JPH0743521B2 - Silver halide color photographic light-sensitive material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a silver halide color photographic light-sensitive material having high sensitivity and excellent graininess.

(Background Art) In recent years, as a silver halide photographic light-sensitive material, particularly a photographic light-sensitive material, an ultra-high-sensitivity light-sensitive material typified by ISO1600 film has been required. For higher sensitivity,
Various methods have been studied so far, such as increasing the size of silver halide grains, activating couplers and promoting development. To increase the size of silver halide, use the GC funnel (Fa
rnell), JB Chanter, “Journal of Photographic Science”, Vol. 9, page 75 (1961). However, the increase in sensitivity cannot be expected so much, and it is accompanied by various side effects due to the increase in size. For example, increasing the size of silver halide tends to cause deterioration of graininess, increase of thickness of emulsion layer, and deterioration of storage stability. Further, the conventional high-activity couplers and high sensitization due to development acceleration, etc. are accompanied by notable deterioration of graininess, and have a drawback that they do not sufficiently contribute to sensitivity. Regarding the acceleration of development, addition of various development accelerators such as hydrazine compounds to the emulsion layer or the developer, mainly for black and white sensitizers, has been studied so far. Often accompanied by deterioration, it was not practical.

Therefore, a coupler has been proposed which releases a development accelerator or a fogging agent imagewise. For example, U.S. Pat.
No. 618, a coupler releasing an acylhydrazine, JP-A-59-50439 discloses a coupler releasing a thiocarbonyl compound, and JP-A-59-170840 discloses a mercapto-eliminating hydrazine-releasing coupler. No. 158552 describes couplers having adsorbing groups which release fogging agents or development accelerators.

(Problems to be Solved by the Invention) Certainly, these compounds have realized high sensitivity. However, defects such as poor graininess in the low-exposure region have become apparent as compared with those compounds in which the sensitivity is not increased.

On the other hand, some combinations of so-called monodisperse emulsions and functional compounds, which have a small variation coefficient with respect to the grain size of silver halide grains, have been proposed. For example, JP-A-58-100847 proposes the combined use of a monodisperse emulsion and a compound (so-called DIR compound) which releases a diffusible development inhibitor by the reaction of an oxidized product of a color developing agent. When combined with each other, the gradation becomes softer and the sensitivity is further lowered, which expresses a photographic performance which is completely different from that of the present invention, and there is a problem that graininess on the high exposure side, which is a drawback of the monodisperse emulsion, is worsened. Atsuta In addition, JP-A-59-131936 proposes the combined use with a coupler that forms a diffusible dye, but unlike the present invention, this combination does not cause an increase in sensitivity, and the granularity in the high-exposed area does not occur. Does not improve.

Therefore, an object of the present invention is to provide a silver halide color photographic light-sensitive material having high sensitivity and excellent graininess.

(Means for Solving the Problems) The above object of the present invention is to provide a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, and the silver halide grains contained in the emulsion layer. Coefficient of variation S / (S is the standard deviation of particle size,
Is a monodisperse emulsion having at least one type of layered structure having a grain size distribution of 0.25 or less, and having a standard deviation of iodine distribution between grains of 20% or less, And a halogen which is characterized by containing a fogging agent or a development accelerator or a compound which releases a precursor thereof according to the amount of developed silver when the emulsion layer is developed with an aromatic primary amine developing agent. Achieved with silver halide color photographic light-sensitive materials.

The reason why the structure of the present invention improves the sensitivity and the graininess is not clear, but at present, it can be considered as follows.

A compound (hereinafter simply referred to as FR compound) that releases a fogging agent or development accelerator or precursors thereof (hereinafter simply referred to as FA compound) imagewise in accordance with the amount of developed silver.
In the light-sensitive material containing ## STR3 ##, the FA compound released with the development of electrons injects electrons into the undeveloped silver halide grains in the vicinity of the silver halide grains where the development is started, or forms silver sulfide nuclei. By increasing the development starting point, the current state promoting action is brought about, and preferable effects such as an increase in sensitivity, an increase in contrast, and an acceleration in development are exhibited.

With ordinary dispersible silver halide grains, undeveloped grains of a relatively small size in the vicinity of the emulsion grains in which the FA compound released with development has begun development can be developed, and in the high-exposure region In the low-exposure region, the number of particles that start development is small, so a large dye cloud is formed around these particles and it is thought that the graininess deteriorates. .
On the other hand, when the monodisperse silver halide grains of the present invention having a relatively uniform grain size and the FR compound are used together, in the low exposure region, the number of grains that can start development is usually a polydisperse grain size. As compared with the emulsion of No. 1, the deterioration of graininess in the low-exposed area is small. In the high-exposure region, when only monodisperse silver halide emulsions having a relatively uniform grain size are used, only a large dye cloud is aggregated, resulting in uncolorable portions, resulting in grain deterioration (grain loss). However, due to the development-accelerating effect of the FA compound, the disappearance of particles occurs and the particles are improved. Therefore, it is believed that the combination of the present invention improves graininess over the entire exposed area.

The present invention will be specifically described below.

The FR compounds effective in the present invention include the following.

(I) A coupler which couples with an oxidation product of an aromatic primary amine developing agent to release an FA compound. (Ii) A coupler which couples with an oxidation product of an aromatic primary amine developing agent to form a diffusible colored or A coupler that forms a non-coloring dye and the diffusible dye acts as a FA compound. (Iii) An oxidation-reduction reaction occurs with the oxidation product of the developing agent, and a FA compound is generated by a decomposition reaction that follows the oxidation reaction. A redox compound that emits.

The above compounds (i), (ii) and (iii) are represented by the following general formulas [1], [2] and [3], respectively.

[1] Cp-FB [2] FB-Cp-BALL [3] RED-FB In the above formula, the FB group represents-(TIME) m- (L) n-FA. Here, the FA group represents a group capable of fogging silver halide or a group capable of promoting development, L represents a divalent linking group, and TIME represents a timing group. It is particularly preferable when the FA group has a group capable of adsorbing to silver halide. m and n each represent 0 or 1. Further, Cp represents a coupler residue capable of coupling reaction with an oxidation product of an aromatic primary amine developing agent, BALL represents a diffusion resistant group, and RED represents a cross-linkage with an oxidation product of an aromatic primary amine developing agent. Represents a compound residue that can be oxidized.

