB), zl and Z1□ each represent an atomic group necessary to form a benzene ring or a naphthalene ring condensed to an oxazole ring. The heterocyclic nucleus formed may be substituted with various substituents, and these preferred substituents are halogen atoms, aryl groups, alkyl groups or alkoxy groups. A more preferred substituent is a halogen atom, a phenyl group or a methoxy group, and the most preferred substituent is a phenyl group.

According to a preferred embodiment of the present invention, Zll and zl2 are both benzene rings fused to an oxazole ring, and at least one of these benzene rings has a
The position is substituted with a phenyl group, or the 5-position of one benzene ring is substituted with a phenyl group.
The benzene ring is substituted with a phenyl group at the 5-position, and a halogen atom at the 5-position of the other benzene ring.

R and R+□ each represent an alkyl group, an alkenyl group or an aryl group, preferably an alkyl group. More preferably, R11 and R12 are each an alkyl group substituted with a carboxyl group or a sulfo group, most preferably a sulfoalkyl group having 1 to 4 carbon atoms. Most preferred is a sulfoethyl group.

R1! represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, preferably a hydrogen atom or an ethyl group.

Examples include anions such as C2H, So, -, and the like. m represents l or 0. However, when the compound forms an inner salt, m represents 0.

When the silver halide emulsion according to the present invention is used as a red-sensitive emulsion, spectrally sensitized with a sensitizing dye represented by the following general formula (C) or a sensitizing dye represented by the following general formula [D]. is preferred. Particularly preferred sensitizing dyes are compounds represented by the general formula CD).

General formula CC) (Xe)n-+ General formula CD) (Xe)n-+ In general formula (C) and general formula [D], R2° represents a hydrogen atom or an alkyl group, and R1-R6 each represent Represents an alkyl group or an aryl group, and Z2□.

Z2□, Z24 and Z25 each represent an atomic group necessary to form a benzene ring or naphthalene ring fused to a thiazole ring or selenazole ring, and zl3 represents a hydrocarbon atomic group necessary to form a 6-membered ring. , n represents 1 or 2, Z represents a sulfur atom or a selenium atom, and Xe represents an anion.

In the above general formula, the alkyl group represented by R includes a methyl group, an ethyl group, and a propyl group, and R2° is preferably a hydrogen atom, a methyl group, or an ethyl group. Particularly preferred are a hydrogen atom or an ethyl group.

R11+ R22+ R23 and R24 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 , carboxyethyl, ethoxycarbonylmethyl, sulfoethyl, sulfopropyl, sulfobutyl, β-hydroquine-γ-sulfopropyl, sulfate furovir, allyl, benzyl, etc.) and aryl groups (this aryl group has a substituent). For example, phenyl, carboxyphenyl,
Z21+ z22+ Z 2a or z2sr=yoF) The heterocyclic nucleus to be subjected to MR may have a substituent, and the preferable substituent is a halogen atom. , aryl group,
It is an alkyl group or an alkoxy group, and more preferably a halogen atom (for example, a chlorine atom), a phenyl group, or a methoxy group.

X0 anion (for example, CQ-1Br-1!-1 represents 1 or 2).

However, when the compound forms an inner salt, a represents 1.

Table-B shows general formulas (A) and C that are preferably used in the present invention.
Typical specific examples of the sensitizing dye represented by B), [:C] or [D] are shown below.

The amount of the sensitizing dye represented by the above general formula [:A), [B], I:c] or [D] is not particularly limited, but is approximately lXl0-' to lx10-' per mole of silver halide. '
It is preferably used in a molar range, more preferably 5
X 10-' to 5 X 10-' moles.

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), and in some cases diluted with water; 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 disclosed in U.S. Patent No. 3,46
As described in Japanese Patent Publication No. 9,987, a method of dissolving a dye in a volatile organic solvent, dispersing the solution in a hydrophilic colloid, and adding this dispersion, 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.
No. 605, No. 2,996.287, No. 3,425.8
The method described in No. 35 and the like can also be used.

