JPH02216147A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To enhance shelf life of a photosensitive material and a latent image, and stability against variance of processing conditions by forming at least one of color sensitive layers having single layer structure. CONSTITUTION:The photosensitive material is provided with at least blue-, green-, and red-sensitive silver halide emulsion layers and a yellow filter layer on a substrate. The emulsion layers contain a development inhibitor releasing (DIR) compound and the filter layer contains a yellow dye, such as a compound of formula in which R1 is aryl or alkoxy; each of R2 and R3 is alkyl; R4 is H or a substituent; R5 is aryl; and n is 1 - 4. At least one of the color sensitive layers has single layer structure and the single layer structure includes the case in which plural same color sensitive emulsion layers having the same kind of coupler and the same grain particle and the like are formed in a continuous layer.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to a silver halide color photographic light-sensitive material suitable for full-color photography, and particularly to a negative-working silver halide color photographic material in which at least one color-sensitive layer is a single layer. This invention relates to silver color photographic materials.

[Prior Art] Currently, the so-called negative-positive method, in which color photographs are taken using color negative film and enlarged onto color vapor to produce color prints, is widely used.

One reason for this is that color negative film has a very wide exposure latitude, and the probability of failure during shooting is extremely low, allowing even general users without specialized knowledge to easily take color photos.

"Having a wide exposure latitude" means that in the so-called characteristic curve where the horizontal axis is the exposure amount and the vertical axis is the color density,
Good gradation over a wide exposure range from shadow areas with low exposure to highlight areas with high exposure.

If this gradation is poor, the color reproducibility and tone reproducibility of the dye image will deteriorate.

Unlike color reversal film and color vapor, color negative film is a photosensitive material that requires strict control of gradation over a wider exposure range.
For this reason, in the currently commercially available color negative film for photography, each color-sensitive layer for blue, green, and red light is divided into a high-sensitivity layer containing silver halide grains with large grain sizes and a high-sensitivity layer containing silver halide grains with small grain sizes. The so-called I) has a multilayer structure including a plurality of emulsion layers including a low-speed layer, and further produces a development inhibitor as a result of reaction with an oxidized product of a developing agent.
IR compounds are used.

This technology is unique to color negative film;
In particular, DIR compounds improve not only gradation but also the sharpness of dye images.
It also improves graininess and color reproducibility, and is essential for color negative films.

Techniques for strictly controlling such gradations, so-called improving gradation stability, include, for example, Japanese Patent Application Laid-Open No. 60-24494.
4, etc., and specifically, after chemically sensitizing silver halide emulsions with the same average grain size, sensitizing dyes are added to each emulsion in different molar ratios and mixed again. It is shown.

Furthermore, color negative films are processed in different laboratories and are therefore processed under highly variable processing conditions compared to color reversal films. Therefore, color negative films are particularly required to have a high degree of stability against fluctuations in processing conditions.

[Problems to be Solved by the Invention] However, as described above, color negative films have a multilayer structure using multiple emulsion layers containing silver halide grains with different grain sizes, and furthermore, a DIR compound is used to strictly control the gradation. As a result, the photographic exposure and storage stability of the material (hereinafter abbreviated as photosensitive material storage) are poor against external conditions such as temperature and humidity. Preservability against external conditions (hereinafter abbreviated as latent image preservation)
is inferior. Furthermore, as mentioned above, although a high degree of stability is required for processing conditions, processing stability has not been solved, and gradation is difficult to achieve due to poor stability of processing conditions. It has the disadvantage that deterioration occurs and color reproducibility and tone reproducibility deteriorate. Furthermore, JP-A No. 60-24494
The method described in Publication No. 4 has a problem in that during the stagnation period up to the coating of the remixed emulsion, dye adsorption equilibrium occurs between particles, which is undesirable.

Therefore, the present inventors investigated the causes of deterioration of gradation, color reproducibility, and tone reproducibility, and found that yellow colloidal silver in yellow filters, which have been conventionally used for the purpose of improving color reproducibility, It was also found that this was caused by

[Object of the Invention] The first object of the present invention is to provide a silver halide photographic light-sensitive material that has excellent storage stability and latent image storage stability.

A second object of the present invention is to provide a silver halide color photographic material that exhibits excellent stability against fluctuations in processing conditions.

[Structure of the Invention] The above-mentioned objects of the present invention are to provide a silver halide color comprising at least blue-sensitive, green-sensitive and red-sensitive silver halide emulsion layers and a yellow filter layer on a support. The photographic light-sensitive material has a DIR compound, the yellow filter layer contains a yellow dye, and at least one of the blue, green and red color-sensitive layers has a single layer structure. This was achieved using silver halide color photographic materials.

The present invention will be explained in more detail below.

The DIR compound used in the present invention is shown below, and the use of this DIR compound is even more preferable in terms of graininess.