Each of the general formulas [1], [2] and [3] will be described below.

In the general formula [1], the FB group is a group bonded to the coupling position of the coupler and released during the coupling reaction with the oxidation product of the aromatic primary amine developing agent.

Here, a typical example of a yellow coupler among the couplers is U.S. Pat.Nos. 2,875,057, 2,407,210, and 3,265,50.
6, No. 2,298,443, No. 3,048,194, No. 3,447,928, etc. Of those yellow couplers,
Acylacetamide derivatives such as benzoylacetanilide and pivaloylacetanilide are preferred.

Therefore, as the yellow coupler residue (Cp), those represented by the following general formulas [I] and [II] are preferable.

In addition, * represents a bonding position of the FB group (hereinafter, represented by the general formula [I
X) until the same).

Here, R ₁ represents diffusion resistance having a total carbon number of 8 to 32, R ₂ represents a hydrogen atom, a total of 1 to 9 halogen atoms, a lower alkyl group, or a lower alkoxy group, or a total carbon number of 8 to 32.
Represents a nondiffusible group. When R ₂ is ₂ to 9, they may be the same or different.

A typical example of a magenta coupler is U.S. Pat.
No., No. 2,369,489, No. 2,343,703, No. 2,311,082,
3,152,896, 3,519,429, 3,062,653, 2,9
It is described in No. 08,573. Of these magenta couplers, pyrazolone or pyrazoloazoles (pyrazolopyrazole, pyrazoloimidazole, pyrazolotriazole, pyrazolotetrazole, etc.) are preferable.

Therefore, as the magenta coupler residue (Cp), those represented by the following general formulas [III], [IV] and [V] are preferable.

Here, R ₁ represents a diffusion resistant group having a total carbon number of 8 to 32,
R ₂ represents a halogen atom, a lower alkyl group, a lower alkoxy group, a phenyl group, or a substituted phenyl group. Z
Represents a group of non-metal atoms necessary for forming a 5-membered azole ring containing 2 to 4 nitrogen atoms, and the azole ring may have a substituent (including a condensed ring).

A representative example of a cyan coupler is U.S. Pat.
No., No. 2,895,826, No. 3,002,836, No. 3,034,892,
2,474,293, 2,423,730, 2,367,531, and 3,041,236. Of those cyan couplers, phenols or naphthols are preferable.

Therefore, as the cyan coupler residue (Cp), those represented by the following general formulas [VI] and [VII] are preferable.

In the formula, R ₁ represents an alkyl group, an aryl group, a heterocyclic group, or an amino group, and these groups may be further substituted. Representative examples of the substituted amino group include an arylamino group and a nitrogen-containing heterocyclic group.

R ₂ represents a halogen atom, an alkyl group, an alkoxy group, an acylamino group, or an alkoxycarbonyl group, and these groups may be further substituted. When R ₂ is ₂ to 3, they may be the same or different from each other, and R ₂ is ₂ to each other.
They may be linked together to form a 5- or 6-membered saturated or unsaturated carbocycle or heterocycle. These rings may be further substituted. As the hetero atom forming the hetero ring,
Examples include nitrogen, oxygen, and sulfur. Specific examples of the ring in which the above heterocycle is condensed include 3,4-dihydrocarbostyryl and the like.

R ₃ represents an alkyl group or an aryl group, and these groups may be further substituted.

R ₄ has the same meaning as R _2, and when two R ₄ are linked to each other to form a 5- or 6-membered saturated or unsaturated carbocycle or heterocycle, the groups which may be further substituted on these rings are the same as those mentioned above. The groups listed for R ₂ can be applied, and further, a sulfonamide group and the like can be applied.

In order to impart diffusion resistance to the FR compound having a coupler residue represented by the general formula [VI] or [VII], R ₁ and R ₂ or R ₃
And the total carbon number of R ₄ is preferably 8 to 80.

The FA group is the most basic functional group that expresses the functions of FR compounds. As this group, a reducing compound (hydrazine,
Hydrazide, hydrazone, hydroquinone, catechol, p-aminophenol, p-phenylenediamine,
1-phenyl-3-pyrazolone, enamine, aldehyde, polyamine, acetylene, aminoborane, tetrazolium salt, quaternary salt represented by ethylenebispyridinium salt, carbazic acid, etc.), or a compound capable of forming silver sulfide during development (thio). Such as urea, thioamide, dithiocarbamate, rhodanine, thiohydantoin, thiazolidinethione, And those having a partial structure of 1). Also The partial structure of Due to the tautomeric structure of TIME, Cp or
May be combined with RED.

TIME represents a timing group, which is described in US Pat.
248,962, as described in JP-A-57-56837 and the like, utilizing an intramolecular substitution reaction, British Patent 2,072,363A, JP-A-57-154234, JP-A-57-188035, JP Showa 54-98728
And the like, which utilize electron transfer through a co-injection system in the molecule as described in No.

The divalent linking group represented by L is an alkylene group,
Alkenylene group, phenylene group, naphthylene group, -O
-, - S -, - SO -, - SO 2 -, - N = N-, carbonamido group, thioamide group, a sulfonamido group, a ureido group, a thioureido group and a group selected from the group consisting of heterocyclic group Is used.

The above FA group, TIME, and / or FB group consisting of L,
It is particularly preferable to have a group capable of adsorbing to silver halide (this adsorbable group may be any of FA, TIME, and L). The group capable of adsorbing to silver halide has a nitrogen-containing heterocyclic group having a dissociable hydrogen atom, a heterocyclic group having at least one nitrogen atom and another hetero atom in the ring, and a mercapto group. Heterocyclic group, quaternary salt, thiols, And a group derived from a compound having a partial structure of.

In the general formula [2], the FB group is bonded to the non-coupling position of the coupler. The BALL group is a group which is bonded to the coupling position of the coupler and is released during the coupling reaction with the oxidation product of the aromatic primary amine developing agent. Here, Cp and FB have the same meanings as described in the general formula [1].