The sensitizing dyes contained in the silver halide emulsion according to 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. You may. When adding them separately, the order, time and interval can be arbitrarily determined depending on the purpose.

The timing of adding the sensitizing dye used in the present invention to the emulsion is as follows:
It may be added 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 silver halide photographic light-sensitive material of the present invention having the above structure can be used, for example, as a color negative film, a positive film, or a color photographic paper. In such cases, the effects of the method of the present invention are effectively exhibited.

The silver halide photographic material of the present invention, including this color photographic paper, may be for monochrome use or for multicolor use. In the case of multicolor silver halide photographic materials, in order to perform subtractive color reproduction, a photographic coupler is usually used.
It has a structure in which a silver halide emulsion layer containing magenta, yellow, and yellow couplers and a non-light-sensitive layer are laminated on a support in an appropriate number and order of layers. may be changed as appropriate depending on the important performance and purpose of use.

When the present invention is applied to a multicolor light-sensitive material, the specific layer structure includes, on a support, a yellow dye image forming layer, an intermediate layer, a magenta dye image forming layer,
Particularly preferred is an arrangement consisting of an intermediate layer, a dye image forming layer, an intermediate layer, and a protective layer.

The dye image-forming coupler used in the silver halide light-sensitive material of 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. Ru.

Yellow dye image-forming couplers include a/lylacetamide type couplers and benzoylmethane type couplers, and these are described, for example, in U.S. Pat.
, No. 057, No. 2,908,573, No. 2,908,
No. 513, No. 3,227.155, No. 3,227.5
No. 50, No. 3,253.924, No. 3,265,50
No. 6, No. 3,277.155, No. 3,341,331
No. 3,369,895, No. 3,384,657, No. 3,408.194, No. 3,415,652,
German Patent No. 3,447,928, German Patent No. 3,551,155, German Patent No. 3,582,322, German Patent No. 3,725,072, German Patent No. 1,547.868, German Patent No. 2,057.941, 2.162.899, 2,163.812,
No. 2,213,461, No. 2,219,917, No. 2261.361, No. 2,263.875, Japanese Patent Publication No. 49-13576, Japanese Patent Publication No. 29432-1972, No. 48- No. 66834, No. 49-10736, No. 49-
No. 122335, No. 50-28834, No. 50-13
No. 2926, No. 55-144240, No. 56-870
It is described in No. 41.

Magenta dye image-forming couplers include 5-pyrazolones, pyrazolotriazoles, pyrazolinobenzimidazoles, indasilones, and anoacetyl couplers, such as those described in U.S. Pat.
No. 8, No. 3,061,432, No. 3,062゜653
No. 3,127,269, No. 3,311,476, No. 3,152゜896, No. 3,419.391,
3.519.429, 3.558.

No. 318, No. 3,684,514, No. 3,705,8
No. 96, No. 3.888゜680, No. 3,907,57
No. 1, No. 3.928.044, No. 3,930°861
No. 3,930,816, No. 3,933,500, JP-A No. 49-29639, No. 49-111631, No. 49-12953'8, No. 51-112341, No. 52-58922 No. 55-62454, No. 5
No. 5-118034, No. 56-38643, No. 56-
No. 135841, Special Publication No. 46-60479, No. 52-
No. 34937, No. 55-29421, No. 55-356
96, British Patent No. 1,247,493, Belgian Patent No. 769,116, West German Patent No. 2,156,111, Japanese Patent Publication No. 46-60479, Japanese Patent Publication No. 125732-1980, Japanese Patent Publication No. 59-228252, No. 59-162548,
No. 59-171956, No. 60-33552, No. 6
Publications No. 0-43659, West German Patent No. 1,070,03
No. 0 and US Pat. No. 3,725,067.

Cyan dye image-forming couplers include phenolic,
It is a typical naphthol coupler, and US patents 2 and 3
No. 06.410, No. 2,356,475, No. 2,36
2゜598, 2,367.531, 2.369
, No. 929, No. 2,423゜730, No. 2.474,
No. 293, No. 2,476.008, No. 2.498゜4
No. 66, No. 2,545,687, No. 2,728,66
No. 0, No. 2,772゜162, No. 2,895.826
No. 2,976.146, No. 3, 002.