In the present invention, a DIR compound refers to a compound that releases a development inhibitor or a compound capable of releasing a development inhibitor upon reaction with an oxidized product of a color developing agent.

The development suppression mentioned above! Compounds capable of releasing 1Ilfq may be those that release the development inhibitor imagewise or non-imagewise.

Examples of those that are released in an imagewise manner include those caused by reaction with an oxidized product of a developing agent; examples of those that are released in a non-imagewise manner include, for example, TI)'II! described below. Examples include those that utilize groups.

Representative structural formulas are shown below.

General formula (D-1) A-(Y)m A represents a coupler residue, m represents 1 or 2,
Y represents a group that binds to the coupling position of the coupler residue 5A and leaves by reaction with the oxidized product of the color developing agent, and represents a development inhibitor group or a group capable of releasing the development inhibitor.

In general formula (D-1), Y typically has the following form (
It is represented by D-2) to (D-20).

-Format (D-2) General formula (D-3) General formula (D-4) General formula (D-5) General formula (D-6) General formula (D-7) General formula (D-8) General Formula (D-9) dff In the general formulas (D-2) to (D-7), Rat is a hydrogen atom, a halogen atom, or an alkyl, alkoxy,
Acylamino, alkoxycarbonyl, thiazolidinylideneamino, aryloxycarbonyl, acyloxy, carbamoyl, N-alkylcarbamoyl, N, N-
Represents each group of dialkylcarbamoyl, nitro, amino, N-arylcarbamoyloxy, sulfamoyl, N-alkylcarbamoyloxy, hydroxy, alkoxycarbonylamino, alkylthio, arylthio, aryl, peterocycle, cyano, alkylsulfonyl or aryloxycarbonylamino . n represents 0, l or 2, and when n is 2, each Rd may be the same or different.

The total number of carbon atoms contained in n Rd is 0 to 10. Further, the number of carbon atoms contained in Rd in form (D-6) is 0 to 15.

X in the above-format (D-6) represents an oxygen atom or a sulfur atom.

In general formula (D-8), Rd represents an alkyl group, an aryl group, or a heterocyclic group.

- In the format (D-9), Rdl represents a hydrogen atom or each group of alkyl, cycloalkyl, aryl, or petero ring, and Rd represents a hydrogen atom, a halogen atom, or alkyl, cycloalkyl, aryl, acylamino,
Represents each group of alkoxycarbonylamino, aryloxycarbonylamino, alkanesulfonamide, cyano, peterocycle, alkylthio, or amino.

When Rat, Rdt, Rds or Rd represents an alkyl group, this alkyl group may have a substituent and may be either linear or branched.

When Rat, Rdz, Rds or Rd represents an aryl group, the aryl group includes those having a substituent.

When Rdt , Rdt , Rd3 or Rd4 represents a heterocyclic group, the two heterocyclic groups include those having a substituent, and the heteroatom is at least one selected from a nitrogen atom, an oxygen atom, and a sulfur atom. A 5- or 6-membered monocyclic or condensed ring containing 5- or 6-membered rings is preferred, and is selected from, for example, pyridyl, quinolyl, furyl, benzothiazolyl, oxasilyl, imidazolyl, thiazolyl, triazolyl, benzotriazolyl, imide, and oxazine.

In the general formula (D-1?), the number of carbon atoms contained in Rdz is 0 to 15.

In the above-format (1)-9), the total number of carbons contained in Rd3 and Rd is 0 to 15.

-Format (D-10) (TIME)n -! In the NHI B I T formula, TI
The ME group is a group that is bonded to the coupling position of A and can be cleaved by reaction with the oxidized form of the color developing agent. After being cleaved by the coupler, it is cleaved sequentially, and finally the INHIBIT group is released under appropriate control. This is a possible group. 0 is 1 to 3, and when 2.3, each TIME group may be the same or different. INHIBITi is a group that becomes a development inhibitor upon release (for example, a group represented by the above-mentioned formats (D-2) to (D-9)).

In the -format (D-10), the -TIME group is typically represented by the following -formats (D-11) to (D-19).

General formula (D-11) General formula (D-12) General formula (D-13) General formula <o-x7) General formula (D-14) General formula (D-15) General formula (D-18) General formula (D-16) General formula (D-19) Rd.