The nondiffusible group represented by BALL may have a size and shape that give the coupler nondiffusibility, and may be a polymer having a plurality of leaving groups linked to each other. It may have a group and / or an aryl group. In the latter case, the total carbon number of the alkyl group and / or aryl group is preferably about 8 to 32. BALL has a group for bonding to the coupling position of Cp, and typical examples thereof include -O- and-.
S-, -N = N-, And -N, which constitutes a heterocycle.

In the general formula [3], RED has a skeleton of hydroquinone, catechol, o-aminophenol, or p-aminophenol (both of which include condensed rings), and an aromatic primary amine developing agent. Represents a group that cross-oxidizes with the oxidant of and releases the FB group upon alkaline hydrolysis. RED may have a protecting group (for example, an acyl group) which is eliminated in the developing solution. FB has the same meaning as described in the general formula [1], but when FB is directly connected to the RED benzene ring, -O-, -S-, -N = N-, And linked to RED via any of the groups of -N constituting the heterocycle, and RED is an o-aminophenol or p-
Aminophenol skeleton (including condensed ring)
And FB is not directly linked to their benzene ring, FB is Via (i.e., forming a sulfonamide group).

Next, represented by the general formulas [1], [2], and [3].
Specific examples of FR compounds are shown below, but the invention is not limited thereto.

Examples of compounds represented by the general formula [1] Examples of compounds represented by the general formula [2] Examples of compounds represented by general formula [3] These compounds of the present invention are based on generally known compounds, and are based on JP-A-57-150845, JP-A-57-138636, and US Pat.
4,377, 3,253,924, JP 59-50439, JP 60
-37556, Japanese Patent Application No. 58-214808 and the like.

Of the FR compounds used in the present invention, the preferred one is FB
Group adsorbed to silver halide in the inside (Japanese Patent Application Laid-Open No. 59-158552)
No.) has the same meaning as the adsorptive group defined in No.).

The FR compounds used in the present invention may be a combination of two or more kinds.

To introduce the FR compound of the present invention into the silver halide emulsion layer, a known method such as the method described in US Pat. No. 2,322,027 can be used. For example, phthalic acid alkyl ester (dibutyl phthalate, dioctyl phthalate, etc.),
Phosphoric acid ester (diphenylphosphonate, triphenylphosphonate, tricresylphosphonate, dioctylbutylphosphonate), citric acid ester (eg tributyl acetylcitrate), benzoic acid ester (eg octyl benzoate) , Alkyl amides (eg diethyl lauryl amide), fatty acid esters (eg dibutoxyethyl succinate, diethyl azelate), trimesic acid esters (eg tributyl trimesate), etc., or an organic solvent having a boiling point of about 30 ° C. to 150 ° C., For example, it is dissolved in a lower alkyl acetate such as ethyl acetate or butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, etc., and then dispersed in a hydrophilic colloid. To be done. The high boiling point organic solvent and the low boiling point organic solvent may be mixed and used.

Further, the dispersion method using a polymer described in JP-B-51-39853 and JP-A-51-59943 can also be used.

When the FR compound of the present invention has an acid group such as carboxylic acid or sulfonic acid, it is introduced into the hydrophilic colloid as an alkaline aqueous solution.

Further, the addition amount of the FR compound used in the present invention is 10 ^-9 to 10 per 1 mol of silver in the silver halide emulsion containing the FR compound.
^-1 mol, preferably 10 ^-8 to 10 ^-2 mol.

The monodisperse emulsion according to the present invention is an emulsion having a grain size distribution with a variation coefficient S / relating to the grain size of silver halide grains being 0.25 or less. Here, the average particle size and S are standard deviations related to the particle size. That is, the grain size of each emulsion grain is ri
And when the number is ni, the average particle is And its standard deviation S is Is defined as

The term "individual grain size" as used in the present invention refers to a silver halide emulsion as described in "The Theory of the Photographic Process" by TH James et al.
e Theory of the Photographic Process) 3rd Edition 36-43
Methods well known in the art (usually electron microscopy), as described on page, published by Macmillan (1966).
It is a diameter equivalent to the projected area corresponding to the area projected in the case of minute photographing in. Here, the projected equivalent diameter of a silver halide grain is defined by the diameter of a circle equal to the projected area of a silver halide grain as described in the above-mentioned book. Therefore, the shape of the silver halide grains is not spherical (for example, cubic,
In the case of an octahedron, a tetradecahedron, a flat plate, a potato, etc.), the average particle size and its deviation S can be obtained as described above.

The variation coefficient relating to the grain size of the silver halide grains is 0.25 or less, preferably 0.20 or less, more preferably 0.15 or less.

The size of silver halide grains is not particularly limited, but 0.4 μ
m to 5 μm is preferable, and further 0.8 μm to 4
It is preferably μm, particularly 1.4 μm to 3.5 μm.

The types of silver halide grains are hexahedron, octahedron, dodecahedron,
It may have a regular crystal form (normal crystal grain) such as a tetradecahedron, or may have an irregular crystal form such as a sphere, a globular form, or a flat form.

Particularly preferred are normal crystal grains.

In the case of normal crystal grains, grains having a (111) plane of 50% or more are particularly preferable. Even in the case of irregular crystal form, the (111) plane is 50
Particles having a percentage of at least% are particularly preferred. The plane ratio of the (111) plane can be determined by the Kubelka-Munk dye adsorption method. This selects dyes that preferentially adsorb on either the (111) face or the (100) face and that the association state of the dyes on the (111) face and the association state of the dyes on the (100) face are spectrally different. To do. The surface ratio of the (111) plane can be determined by adding such a dye to the emulsion and examining the spectral spectrum with respect to the added amount of the dye in detail. For details of the above dye adsorption method, see Tadaaki Tani, “Nippon Kagaku”, p. 942 (198
4) can be referred to.

The halogen composition of silver halide grains is 60 mol% of silver bromide.
Including the above, silver chloride is preferably 10 mol% or less. The grain is more preferably 2 mol% to 40 mol% of silver iodide, and particularly preferably 7 mol% to 25 mol% of silver iodide. The halogen composition distribution between grains is preferably uniform.