No. 836, No. 3,419.390, No. 3,446,6
No. 22, No. 3,476゜563, No. 3,737, 31
No. 6, No. 3,758,308, No. 3,839゜044
British Patent No. 478.991, British Patent No. 945.542,
1,084.480, 1,377.233, 1,388,024, and 1.543,040, as well as JP-A-47-37425 and JP-A-50-1.
No. 0135, No. 50-25228, No. 50-1120
No. 38, No. 50-117422, No. 50-13044
No. 1, No. 51-6551, No. 51-37647, No. 51-52828, No. 51-108841, No. 53
-109630, 54-48237, 54-6
No. 6129, No. 54-131931, No. 55-320
No. 71, No. 59-146050, No. 59-31953
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 8 or more carbon atoms. Also, these dye-forming couplers only require reduction of two silver ions, even if they are 4-equivalent, requiring reduction of four silver ions to form one molecule of dye. It may be either 2-equivalent.

As the binder (or protective colloid) used in the silver halide photographic light-sensitive material of the present invention, it is advantageous to use gelatin, but other materials include seratin derivatives, graft polymers of gelatin and other polymers, proteins, Hydrophilic colloids such as sugar derivatives, cellulose derivatives, synthetic hydrophilic polymeric substances such as monopolymers or copolymers can also be used.

The silver halide photographic material of the present invention further includes a hardening agent,
Color clouding prevention agent, image stabilizer, ultraviolet absorber, binder,
Additives such as latex, surfactants, matting agents, lubricants, and antistatic agents can be used as desired.

An image can be formed on the silver halide photographic material of the present invention by subjecting it to color development treatment known in the art.

The color developing agent used in the color developing solution in the development of the silver halide photographic light-sensitive material of the present invention is an aminephenol type or a p-phinidine diamine type that is widely used in various color photographic processes. Including derivatives.

In addition to the above-mentioned primary aromatic amine color developing agent, known developer component compounds may be added to the color developing solution applied to the development of the silver halide photographic light-sensitive material of the present invention. .

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

Color development temperature is usually 15°C or higher, generally 2
It is in the range of 0 to 50°C. For quick development, 30°
It is preferable to carry out the test at C or higher. In addition, conventional processing takes 3 to 4 minutes, but the color development time of the silver halide color photographic material of the present invention, which is intended for rapid processing, is generally within 20 to 60 seconds. The time is preferably 30 to 50 seconds, and more preferably 30 to 50 seconds.

After color development, the silver halide photographic material of the present invention is subjected to bleaching and fixing. 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.

〔Example〕

Examples of the present invention are shown below, but the present invention is not limited thereto.

The structural formulas of the additives used in the examples are summarized in Table-
Shown in 〇.

Example 1 On a paper support laminated with polyethylene on one side and polyethylene containing titanium oxide on the other side, each layer having the structure shown below was coated on the side of the polyethylene layer containing titanium oxide. A multilayer silver halide color photographic material was prepared.

The coating solution was prepared as follows.

1st layer coating liquid Yellow coupler (Y-1) 26.7g, dye image stabilizer (ST-1) lo, Og, dye image stabilizer (ST-2) 6.67g, additive (HQ-1) )
0.67g and high boiling point organic solvent (DNP) 6.67
Add and dissolve 60m of ethyl acetate (2) to g and dissolve this solution.
A yellow coupler dispersion was prepared by emulsifying and dispersing the mixture into 220 mQ of a 10% gelatin aqueous solution containing 7 mQ of 0% surfactant (SU-1) using an ultrasonic homogenizer.

This dispersion was mixed with a blue-sensitive silver halide emulsion (containing 10 g of silver) prepared under the following conditions to prepare a first layer coating solution.

The second to seventh layer coating solutions were also prepared in the same manner as the first layer coating solution.