-O-(Ch-N -CO- Rdt Rdh - In the formulas (D-11) to (D-15) and (D-18), Rd is a hydrogen atom, a halogen atom, or an alkyl, cycloalkyl, alkenyl, Represents a multigroup of aralkyl, alkoxy, alkoxycarbonyl, anilino, acylamino, ureido, cyano, nitro, sulfonamide, sulfamoyl, carbamoyl, aryl, carboxy, sulfo, hydroxy or alkanesulfonyl, forming (D-11) to (D -13), (D-15
), (D-18), Ras may combine with each other to form a condensed ring, - formation (D-11), (D-1
4), (D-15) and (D-19), Rd
h represents an aralkyl, alkenyl, alkyl, cycloalkyl, heterocycle or aryl group, and -formation (
In D-16) and (D-17), Rd? represents a hydrogen atom or a polygroup of alkyl, alkenyl, aralkyl, cycloalkyl, heterocycle or aryl, -
Rd and Rd in Formula 1 (D-19) each represent a hydrogen atom or an alkyl group (preferably an alkyl group having 1 to 4 carbon atoms), and -formation (D-11), (D-1
5) to (D-18), k represents Oll or an integer of 2, - formation (D-11) to (D-13), (D-
15), l in CD-18) represents an integer of 1 to 4, m in -formation (D-16) represents an integer of 1 or 2, and when 1 and m are 2 or more, each Rds 5Rdv may be the same. may be different, - n in formation (D-19)
represents an integer from 2 to 4, n Rds and Rd may be the same or different, and -i formula (D-16)
B in ~(D-18) represents the same meaning as oxygen. )
In the - formation (D-16), = 2 represents that it may be a single bond or a double bond, and in the case of a single bond, m is 2, and in the case of a double bond, m is 1.

-Formation (D-20) -fTT+r-3R-(-T 2 amount I N Hr B
In the I T formula, T1 is S RfT#I N HI B I
The component that cleaves T is SR.
After N H1BIT is generated, by reaction with the oxidized form of the developing agent, T2 is (T, after INHIBIT is generated, the component that cleaves INHIBIT is , INHIBIT is before development suppression, and ! and m each represent O or 1.

The component represented by SR may be one that generates the above-mentioned component by reaction with the oxidized form of the developing agent, such as a coupler component that undergoes a camp-reaction reaction with the oxidized form of the developing agent, and an oxidized form of the developing agent. Examples include redox components that undergo redox reactions.

Coupler components include acylacetanilides, 5-
Pyrazolones, virazoloazoles, phenols, naphthols, acetophenones, indanones, carbamoylacetanilides, 2 (5H)-imidacylones, 5-isoxacilones, uracils, homophthalimides, oxacilones, 2.5 -Dediazoline-
In addition to 1,1-dioxides, triazolothiadiazines, indoles, yellow couplers, magenta couplers, and cyan couplers, those that produce various dyes or those that do not produce dyes may be used.

fT T+TS R(T rEI N HI B I
It is preferable that T is bonded to the active site of component A in general formula (D-1).

In addition, when SR is a coupler component, SR is bonded to Ichigo TT+T, Seri T, and IN H1BIT so that it functions as a coupler only after it is cleaved from -JiT.

For example, when the coupler component is a phenol or naphthol, the oxygen atom of the hydroxyl group is the oxygen atom of the hydroxyl group at the 5-position of the tautomer, or the nitrogen atom at the 2-position is the tautomer. , also, acetophenones,
In indanones, the oxygen atom of the hydroxyl group of the tautomer is bonded to 1'fTT+'T, and T, -)--
Preferably, I N HI B I T is bound to the active site of the coupler.

When SR is a redox component, examples include hydroquinones, catechols, pyrogallols, aminophenols (e.g. (p-aminophenols,
O-aminophenols), naphthalene diols (e.g. 1,2-naphthalene diols, 1,4-naphthalene diols, 2,6-naphthalene diol W4), or aminonaphthols (e.g. 1,2-naphthalene diols) , 1.4-aminonaphthols, 2.6-aminonaphthols), and the like.

In addition, when SR is a redox component, SR is cleaved from 6T juice T and first combines with 1+TT+r- and →T NHIBIT to function as a redox component.

Examples of the groups represented by T and T2 include those represented by the aforementioned general formulas (D-11) to (D-19).

Examples of the development inhibitor represented by INHIBIT include those represented by the aforementioned general formulas (D-2) to (D-9).

Among the DIR compounds, preferred are those in which Y has the general formula (D-
2), (D-3), (D-8), (D-10) or (D
-20), (D-10), (D
-20), INHIBIT has the general formula (D-2)
, (D-3), (D-6) (especially -formation (D-6)
is an oxygen atom) or (D-8) is preferable. In the general formula (D-1), the coupler component represented by A includes a yellow image-forming coupler residue, a magenta color direct image-forming coupler residue. groups, cyan image forming coupler residues and colorless coupler residues.

Preferred DIR compounds used in the present invention include, but are not limited to, the following compounds.

Exemplary compound OC+*H core \ R,C0CHCORz -N ■ C (CHHz)+ C00CI(COOC+ zHzs Iiff -CONIICHICHtCOOH -CONHCII□CH, C00CH.