The most preferable halogen composition of the monodisperse emulsion grains used in the present invention is a grain having substantially two distinct layered structures consisting of a core portion of a high iodine layer and a shell portion of a low iodine layer. The layered structure particles will be described below.

Part of the core is a high iodine silver halide, and the iodine content is preferably between 10 mol% and the solid solution limit of 45 mol%.

It is preferably 15 to 45 mol%, more preferably 20 to 45 mol%.
40 mol%.

In the core portion, the silver halide other than silver iodide may be either silver chlorobromide or silver bromide, but a high silver bromide ratio is preferred.

The composition of the outermost layer is silver halide containing 5 mol% or less of silver iodide, and more preferably silver halide containing 2 mol% or less of silver iodide.

As the silver halide other than silver iodide in the outermost layer, any one of silver chloride, silver chlorobromide and silver bromide may be used, but a higher silver bromide ratio is preferred.

The definite layered structure here can be determined by an X-ray diffraction method. An example of applying the X-ray diffraction method to silver halide grains is the article by H. Hirschyu, Journal of Photographic Scienc.
e) It is described in pp. 129 et seq. of Volume 10 (1962).
When the lattice constant is determined by the halogen composition, a diffraction peak occurs at a diffraction angle that satisfies the Black condition (2dsin θ = nλ).

The method for measuring X-ray diffraction is described in detail in Basic Analytical Chemistry Course 24, "X-ray Analysis" (Kyoritsu Shuppan), "Guide to X-ray Diffraction" (Rigaku Denki Co., Ltd.) and the like. The standard measurement method is to use Cu as a target, and use the Kβ ray of Cu as a radiation source (control pressure 40 KV, tube current 60 mA) to obtain the diffraction curve of the (220) plane of silver halide. To increase the resolution of the measuring instrument, the width of slits (divergent slits, light receiving slits, etc.), the time constant of the device, the scanning speed of the goniometer,
It is necessary to properly select the recording speed and confirm the measurement accuracy using a standard sample such as silicon.

When the emulsion grains have two distinct layered structures, a diffraction maximum due to silver halide in the high iodine layer and a diffraction maximum due to silver halide in the low iodine layer appear and two peaks appear in the diffraction curve.

Substantially two distinct layered structures mean the diffraction angle (2θ)
When the curve of diffraction intensity vs. diffraction angle of (220) plane was obtained for silver halide using Cu Kβ radiation in the range of 38 ° to 42 °, high iodine containing 10 to 45 mol% of silver iodide was obtained. Of two diffraction peaks corresponding to a layer and a diffraction peak corresponding to a low iodine layer containing 5 mol% or less of silver iodide, and 1 between them.
Two minima appear, and the diffraction intensity corresponding to the high iodine layer is different from the diffraction intensity of the peak corresponding to the low iodine layer.
It refers to the case when it is 1/10 to 3/1. More preferably, the diffraction intensity ratio is 1/5 to 3/1, particularly 1/3 to 3/1.

As an emulsion having substantially two distinct layered structures,
More preferably, the minimum diffraction intensity between the two peaks is 2
Of the two diffraction maxima (peaks), those with weak intensity are preferably 90% or less.

More preferably 8% or less, particularly preferably 60%
It is the following. A method of decomposing a diffraction curve composed of two diffraction components is well known, and is described in, for example, Experimental Physics Course 11 Lattice Defects (Kyoritsu Shuppan).

It is also useful to assume a curved curve as a function such as a Gaussian function or a Lorentz function and analyze it using a curve analyzer manufactured by Du Pont.

Even in the case of an emulsion in which two kinds of grains having different halogen compositions having no distinct layered structure coexist, two peaks appear in the X-ray diffraction.

In order to determine whether the silver halide emulsion is an emulsion having a layered structure or an emulsion in which two kinds of silver halide grains as described above coexist, in addition to the X-ray diffraction method, the EPMA method (El
ectron-Probe Micro Analyzer method).

In this method, a sample in which emulsion grains are well dispersed so that they do not come into contact with each other is prepared and an electron beam is irradiated. Elemental analysis of extremely small parts can be performed by X-ray analysis by electron beam excitation.

By this method, the halogen composition of each grain can be determined by obtaining the characteristic X-ray intensities of silver and iodine emitted from each grain.

If the halogen composition of at least 50 grains is confirmed by the EPMA method, it can be judged whether or not the emulsion has a layered structure.

The emulsion having a layered structure preferably has a more uniform iodine content between grains.

When the distribution of iodine content among particles is measured by the EPMA method, the relative standard deviation must be 20% or less.

To obtain favorable photographic properties in emulsions consisting of silver halide grains having a well-defined layered structure, the core high iodine silver halide must be well covered by the low iodine shell silver halide. The required shell thickness depends on the particle size, but for large particles of 1.0μ and above,
0.05 μm for small particles of 0.1 μm or more and less than 1.0 μm
It is desirable to be covered with the above shell thickness. In order to obtain an emulsion having a definite layered structure, the silver amount ratio of the shell part to the core part is preferably in the range of 1/5 to 5, more preferably 1/5 to 3 and 1/5. The range of ˜2 is particularly preferable.

A silver halide grain having substantially two distinct layered structures means that two regions having different halogen compositions are substantially present in the grain, and the center side of the grain is the core part and the surface side is the Explained as Ciel.

Substantially two means that there may be a third region (for example, a layer existing between the central core part and the outermost shell part) in addition to the core part and the shell part.

However, even if such a third region exists, two peaks (peaks of 2 corresponding to the high iodine portion and the low iodine portion) are obtained when the X-ray diffraction pattern is obtained as described above.
It means that it may exist within a range that does not substantially affect the shape of.

The same applies when the third region is present inside the core portion.