Further, as a hardening agent, (H-1) was added to the second layer and the fourth layer, and (H-2) was added to the seventh layer. As coating aids, surfactants (SU-2), (SU-3) and DOP
: Dioctyl phthalate DIDP: Diisodecyl phthalate PVP : Polyvinylpyrrolidone D
NP: dinonyl 7-thaletate DBP: dibutyl phthalate (preparation method of blue-sensitive silver halide emulsion) The following (liquid A) was added to 1000 nJ of a 2% gelatin aqueous solution kept at 40°C.
and (Liquid B) were simultaneously added while controlling pAg = 6.5 and pH = 3.0 while changing the addition time as shown in Table 1,
Furthermore, the following (solution C) and (solution D) were adjusted to pAg=7.3, p
They were simultaneously added over 180 minutes while controlling the H-5.s.

At this time, pAg was controlled by the method described in JP-A-59-45437, and pH was controlled using an aqueous solution of sulfuric acid or sodium hydroxide.

(Liquid A) Sodium chloride 3.42g Potassium bromide 0.03g Add water and make 200mQ (Liquid B) Silver nitrate Add 10g water and make 200m (2 (Liquid C) Sodium chloride 102.7g Potassium bromide l-OgK z (
IrC(1,) 6 x 10-' mol 1 mol AgX Add water and 600 m(
2 (Liquid D) Add 300 g of silver nitrate to water. After adding 600 m+1, desalt using a 5% aqueous solution of Demol N manufactured by Kako Atlas Co., Ltd. and a 20% aqueous solution of magnesium sulfate, and then mix with an aqueous gelatin solution. As shown in Table 1, monodisperse cubic emulsions EMP-1 to EM with different average grain sizes, coefficient of variation (σ/r) -0.07, and silver chloride content of 99.5 mol% were used.
P-3 was obtained.

The above EMP-1 to EMP-3 were chemically ripened for 90 minutes at 50° C. using the following compounds to obtain blue-sensitive silver decagenide emulsions (EmB-1-EmB-28).

The blue-sensitive layer had the emulsion composition of the above EmB emulsion alone or as a blend (5 and 5, respectively).

Sodium thiosulfate 0.8 mg 1 mol 1 mol A Auric acid 0.5 mg 1 mol 1 mol A fixer Listed in Table-2 6X to-' mol/mol Ag
X sensitizing dye B5-15X10-4 mol 1 mol Agx (
Preparation method of green-sensitive silver halide emulsion) The average grain Diameter 0.43
A monodisperse cubic emulsion EMP-2 with a μm1 variation coefficient (σ/r)=0.08 and a silver chloride content of 99.5 mol% was obtained.

For EMP-2, the following compound was used at 55 °C for 12
A green-sensitive silver halide emulsion (Em-
G) was obtained.

Sodium thiosulfate 1.5 mg 1 mol 1 mol A Auric acid 1.0 mg 1 mol 1 mol A fixative SB-55x 10-4 mol/-F-ru Ag
X sensitizing dye B -54x 10-' mol 1 mol AgX
(Preparation method of red-sensitive silver halide emulsion) (Liquid A) and (B
The average particle size was 0.5 in the same manner as EMP-1 except for changing the addition time of liquid) and the addition time of (liquid C) and (liquid D).
A monodispersed cubic emulsion EMP-3 having a coefficient of variation (σ/r) of 0 μm1 and −0.08 and a silver chloride content of 99.5 mol % was obtained.

90°C at 60°C using the following compound for EMP-3.
A red-sensitive silver halide emulsion (E■-R
) is obtained.