Including these, D that can be used in the present invention
Specific examples of IR compounds include U.S. Pat. No. 4,234,678;
3,227.544, 3,617,291, 3.958993, 4,149,866, 3,
No. 933,500, JP-A No. 57-56837, 51
-13239, U.S. Patent No. 2,072゜363, No. 2
．． No. 070.266, Research Disclosure-19
It is described in December 1981 No. 21228, etc.

The DIR compound contains 0, OO per mole of silver halide.
It is preferable to use 1 to 0.1 mol of O, especially o, o
It is preferable to use oi to 0.05 mol.

The DIR compound used in the present invention may be added at any location that affects the development of the silver halide containing the desensitizer described above, preferably in the silver halide emulsion layer, and more preferably in the silver halide emulsion layer. These are an emulsion layer containing silver halide containing the desensitizer and/or another emulsion layer having the same color sensitivity as the emulsion layer.

In the present invention, the position of the yellow filter layer in the photographic light-sensitive material is such that the exposure light reaches the position before the green-sensitive layer and the red-sensitive layer, and before the at least one blue-sensitive layer. It suffices if it is located at a position that the exposure light will reach later.

The yellow dye contained in the yellow filter layer is preferably one represented by the following formula (A) or CB).

General formula (A) General formula [13] R2 and R1 represent an alkyl group, R4 represents a hydrogen atom or a substituent, R1 represents an aryl group, n represents an integer from 1 to 4, represented by R1 or R1 Examples of the aryl group include phenyl group, naphthyl group, etc., with phenyl group being preferred.

The aryl group includes those having a substituent, and the substituent includes a sulfo group (including salts such as potassium group and sodium salt), an amino group (dimethylamino group, etc.), and a sulfonylamino group (methanesulfonylamino, ethane, etc.). sulfonylamino, dodecanesulfonylamino, etc.), alkoxy groups (methoxy, ethoxy, etc.), and R1 is preferably a phenyl group having at least an alkylsulfonylamino group;
3 is preferably a phenyl group having at least a sulfo group.

l-1 In the formula, R8 represents an aryl group or an alkoxy group; CHa / Yl~11 Yl~12 Yl~13 Shii3 l-20 υ In addition to these, yellow dyes include JP-A-61204630
No. 62-32460, No. 62-222248, No. 63-184769, No. 63-271351,
Examples include those described in No. 63-282738, No. 63-296039, and US Pat. No. 4,420,555.

It is preferable to use the yellow dye in the light-sensitive material in an amount of 1 to 1000 .mu./nf, and it is preferable to use the yellow dye in an optical density range of 0.05 to 3.0. Further, the timing of adding the yellow dye to the coating solution is not particularly limited.

A single color-sensitive layer means that the emulsion layer contains a plurality of layers having the same type of coupler, grain size of silver halide grains, halogen composition and crystal habit, and the same ratio of coupler and silver halide. It also includes cases where emulsion layers having the same color sensitivity are arranged as a continuous layer.

Here, "have the same color sensitivity" or "same color sensitivity"
For example, they may be the same in terms of blue sensitivity, green sensitivity, and red sensitivity, and do not need to have completely the same spectral sensitivity characteristics.

In the present invention, it is preferable that the blue-sensitive layer is a single layer, and it is more preferable that both the blue-sensitive and green-sensitive silver halide emulsion layers are a single layer.
Preferably, all of the green-sensitive and red-sensitive silver halide emulsion layers are each car-layers.

When the color-sensitive layer has a single-layer structure, the number of coated layers of photosensitive material is reduced compared to the conventional multi-layer structure, making it possible to form a thin film. Therefore, production efficiency, sharpness, and graininess are improved. The film thickness after drying is 20-3μ.
I is preferable, and 15 to 5 μm is particularly preferable.

Exposure latitude is the width of the amount of received light that produces significantly different exposure effects, and is the exposure range from highlights to deep shadows in the characteristic curve, as described in Photo Chemistry, page 393 (
Shashin Kogyo Shuppansha, 1982).

That is, it is the difference between j2 og)l at two points where the slope of the tangent line at the foot and shoulder of the characteristic curve, where the horizontal axis is ILog'd and the vertical axis is the transmission density, is 0.2.

The light-sensitive material of the present invention preferably has an exposure latitude of 3.0 or more, preferably 3.0 to 3.0, as measured by the above method.
8.0 is particularly preferred.

As a means for widening the exposure latitude of a single silver halide emulsion layer to 3.0 or more, a method of mixing and using silver halide grains having different sensitivities can be used. Specifically, examples include a method in which silver halide grains having different grain sizes are mixed and used, and a method in which a desensitizer is contained in at least a portion of the silver halide grains.

Silver halide grains with different grain sizes used in combination to obtain a wide exposure latitude have an average grain size of 0.2.
A combination of silver halide grains having a maximum average grain size of ~2.0 μm and silver halide grains having a minimum average grain size of 0.05 to 1.0 μm is preferable; One or more types of silver halide grains may be combined.