When the same color-sensitive layer is divided into two or more layers, the layer containing the FR compound and the monodisperse emulsion of the present invention is preferably the most sensitive layer among them, A gelatin layer may be provided between the low-sensitivity layer and the low-sensitivity layer as described in JP-B-49-15495, page 4, or JP-A-57-15553.
As described in No. 6, it is preferable to provide a non-photosensitive layer as an intermediate layer such as providing a coupler-containing layer, and among them, as described in JP-A-59-160135, the intermediate layer Is particularly preferably a non-photosensitive fine grain silver halide emulsion layer.

The photographic emulsion used in the present invention is usually one that has undergone physical ripening, chemical ripening and spectral sensitization. Additives used in such a process are described in Research Disclosure No. 17643 and No. 18716, and the corresponding parts are summarized in the table below.

Known photographic additives that can be used in the present invention are also described in the above-mentioned two Research Disclosures, and the locations described in the table below are shown.

Various color couplers can be used in the present invention, and specific examples thereof are described in the patents described in Research Disclosure (RD) No. 17643, VII-C to G above. As the dye-forming coupler, a coupler which gives the three primary colors of the subtractive color method (that is, yellow, magenta and cyan) by color development is important, and specific examples of the diffusion resistant 4-equivalent or 2-equivalent coupler are the above-mentioned RD17643, VII- C
In addition to the couplers described in the patents described in paragraphs D and D, the following can be preferably used in the present invention.

A typical example of the yellow coupler that can be used in the present invention is a hydrophobic acylacetamide coupler having a ballast group. A specific example is U.S. Pat.
No. 7,210, No. 2,875,057 and No. 3,265,506. In the present invention, it is preferable to use a two-equivalent yellow coupler, and US Pat.Nos. 3,408,194 and 3,4
No. 47,928, No. 3,933,501 and No. 4,022,620 described oxygen atom elimination type yellow coupler or Japanese Examined Patent Publication No. 58-10739, U.S. Patent No. 4,401,752, No. 4,32
6,024, RD13053 (April 1979), US Pat. No. 1,425,02
No. 0, West German Application Publication No. 2,219,917, No. 2,261,361,
Typical examples thereof include nitrogen atom-releasing yellow couplers described in JP-A-2,329,587 and JP-A-2,433,812. The α-pivaloyl acetanilide type couplers are excellent in the fastness of color forming dyes, especially the light fastness, while the α-benzoyl acetanilide type couplers can obtain a high color density.

Examples of magenta couplers that can be used in the present invention include hydrophobic indazolone or cyanoacetyl, preferably 5-pyrazolone and pyrazoloazole couplers having a ballast group. The 5-pyrazolone-based coupler is preferably a coupler in which the 3-position is substituted with an arylamino group or an acylamino group, from the viewpoint of the hue and color density of the color forming dye, and a typical example thereof is U.S. Pat.
1,082, 2,343,703, 2,600,788, 2,9
No. 08,573, No. 3,062,653, No. 3,152,896 and No. 3,936,015. As a leaving group for a 2-equivalent 5-pyrazolone-based coupler, US Pat. No. 4,310,
Nitrogen atom leaving groups described in 619 or U.S. Pat.
The arylthio groups described in 51,897 are particularly preferred.
Further, it has a ballast group described in European Patent No. 73,636. 5
-Pyrazolone couplers provide high color density. Examples of pyrazoloazole-based couplers include U.S. Pat.
879 pyrazolobenzimidazoles, preferably pyrazolo [5,1- described in U.S. Pat.No. 3,725,067
c] [1,2,4] triazoles, Research Disclosure 24220 (June 1984), and pyrazolotetrazoles and Research Disclosure 24230 (June 1984) described in JP-A-60-33552. Month) and JP-A-60-4365
Examples thereof include pyrazolopyrazoles. The imidazo [1,2-b] pyrazoles described in U.S. Pat.No. 4,500,630 are preferable in view of low yellow sub-absorption of the coloring dye and light fastness, and pyrazolo [1,2] described in European Patent 119,860A. 5-b] [1,2,4] triazole is particularly preferred.

Cyan couplers that can be used in the present invention include hydrophobic and diffusion-resistant naphthol-based and phenol-based couplers, and the naphthol-based couplers described in U.S. Pat.No. 2,474,293, preferably U.S. Pat.Nos. 4,052,212 and 4 , 1
Representative examples thereof include oxygen atom elimination type two-equivalent naphthol couplers described in Nos. 46,396, 4,228,233 and 4,296,200. Further, specific examples of the phenol-based coupler are described in U.S. Patent Nos. 2,369,929 and 2,801,171.
No. 2,772,162, No. 2,895,826 and the like.

Cyan couplers which are fast against humidity and temperature are preferably used in the present invention, and typical examples thereof include a phenol having an alkyl group of ethyl group or higher at the meta-position of the phenol nucleus described in U.S. Pat. No. 3,772,002. Cyan couplers, U.S. Pat.Nos. 2,772,162 and 3,758,308,
No. 4,126,396, No. 4,334,011, No. 4,327,173
, German Patent Publication No. 3,329,729 and European Patent No. 121,3
2,5-diacylamino-substituted phenol-based couplers described in U.S. Patent No. 65, and U.S. Pat.Nos. 3,446,622 and 4,3.
No. 3,999, No. 4,451,559 and No. 4,427,767, which have a phenylureido group at the 2-position, and 5
Examples thereof include a phenol-based coupler having an acylamino group at the -position.

In order to correct the unnecessary absorption of the chromophore, it is preferable to mask the color sensitive material for photographing with a colored coupler. U.S. Pat.No. 4,163,670 and JP-B-57-
Typical examples are yellow colored magenta couplers described in 39413 and the like, or magenta colored cyan couplers described in U.S. Pat. Nos. 4,004,929 and 4,138,258 and British Patent 1,146,368. Other colored couplers are described in RD17643, paragraphs VII-G above.

The graininess can be improved by using a coupler in which the color forming dye has an appropriate diffusibility. Such couplers are
Specific examples of magenta couplers are described in U.S. Pat. No. 4,366,237 and British Patent 2,125,570, and specific examples of yellow, magenta or cyan couplers are described in European Patent No. 96,570 and West German Patent Publication No. 3,234,533.