Sodium thiosulfate 1.8mg/mol AgX
Chloroauric acid 2. Qmg/mol AgX
Stabilizer SB-55x IQ-'-E-ru 1 mol Ag
X-sensitizing dye D-61

Processing process Temperature Time Development color development 3
Bleach fixing at 5.0±0.3°C for 45 seconds 35.0±0.
5°045 seconds stabilization 30-34°C 90 seconds drying 60-80°C 60 seconds Color developer Pure water 800m12 triethanolamine

lOgN, N-diethylhydroxylamine
5g potassium bromide 0.
02g Potassium chloride 2g Potassium sulfite 0.3g 1-Hydroxythiethylene 1.1-diphosphonic acid 1.0g Ethylenediaminetetraacetic acid 1.0g Catechol-3
,5-disulfonate disodium l・0gN-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-amine aniline sulfate
4.5g Fluorescent brightener (4,4'-diaminostilbendisulfonic acid derivative) 1.0g Potassium carbonate 27g Add water to bring the total amount to 112, and adjust the pH to -10.10. At this time, use sulfuric acid and potassium hydroxide to adjust the pH to 9, 8, 1.
Color developing solutions of 0, 1, 10, 3, 10, and 5 were also prepared.

Bleach-fix solution Ferric ammonium dihydrate ethylenediaminetetraacetic acid 60g ethylenediaminetetraacetic acid 3g ammonium thiosulfate (70% aqueous solution) 100m + 2 ammonium sulfite (40% aqueous solution) 27.5m12 Add water to bring the total volume to 1a, add potassium carbonate or glacial acetic acid at pH = 5
．． Adjust to 7.

Stabilizing liquid 5-chloro-2-methyl-4-isothiazolin-3-one 1.0 g ethylene glycol 1.0 g 1-hydroxyethylidene-1,1-diphosphonic acid 2.0 g ethylenediaminetetraacetic acid 1.0 g ammonium hydroxide (20 % aqueous solution) 3.0g optical brightener (4
, 4'-diaminostilbendisulfonic acid derivative)
Add 1.5 g of water to make the total amount Iff, and adjust p+ (-7.0 with sulfuric acid or potassium hydroxide).

The density of the treated sample was measured using a photoelectric densitometer equipped with B7 (Luther), and the gradation values calculated from the obtained values are shown in Table 2.

*γ1: Slope of the sensitometric curve at a concentration of 0.8 to 1.6 (tan value) γ2: Slope of the sensitometric curve at a concentration of 0.3 to 0.8 (tan value) Furthermore, the obtained sample was to increase the pt+ of the color developer to 1
Prints were produced using a processing solution adjusted to 0.1, and the gradation reproducibility was visually checked.

○: Smooth depiction from highlight to shadow.

×: Unsatisfactory depiction with blown highlights and crushed shadows.

From Table 2, samples coated with single emulsion (No. 1 to 12)
) is relatively less gradation variation (
γ1. γ2) is stable, but the gradation reproducibility in print evaluation is poor because of the high contrast. On the other hand, when the emulsions are blended, γ1. Samples outside the present invention (NO, 13 to 16), which have a small difference in average particle diameter, have a soft tone in both γ2, but the degree of soft tone is small, and the gradation reproducibility is poor. Average particle size is 0.
Sample blended with emulsions separated by 0.05 μm or more (No. 1
Samples No. 7 to 28) are excellent in that they have a large softening of gradation and improved depiction on prints, but samples (No. 1
9.20.25.26), the gradation fluctuations due to pn fluctuations are significantly large and lack stability.

In contrast, the sample of the present invention (No. 17°18
, 21 to 24, 27, and 28) had small variations between processing solutions and good gradation reproducibility on prints, and were found to be overall excellent color photosensitive materials.

Example 2 Blue-sensitive silver chlorobromide emulsions EMP-1 and EM used in Example 1
P-3 is used to convert the sensitizing dye during chemical ripening into Exemplary Compound A
-1(l x 10-' mol/mol AgX) and a
A-12 (4X IQ-' mol/mol Ag
2, respectively 9. Qx 10-'%/L=/mol AgX and 8.5X 10-'mol 1 mol AgX added.

As shown in Table 3, each blended emulsion was coated with the same layer structure as in Example 1 by changing the type of stabilizer, and sensitometry was performed using a color developer with a changed pH and the same method as in Example 1 was carried out. A print evaluation was performed.

The results are shown in Table-3.