Further, the average grain size of the silver halide grains having the maximum average grain size is 1.5 to 4% of the average grain size of the silver halide grains having the minimum average grain size.
Preferably, it is 0 times.

In order to obtain a wide exposure latitude, it is possible to mix and use silver halide grains with different average grain sizes. If used, the difference in average grain size can be reduced without changing the sensitivity of silver halide grains, and furthermore, it is possible to mix and use silver halide grains having the same average grain size and different sensitivities.

That is, by using silver halide grains containing a desensitizer, exposure latitude can be obtained even if the coefficient of variation of the entire grain is reduced.

Therefore, these silver halide grains having a small coefficient of variation that are exposed to the same environment are preferred because their photographic performance is stabilized against changes over time and fluctuations in development processing. Furthermore, from the perspective of production technology, it is also possible to chemically sensitize a mixed system of silver halide grains with different sensitivities in the same batch.

Various desensitizers can be used, such as metal ions, antifoggants, stabilizers, and desensitizing dyes.

In the present invention, a metal ion doping method is preferred. Metal ions used for doping include group ib, group II b, group III a, and group III in the periodic table of elements.
Examples include metal ions of group b, group IV b, group Va, and group II. Preferred metal ions include Au, Zn
%Cd%Tit, Sc, Y, Bt, Fe1Ru, Os,
Examples include metal ions of Rh, Ir, Pd, Pr, Sm, and Yb. Particularly preferably Rh, Ru, Os, 1
It is r. These metal ions can be used, for example, as halide complex salts, and the pH of the AgX suspension system during doping is preferably 5 or less.

The doping amount of these metal ions varies depending on the type of metal ion, the particle size of the silver halide grains, the doping position of the metal ion, the desired sensitivity, etc.
Preferably 10-17 to 10-2 mol per 1 mol,
Furthermore, 10-12 to 10-3 mol is preferable, especially 1
0-9 to 10-' mol is preferred.

Further, by varying the type of metal ion, doping location, and doping amount, various different sensitivity qualities can be imparted to the silver halide grains.

If the doping amount is less than 10-2 mol/AgX mol, it will not have a large effect on grain growth, so silver halide grains with a narrow grain size distribution are adjusted under the same grain growth conditions and even under the same batch growth. be able to.

It is also possible to prepare silver halide grains with different doping conditions so that they can be put to practical use, then mix them in a predetermined ratio to form the same batch, and then chemically sensitize the grains. Each silver halide grain receives a sensitizing effect based on its properties, and an emulsion having a wide exposure latitude can be obtained depending on the sensitivity difference and mixture ratio.

The anti-capri agents or stabilizers include azoles (e.g., benzthiazolium salts, indazoles, triazoles, benztriazoles, benzimidazoles, etc.), heterocyclic mercapto compounds (e.g., mercaptotetrazoles, mercaptothiazoles, mercapto thiadiazoles, mercaptobenzthiazoles, mercaptobenzimidazoles, mercaptopyrimidines, etc.) azaindenes (e.g., tetraazaindenes, pentaazaindenes, etc.), the acid decomposition products (e.g., adenine, guanine, etc.), benzenethiosulfonic acids, Examples include thioketo compounds.

Examples of desensitizing dyes include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holoporacyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes.

The location of the desensitizer is preferably mixed inside the silver halide grains from the viewpoint of storage stability of the photosensitive material, stagnation stability of the coating solution, etc. Even if its distribution is uniform, It may be localized at the center of the particle or at an intermediate position, or may gradually decrease from the center of the particle toward the outside.

From the viewpoint of production efficiency, it is preferable that the seed particles be localized in the center of the particles, and if a method using seed particles with a small coefficient of variation is used, the steps after particle growth can be performed in the same batch.

In the light-sensitive material of the present invention, it is desirable that at least one color-sensitive layer (for example, a blue-sensitive layer) contains desensitizer-containing^gX particles, preferably a blue-sensitive layer, and more preferably a blue-sensitive layer. This is the case when the light-sensitive layer and the green-sensitive layer, most preferably all the color-sensitive layers, contain desensitizer-containing ^1°X particles.

In addition, the coefficient of variation defined by the ratio S/F of the standard deviation (S) of the grain size to the average grain size ('F) of the entire silver halide grains contained in each silver halide emulsion layer is 0.4 or less. is preferable, 0.33 or less is more preferable, 0.25 or less is still more preferable, and 0.20 or less is particularly preferable.

Average grain size (7) refers to the grain size (in the case of cubic silver halide grains, the length of its side, or in the case of grains with a shape other than a cube, when converted to a cube having the same volume) When the number of particles of ri (length of one side) is ni, it is defined by the following formula.

The relationship between particle size distribution is described in "Empirical relationship between sensitometric distribution and particle size distribution in photography," The Photographic Journal, Vol. LXXIX (1949) 330.
This can be determined using the method described in the article by Tribel and Smith on pages ~338.