The dye-forming coupler and the above-mentioned special coupler may form a dimer or higher polymer. Typical examples of polymerized dye forming couplers are described in US Pat. Nos. 3,451,820 and 4,080,211. Specific examples of polymerized magenta couplers are described in US Pat. No. 2,102,173 and US Pat. No. 4,367,282.

Couplers that release a photographically useful residue with the cuprig can also be preferably used in the present invention. As the DIR coupler releasing the development inhibitor, the couplers of the patents described in the above-mentioned RD17643, VII to F are useful.

A preferred combination with the present invention is JP-A-57-151.
Developer inactivation type represented by 944; U.S. Pat. No. 4,248,962
And the timing type represented by JP-A-57-154234; the reaction type represented by JP-A-59-39653, and particularly preferable are JP-A-57-151944 and JP-A-58-217932. ,
Developer inactivation type DIR couplers described in Japanese Patent Application Nos. 59-75474, 59-82214, 59-82214 and 59-90438, and Japanese Patent Application No. 59-39653. It is a reactive DIR coupler.

Suitable supports that can be used in the present invention include, for example, the aforementioned R
Page 28 of D.No.17643 and page 647 of the same, No.18716 From right column 6
See page 48, left column.

The color photographic light-sensitive material according to the present invention has the above-mentioned RD.
Development can be carried out by a usual method described on pages 28 to 29 of 643 and 651, left column to right column of No. 18716.

The color photographic light-sensitive material of the present invention is usually subjected to washing treatment or stabilizing treatment after development, bleach-fixing or fixing treatment.

In the water washing step, it is general to carry out countercurrent water washing of two or more tanks to save water. A typical example of the stabilizing treatment is a multistage countercurrent stabilizing treatment as described in JP-A-57-8543 instead of the water washing step. In the case of this step, a countercurrent bath of 2 to 9 tanks is required. Various compounds are added to the stabilizing bath for the purpose of stabilizing the image. For example, various buffers (eg borate, metaborate, borax, phosphate, carbon salt, potassium hydroxide, sodium hydroxide, ammonia water mono) for adjusting the membrane pH (eg pH 3 to 8). Representative examples thereof include carboxylic acid, dicarboxylic acid, polycarboxylic acid and the like) and formalin. In addition, water softener (inorganic phosphoric acid,
Aminopolycarboxylic acids, organic phosphoric acids, aminopolyphosphonic acids, phosphonocarboxylic acids, etc.), bactericides (benzisothiazolinone, irithiazolone, 4-thiazolinebenzimidazole, halogenated phenols, etc.), surfactants, fluorescent enhancement Various additives such as whitening agents and hardening agents may be used, and two or more kinds of the same or different target compounds may be used in combination.

Further, it is preferable to add various ammonium salts such as ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, and ammonium thiosulfate as a film pH adjuster after the treatment.

The present invention can be applied to various color light-sensitive materials. Typical examples include color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers. The present invention also relates to Research Disclosure 17123 (July 1978).
It is also applicable to a black and white light-sensitive material using a mixture of three-color couplers described in (Mon.).

Example 1 Sample 10 was prepared by coating the emulsion layer and protective layer shown below on a cellulose triacetate film support provided with an undercoat layer to evaluate the effectiveness of the application of the present invention.
Created 1. The coating amount of each substance is shown in parentheses in g / m ² or ml / m ² .

(Sample 101) (1) Emulsion layer Emulsion A described below (2.1 × 10 ⁻² mol / m ^{2 in} terms of silver) Coupler a (1.5 × 10 ⁻³ mol / m ² ) Tricresyl phosphate (1.10 g / m ² ) Gelatin (2.30 g / m ² ) (2) Protective layer 2,4-dichlorotriazine-6-hydroxy-s-triazine sodium (0.08 g / m ² ) Gelatin (1.80 g / m ² ) (Sample 102- 104) In the same manner as in Sample 101, except that Emulsion A in Sample 101 was replaced with Emulsions B, C, and D described later, respectively.
Samples 102, 103 and 104 were made.

(Sample 105 through 112) FR compounds of the present invention the emulsion layer of the sample 101 to 104 (I-8) and (III-11) was applied in such a manner that a 0.5 mg / m ² and 0.8 mg / m ^2, respectively Samples 105 to 108 and Samples 109 to 112 were prepared in the same manner as Samples 101 to 104 except for.

After leaving these samples for 14 hours under the conditions of 40 ° C and 70% relative temperature, they are used for 48 hours using A light source and color temperature conversion filter.
After the temperature was adjusted to 00 ° K and imagewise exposure of maximum 2 CMS was given, the following color development processing was performed at 38 ° C.

Granularity was also measured using the conventional RMS method. The measurement aperture used was 48μ. The results are shown in Table 1.

Color development 2 minutes 45 seconds Floating 6 minutes 30 seconds Water washing 2 minutes 10 seconds Settling 4 minutes 20 seconds Water washing 3 minutes 15 seconds Stability 1 minute 05 seconds The treatment liquid composition used in each process is as follows. It was

Color developer Diethylenetriaminepentaacetic acid 1.0g 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0g Sodium sulfite 4.0g Potassium carbonate 30.0g Potassium bromide 1.4g Potassium iodide 1.3mg Hydroxylamine sulfate 2.4g 4- (N- Ethyl-N-β-hydroxyethylamino)
-2-Methylaniline sulfate 4.5g Add water 1.0l pH10.0 Bleaching solution Ethylenediaminetetraacetic acid ferric ammonium salt 100.0g Ethylenediaminetetraacetic acid disodium salt 10.0g Ammonium bromide 150.0g Ammonium nitrate 10.0g Add water 1.0l pH6.0 Fixer Ethylenediaminetetraacetic acid disodium salt 1.0g Sodium sulfite 4.0g Ammonium thiosulfate aqueous solution (70%) 175.0ml Sodium bisulfite 4.6g Water is added 1.0l pH6.6 Stabilizer Formalin (40%) 2.0 ml Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization ≈ 10) 0.3g Water added 1.0l From Table 1, in Samples 101 to 104 not using the FR compound, Samples 103 and 104 using emulsions having good monodispersity are slightly higher in sensitivity and low exposure than Samples 101 and 102 using emulsions having poor monodispersity. It can be seen that the graininess in the area is good, but the graininess in the high exposure area is not good. On the other hand, the sample of the present invention using both the FR compound and the emulsion with good monodispersity has significantly higher sensitivity than the sample without the FR compound and using the emulsion with good monodispersity, and is Despite the higher sensitivity than Samples 105, 106, 109, and 110, which also used emulsions with poor dispersibility, the granularity in the low-exposed areas was good, demonstrating the effectiveness of the present invention.