From Table 3, the single emulsion systems (sample Nos. 29 to 38) are as follows:
Example 1 was reproduced, and the gradation variation with respect to pH change was relatively good, but the gradation was hard, the highlights were skipped on the print, and the shadows were crushed, and the gradation reproducibility was poor. Ta.

On the other hand, blended emulsion systems (sample Nos. 39 to 56)
), the gradation was softened by blending, details in highlights and shadows were well reproduced, and gradation reproducibility was excellent.

However, pksp is applied to the emulsion with a large average grain size (EMP-3).
Sample using a stabilizer with a large value (No, 43.44.4
7°51 to 56), as in Example 1, had large gradation changes due to pH fluctuations and lacked stability.

On the other hand, the sample of the present invention (N
o, 39-42, 45, 46, 48-50), the gradation is stable against pH fluctuations, and it is clear that both image quality and stability are excellent.

In addition, the samples used in both emulsions in which SA'-7, SB-1, and 5B-2, which are preferred compounds for the present invention, are blended with stabilizers Z-1 and Z-2 have gradations. It has been found that the variation is more stable and that the use of SB-1 and SB-2 in particular gives the best results.

Furthermore, in Example 2, a mixture of exemplified sensitizing dyes A-1/A-12 was used, which was found to be more advantageous in sensitivity than the sensitizing dye used in Example 1.

Example 3 In the physical ripening recipe of Example 1, the addition times of (Liquid A) and (Liquid B) were changed as shown in Table 4 to produce silver halide grains having various average particle sizes. Formed and also Table-4
Sodium thiosulfate, chloroauric acid, sensitizing dyes and stabilizers (listed in Table 5) were added and chemically ripened to obtain blue-, green-, and red-sensitive silver halide emulsions.

The obtained silver halide emulsions were each blended at a ratio of 5:5 and coated with the layer structure used in Example 1.2 to prepare a silver halide color photographic material (Sample No. 57.
58).

From Table 5, when using a stabilizer with a large pksp value in an emulsion with a large average grain size, not only blue-sensitive emulsions, but also green-sensitive emulsions and red-sensitive emulsions, the gradation fluctuations due to pH fluctuations are significant. It is clear that it will get bigger. In the case of color photosensitive materials, the gradation balance of the three layers of blue, green, and red is extremely important, but in comparison sample No. 57, the color balance was clearly disrupted due to pH fluctuations, and the gradation reproducibility was poor. It turned out that there was a problem.

On the other hand, sample No. 58 of the present invention, in which a stabilizer with a small pksp value was used in an emulsion with a large average grain size, had small gradation fluctuations with respect to pH fluctuations, and the gradation balance of the three layers was disrupted. It is clear that this is a color photographic material with extremely stable color balance.

Table-A SA-ISA-2 SA-33A-4 -r"), 3゜-r゛>3□ 5A-5SA-6 SA-7SA-8 5B-1sB-2 SB-3SB-4 SB55B-6 SB -7 -N N-N Table-B (CHxhSO3w(CHz)ssOINaHs A-6 A-11 (CHJzSO3” Shiri, Shiuun-
I B-8 Shi2ns Shizn60H・0H
・O)! Uxtls,.

-tO C.H. 0.1.1.C-12 C-13 I C2L　　　　　　　　　(CH2)sSOs.

-I -I 5T-2 ST-3 ST-4 CsH++(t) I3 HQ-I HQ-2HQ-3HQ
-4 Q-5 HBS-1 I-1 I-2 I-3 KOs S KO, SI-4 U-1 U-2 U-3 C(CHzSOzCH-CHz)a

Claims (1)

[Claims] In a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, at least one of the silver halide emulsion layers has a silver chloride content of 90
silver chlorobromide in a mole % or more, each having an average particle size of 0.
Contains monodisperse silver halide grains that differ by 0.05 μm or more,
A silver halide color photographic light-sensitive material characterized in that a stabilizer having a larger complex solubility product (pksp value) with a silver salt is adsorbed to the silver halide grains as the average grain size becomes smaller.