The silver halide emulsion used in the light-sensitive material of the present invention includes:
Any conventional silver halide emulsion can be used, but silver halide containing substantially iodine in the halogen composition (for example, silver iodobromide, silver iodochlorobromide) is preferred;
In particular, silver iodobromide is preferable from the viewpoint of sensitivity, and the amount of iodine is 1
It is preferably mol% or more and ±20 mol% or less, particularly preferably 3.5 mol% or more and 12 mol% or less.

The emulsion can be chemically sensitized by a conventional method to achieve luster, and can be optically sensitized to a desired wavelength range using a sensitizing dye.

Antifoggants, stabilizers, etc. can be added to the silver halide emulsion. Gelatin is advantageously used as binder for the emulsion.

The emulsion layer and other wood-philic colloid layers can be hardened, and can also contain a plasticizer and a dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer.

A coupler is used in the emulsion layer of a light-sensitive material for color photography.

Furthermore, by coupling with a colored coupler having a color correction effect, a competing coupler, and an oxidized form of a developing agent, a developer, a silver halide solvent, a toning agent, a hardening agent, an antifoggant, and a chemical sensitizer can be obtained. Compounds that release photographically useful fragments such as spectral sensitizers, spectral sensitizers, and desensitizers can be used. The photosensitive material can be provided with auxiliary layers such as a filter layer, an antihalation layer, and an antiirradiation layer. These layers and/or the emulsion layer may contain dyes that are washed out or bleached from the light-sensitive material during the development process.

A formalin scavenger-1 fluorescent whitening agent, a matting agent, a lubricant, an image stabilizer, a surfactant, a color fog preventive agent, a development accelerator, a development retardant, a bleach accelerator, etc. can be added to the photosensitive material.

As the support, there may be used paper laminated with polyethylene or the like, polyethylene terephthalate film, lighter paper, cellulose triacetate, or the like.

The photosensitive material of the present invention is particularly useful as a negative photosensitive material.

To obtain a dye image using the photosensitive material of the present invention, after exposure,
Commonly known color photographic processing can be performed.

In the following margin [Examples] The present invention will be explained in more detail with reference to Examples.
The present invention is not limited to these examples. Prior to the Examples, silver halogen emulsions used in the Examples were prepared.

Migami 1” U1λ! 1. While controlling the pAg and pH in the reaction vessel, and simultaneously adding silver nitrate aqueous solution, potassium iodide aqueous solution, and potassium bromide aqueous solution while controlling the addition time, After precipitation and desalting using pHM solid gelatin, gelatin was added to prepare a seed emulsion. The obtained emulsion is called NE-1.

In addition, a seed emulsion was prepared in the same manner as above except that 3RhC1s was added to the reaction vessel (NE-2). The emulsion and its contents are shown in Table-1.

Table-1 Put the above seed emulsion and gelatin aqueous solution into a reaction pot.
While controlling pAg and pH in the reaction vessel, add ammoniacal silver nitrate aqueous solution, potassium iodide aqueous solution, and potassium bromide aqueous solution in proportion to the surface area during particle growth, and add potassium bromide aqueous solution at an appropriate particle size. (C
Instead, it was added continuously. After precipitating and desalting in the same manner as the seed emulsion, gelatin was added and redispersed to obtain pA37.8, p
) An emulsion of 16.0 was obtained. In this way, the silver iodobromide emulsion EM-1 with a high iodine content inside the grains is produced □ EM −
4 was prepared.

Table 2 shows the emulsions and their contents.

Margins Below Margins Example 1 Trial No. 1018 Multilayer color photosensitive material No. 101 having a multilayer structure having the following composition on a subtracted cellulose acetate support.
was created.

The coating amount is the amount expressed in gem" units for silver halide and colloidal silver, and the amount expressed in gem" units for additives and gelatin, and the amount for sensitizing dyes, couplers, and DIR. The chemical composition is expressed as the number of moles per mole of silver halide in the same layer. The emulsions contained in each color-sensitive emulsion layer were optimally sensitized using sodium thiosulfate and chloroauric acid.