Emulsions A to D used here were prepared as follows.

Preparation of emulsion A and emulsion B 200 g of inert gelatin, 950 g of potassium bromide and potassium iodide
A solution of 19.2g and 71.9g dissolved in 9.8l of aqueous solution at 75 ℃
The solution is prepared by stirring with 1,000g of silver nitrate.
7.0 l were added over 80 minutes to give a silver iodobromide content of 2 mol% and 7.
5 mol% silver iodobromide emulsions A'and B'were obtained. These emulsions were desalted by a usual method, and then 12 mg and 15 mg of sodium thiosulfate and 12 mg of chloroauric acid were added and ripened at 60 ° C. for 50 minutes for chemical sensitization. These emulsions were designated as Emulsion A and Emulsion B, respectively.

Emulsion A had an average grain size of 1.6 μm and a coefficient of variation S / of 0.39. Emulsion B had an average grain size of 1.5 μm and a coefficient of variation S / 0.4 of 0.44, showing an emulsion having a wide size distribution.

Preparation of Emulsion C In control double jet method, silver iodide content was 4 mol% in the presence of ammonia, average grain size was 1.4 μm, and coefficient of variation was
An octahedron emulsion of 0.17 was prepared as a core emulsion. After washing this core emulsion with water, pure silver bromide was applied to the shell part until the amount of silver in the core part became equal to that in the shell part. After desalting in the usual way, add sodium thiosulfate 25 mg and chloroauric acid 12 mg to 55
It was aged for 60 minutes at ℃ and chemically sensitized. This emulsion C had an average grain size of 1.8 μm and a coefficient of variation of 0.13.

Preparation of Emulsion D By control double jet method, silver iodide content was 15 mol% in the presence of ammonia, and average grain size was 1.3 μm.
Was prepared and used as the core emulsion. After washing this core emulsion with water, pure silver bromide was applied to the shell so that the amount of silver in the core and the amount of silver in the shell were equal. After desalting by a usual method, 30 mg of sodium thiosulfate and 15 mg of chloroauric acid were added, and the mixture was aged at 55 ° C for 60 minutes and chemically sensitized. Emulsion D had an average grain size of 1.6 μm and a coefficient of variation of 0.12.

Coupler a Example 2 Sample 20 of a multilayer color light-sensitive material having the composition shown below on a transparent cellulose triacetate film support.
Created 1.

The emulsion coating amount was expressed in terms of silver equivalent coating amount.

(Sample 201) 1st layer: anti-halation layer Black colloidal silver 0.18g / m ² UV absorber U-1 0.12g / m ² same gelatin layer containing U-2 0.17g / m ² 2nd layer; Intermediate layer 2 , 5-Di-t-pentadecylhydroquinone 0.18 g / m ² coupler Cp-7 0.11 g / m ² silver iodobromide emulsion 0.15 g / cm ² Gelatin layer containing 3rd layer; first red-sensitive emulsion layer, silver iodobromide emulsion 0.72 g / m ² Sensitizing dye I: 7.0 × 10 ^-5 mol per mol of silver Sensitizing dye II: 2.0 × 10 ^-5 mol per mol of silver Sensitizing dye III: 2.8 × 10 ^-4 per mol of silver Molar sensitizing dye IV: 2.0 × 10 ^-5 mol per 1 mol of silver Coupler Cp-1 0.020g / m ² coupler Cp-2 0.093g / m ² coupler Cp-3 0.31g / m ² coupler Cp-4 0.005 Gelatin layer containing g / m ² 4th layer; 2nd red-sensitive emulsion layer Silver iodobromide emulsion 1.6g / m ² Sensitizing dye I: 5.2 × 10 ^-5 mol per mol of silver Sensitizing dye II: 1.5 × 10 ^-5 mol per mol of silver Sensitizing dye III: 2.1 × 10 ^-4 per mol of silver 1.5 × 10 ^-5 mol coupler moles sensitizing dye IV ... one mol of silver Cp-1 0.051g / m ² coupler ^Cp-2 0.10g / m 2 coupler Cp-3 0.061g / m ² coupler Cp-4 0.003 g / m ² coupler Cp-5 0.046g / m ² gelatin layer fifth layer comprising; third red-sensitive emulsion layer silver iodobromide emulsion 1.6 g / m ² Sensitizing dye I: 5.5 × 10 ^-5 mol per mol of silver Sensitizing dye II: 1.6 × 10 ^-5 mol per mol of silver Sensitizing dye III: 2.2 × 10 ^-5 per mol of silver gelatin layer sixth layer containing 1.6 × 10 ^-5 mol coupler Cp-3 0.050g / m ² coupler Cp-5 0.45g / m ² moles sensitizing dye IV ... 1 mol of silver; the intermediate layer gelatin layer 7 Layer: First green-sensitive emulsion layer Silver iodobromide emulsion 0.55 g / m ² Sensitizing dye V: 3.8 × 10 ^-4 mol per mol of silver Sensitizing dye VI: 3.0 × 10 ^-5 mol per mol of silver Sensitizing dye VII: 1.2 × 10 ^-4 per mol of silver mole coupler Cp-6 0.29g / m ² coupler Cp-7 0.040g / m ² coupler Cp-8 0.055 g / m ² coupler Cp-9 0.015g / m ² eighth layer: second green-sensitive emulsion layer silver iodobromide Silver emulsion 1.5g / m ² Sensitizing dye V: 2.7 × 10 ^-4 mol per mol of silver Sensitizing dye VI: 2.7 × 10 ^-5 mol per mol of silver Sensitizing dye VII: 8.5 × 10 ^-5 per mol of silver gelatin layer ninth layer comprising a molar coupler Cp-6 0.25g / m ² coupler Cp-7 0.013g / m ² coupler Cp-8 0.009g / m ² coupler Cp-9 0.006g / m ^2; the third green-sensitive emulsion Layer Silver iodobromide emulsion 1.5 g / m ² Sensitizing dye V: 3.0 × 10 ^-4 mol per mol of silver Sensitizing dye VI: 2.4 × 10 ^-5 mol per mol of silver Sensitizing dye VII: 9.5 × 10 ^-5 per mol of silver mole coupler Cp-10 0.070g / m ² coupler Cp-7 0.013g / m ² tricresyl phosphine gelatin layer tenth layer containing benzoate 0.40 g / m ^2; the yellow filter layer yellow colloidal silver 0.04g / m ^{2 2,} gelatin layer containing a 5-di -t- pentadecylhydroquinone 0.031 g / m ² 11th layer; first blue-sensitive emulsion layer silver iodobromide emulsion 0.32 g / m ² Coupler Cp-11 0.77g / m ² Coupler Cp-12 0.030g / m ² Gelatin layer containing tricresyl phosphate 0.52g / m ² 12th layer; 2nd blue-sensitive emulsion layer Silver iodobromide emulsion 0.40g / m ² Coupler Cp-11 0.25 g / m ² tricresyl phosphate 0.17 g / m ² Sensitizing dye VIII ... Gelatin layer containing 2.2 × 10 ^-4 mol per 1 mol of silver 13th layer: Fine grain emulsion layer Iodobromide Silver emulsion 0.25g / m ² 14th layer; third blue-sensitive emulsion layer Emulsion E 1.00 g / m ² coupler Cp-11 0.22 g / m ² FR compound (I-6) 0.5 mg / m ² tricresyl phosphate of the present invention 0.14 g / m ² sensitizing dye VIII ... 2.3 × 10 ^-4 mol per 1 mol of silver Fifteenth layer; first protective layer UV absorber U-1 0.14 g / m ² UV absorber U-2 0.22 g / gelatin layer 16 layer comprising m ^2; second protective layer of polymethyl methacrylate particles (diameter 1.5 microns) 0.05 g / m ² silver iodobromide emulsion 0.30 g / m ² In addition to the above composition, a gelatin hardener H-1 and a surfactant were applied to each layer.

Compound Sensitizing dye (Samples 202 to 212) Samples 202 to 212 were prepared in the same manner as Sample 201, except that the emulsion E contained in the 14th layer of Sample 201 was replaced with the emulsions F to P.

(Samples 213 to 224) FR compounds (I to 6) contained in the 14th layer of Samples 201 to 212
Samples 213--2 are the same as Samples 201-212 except that
24 created.

Samples 201 to 224 were exposed in the same manner as in Example 1 and then subjected to the same color development process as in Example 1.

It can be seen from Table 2 that the samples to which the present invention is applied are obviously more sensitive and have better granularity than the samples 201, 202 and 212 using emulsions having poor monodispersity. Further, when the FR compound is not used, the overall reduction is obtained, and it can be seen that the grain in the highly exposed portion of the emulsion having good monodispersity is not as good as the grain using the FR compound.

As described above, the effectiveness of the present invention is clear.

Emulsions E to P used here are as follows.

Preparation of Emulsion E and Emulsion F 200 g of inert gelatin, 950 g of potassium bromide and potassium iodide
19.5g and 97.5g each dissolved 9.8l aqueous solution at 80 ℃
The solution is prepared by stirring with 1,000g of silver nitrate.
7.0 l were added during 60 minutes and 80 minutes to obtain silver iodobromide emulsions E'and F'having a silver iodide content of 2 mol% and 10 mol%. After desalting these emulsions by a conventional method, 10 mg and 20 mg of sodium thiosulfate and 5 mg and 10 mg of chloroauric acid were added, respectively, and sensitized at 57 ° C. for 50 minutes and 75 minutes to chemically sensitize to obtain emulsions E and F. It was Emulsion E had an average particle size of 1.8 μm and a coefficient of variation of 0.43. The average grain size of emulsion F is 1.6μ.
m, the coefficient of variation was 0.47.

Preparation of Emulsions G to P Eight kinds of octahedral monodisperse silver iodobromide core emulsions having AgI contents of 0 to 40 mol% as shown in Table 3 were subjected to control double in the presence of ammonia. It was prepared by the jet method. The average particle size of each was 1.6 μm. As a result of X-ray diffraction of these emulsion grains, a sharp peak was obtained at the diffraction angle corresponding to each AgI content, and it was confirmed that the iodine content between grains was uniform.

After washing the above core emulsion with water, pure silver bromide was applied to the shell by the control double jet method until the amounts of silver in the core and the shell became equal.

After desalting these emulsions, sodium thiosulfate and chloroauric acid were added, and each was optimally chemically sensitized to obtain emulsions G to P. Table 3 shows the iodine content of the core and shell of these emulsions by X-ray diffraction and the average grain size variation coefficient. In addition, the intergranular iodine distributions of emulsions G to P were measured by an X-ray microanalyzer for each of about 200 grains.
The AgI content was within ± 20% of the AgI content. From this result, it can be considered that the AgI content of each particle is relatively uniform, and the clear peaks appearing in the X-ray diffraction reflect the clear layered structure in each particle. The outer shape of the grains after shelling was octahedron or tetradecahedron with very few (100) faces.

Continuation of the front page (56) References JP 61-212842 (JP, A) JP 61-194443 (JP, A)

Claims (1)

[Claims] 1. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support,
At least one layered structure having a grain size distribution with a variation coefficient S / (S is a standard deviation relating to grain size, is an average grain size) relating to the grain size of silver halide grains contained in the emulsion layer is 0.25 or less. A monodisperse emulsion comprising an emulsion having a standard deviation of iodine distribution between grains of 20% or less, and developed silver when an aromatic primary amine developing agent is used in the emulsion layer. A silver halide color photographic light-sensitive material comprising a fogging agent or a development accelerator or a compound which releases a precursor thereof in an amount corresponding to the amount.