Margin layer below Main composition 1st layer (HC) Black colloidal silver (halation gelatin prevention layer) Ultraviolet absorber UV-1 Ultraviolet absorber UV-2 Dioctyl phthalate (abbreviated as DOP) Second layer (IL-1) Gelatin (Interlayer) Anti-staining agent (AS-1) DOP Third layer (R-1) EM-2 (First red-sensitive emulsion layer) Gelatin sensitizing dye ■ Sensitizing dye II Coupler (C-1) Coupler (cc -1) DIR compound (D-23) DIR compound (D-42) DOP 4th layer (R-2) EM-1 Usage amount 0.20 1.5 0.1 0.2 0.03 2.0 0 .1 0.1 1,2 1.1 sxio-'lXl0-' 0, 0B5 0, 005 0, 0015 0, 002 0, 6 1, 3 (Second red-sensitive emulsion layer) Gelatin sensitizing dye I Sensitization Dye II Coupler (C-2) Coupler (C-3) Coupler (CC-1) DIR compound (D-42) DOP 5th layer (IL-2) Gelatin (intermediate layer) AS-1 DOP 6th layer (G -1) EM-2 (1st green emulsion layer) Gelatin sensitizing dye! ! ! Sensitizing dye ■ Coupler (M-2) Coupler (CM-1) DIR compound (D-23) DIR compound (D-28) Tricresyl phosphate 1.1 3X10-'txio-' 0, 007 0, 027 0 .0015 0.001 0.2 0,8 0,03 0.1 1.3 1,2 2.5xlO-+ 1.2X10-4 0, 09 0, 004 o,oot O,003 0,5 (Below (abbreviated as TCP) 7th layer (G-2) EM-1 (second green-sensitive emulsion layer) Gelatin sensitizing dye III Sensitizing dye■ Coupler (M-1) Coupler (CM-1) DIR compound (D-26 ) CP 8th layer (YC) Gelatin (yellow yellow colloidal silver filter layer) AS-1 CP 9th layer (B-1) EM-2 (1st blue emulsion layer) Gelatin sensitizing dye V Coupler (Y-1 ) CP 10th layer (B-2) EM-1 (Second blue-sensitive emulsion layer) Gelatin 1, 4 0, 8 1.5X10-' t, oxio-' 0, 03 0, 002 o, oot O13 0, 6 0,08 0,10,3 0,5 1,1 1,3XIC)" 0,29 0,20,5 1.2 Sensitizing dye V lXl0-' coupler (
Y-1) 0.08 DIR compound (D-42) 0.003TCP
0. 1 11th layer (Pro
-1) Gelatin 0.55 (first protective layer) Ultraviolet absorber UV-10,1 Ultraviolet absorber UV
-20,2 DOP 0.03 Silver iodobromide Ag
l 1mo1%0. 5 Average particle size 0.07 μm 12th layer (Pro-2) Gelatin 0
．． 5 (Second protective layer) Polymethyl methacrylate
0. 2 particles (diameter 1.5 μm) Formalin scavenger 3.0 (MS-1) Hardener (H-1) 0.4 In addition to the above components, a surfactant was added to each layer as a coating aid.

C- D CM-1 U ■ - Sensitizing dye■ Sensitizing dye■ Sensitizing dye■ \/ Sensitizing dye I Sensitizing dye II Sensitizing dye■ In the following description, each layer of the above composition is referred to as the above-mentioned HC.
, IL-1, R-1, R-2, IL-2, G-1, G-
2. Use abbreviations such as YC, B-1, B-2, Pro-1, Pro-2, etc.

Next, samples No. 102 to No. 110 were prepared.

Sample No. 102 was prepared in the same manner as Sample No. 101, except that the yellow dye according to the present invention was added in the type and amount shown in Table 3 instead of the YC yellow colloidal silver of Sample No. 101.

Sample No. 103 is B-2 in sample No. 101.
Sample No. except that the emulsion contained in B-1 was changed to an equimolar mixture of EM-1 and EM-2, and the amounts of emulsion, gelatin, and TCP contained in B-1 were increased by 15%.
, 101. (The amount of B-1 sensitizing dye and coupler DIR compound per mole of silver halide is:
It is the same as sample No. 101. ) Sample No. 104 and sample No. 108 are sample No.
Sample No. 103 was prepared in the same manner as Sample No. 103, except that the yellow dye according to the present invention was added in the type and amount shown in Table 3 instead of the YC yellow colloidal silver.

Sample No. 109 is B- in sample No. 104.
Sample No. 104 was prepared in the same manner as Sample No. 104, except that the emulsion contained in Sample No. 1 was replaced with an equimolar mixture of EM-2 and EM-3.

Sample No. 110 was prepared in the same manner as Sample No. 104, except that the emulsion contained in Sample No. 104 was replaced with EM-4.

The samples thus prepared and their contents are shown in Table 3.

Margin below The amount of yellow dye added was expressed in sol/m2.

(Similarly below) Sample No. 101 to sample No. 10 obtained in this way
1llO was evaluated for the storage stability of the photosensitive material and the storage stability of the latent image.

△Shelf life of ヱJL 粲 The 1 L dan sample was divided into two parts, and one part was stored at 50℃ and 80% relative humidity for 7 days, and the other part was stored in a refrigerator (5℃) for 7 days. After that, wedge exposure is performed according to the conventional method, and the following processing steps are performed to determine the gradation preservation property (
Table 4 shows the results of the evaluation of the blue-sensitive layer (described later).

Evaluation method for latent image preservation After dividing the sample into two parts and performing wedge exposure according to the usual method,
One part was stored at 25°C with a relative humidity of 80%, and the other part was stored in a refrigerator at 11i (5°C) for 15 days, and then processed using the following processing steps to preserve the latent image ( The preservation of the gradations (described later) was evaluated.

Table 4 shows the results of the blue-sensitive layer obtained.

A method for evaluating gradation preservation +t will be explained using diagrams.

FIG. 1 shows a reference characteristic curve (broken line) and a characteristic curve to be evaluated (solid line). In addition, FIG. 2 shows each exposure point between the exposure point that gives the minimum density +061 in FIG. 1 and the exposure point of ΔlogH・÷3°0, i5) point gamma values are shown.

Here, from FIG. 2, the absolute value Δγ of the difference in point gamma values at each exposure point between the reference characteristic curve and the characteristic curve to be evaluated is determined. Then, the preservation of gradation was expressed by the value (Δ) which is the average value of Δγ multiplied by 1000 and the value Σ which is the standard deviation σ of Δγ multiplied by 1000. That is, the larger the value of Δ, the larger the difference in point gamma between the two characteristic curves, and the larger the value of Σ, the more uneven the change in gradation becomes, indicating that the preservation of gradation is poor.

Processing process (38℃) Color development 3 minutes 15 seconds Bleaching 6 minutes 30 seconds Water washing 3 minutes 15 seconds
1. Washing with water for 6 minutes and 30 seconds. Stabilizing for 3 minutes and 15 seconds. Drying for 1 minute and 30 seconds. The composition of the treatment liquid used in each treatment step is shown below.

(Color developer) 4-amino-3-methyl-N-ethyl-N-(β-hydroxyethyl) aniline sulfate anhydrous sodium sulfite hydroxylamine 1/2 sulfate anhydrous potassium carbonate potassium bromide nitrilotriacetic acid 3 Sodium salt (monohydrate) Add potassium hydroxide water to adjust to 11 (pH = 1 (bleaching solution) 4.75 g 4.25.g 2.0 g 37.5 g 1.3 g 2.5 g 1 .0 g 0, 02) Ethylenediaminetetraacetic acid iron (III) ammonium salt 100.0 g Ethylenediaminetetraacetic acid iron 2 ammonium salt 10.0 g Ammonium bromide 150.0 g Glacial acetic acid IO, 0 g Water was added to make 11, and ammonia Adjust the pH to 6.0 using water (fixer) Ammonium thiosulfate 175.0g Anhydrous ammonium sulfite 8.6g Sodium metasulfite 2.3g Add water and 1
℃ and adjust the pH to 6.0 using acetic acid.

(Stabilizing liquid) Formalin (37% aqueous solution) 1.5 mft
Konidax (manufactured by Konica Corporation) 7.5+nj
! Add water and bring to 1°C.

Table 4 As is clear from Table 4, the sample of the present invention has a small gradation shift from the highlight to the shadow of the characteristic curve and has excellent gradation preservation in storage of photosensitive materials and latent image storage. You can see that

The yellow dye according to the present invention has a small effect when the blue-sensitive layer is a multi-layer structure (comparison between Sample No. 101 and Sample No. 102), but it has a very large effect when it has a single layer structure (Sample No. 102).
103 and Sample No. 104).

This was unexpected even for the inventors.

Moreover, sample No. 110 is preferable in terms of production efficiency, since physical ripening and chemical ripening can each be performed once in the preparation of the emulsion, compared to other samples.

In addition, 4 of the yellow dye contained in YC of sample No. 104
It was found that even if 0 mol% was replaced with yellow colloidal silver, the effect of the present invention was obtained.

Also, instead of yellow dye YI-5 in sample No. 104, Yl
-2, YI-3, each sample using Yl-11, sample No.
, Yl-9, Yl instead of yellow dye Yl-5 in 109
The effects of the present invention were also observed for each sample using Yl-13 and Yl-19.

Example 2 Sample No. 101 and sample No. 10 prepared in Example 1
4 were used as they were, sample No. 201, and sample No. 201, respectively.

It was set to 202.

Sample No. 203 is G-
Except for 2, the emulsions contained in G-1 were EM-1 and EM-
In place of the equimolar mixture of G-1, an emulsion further contained in G-1,
It was produced in the same manner as Sample No. 202, except that the amounts of gelatin and TCP used were increased by 30%.

(The amount of the sensitizing dye and coupler DIR compound of G-1 per mole of silver halide is the same as that of sample No. 202.) Sample No. 204 has the same R-
Except for 2, the emulsions contained in R-1 were EM-1 and EM-
Sample No. 203 was prepared in the same manner as Sample No. 203, except that the amounts of emulsion gelatin and DOP contained in R-1 were increased by 25% in place of an equimolar mixture of Sample No. 2 and DOP.

(The amount of the R-1 sensitizing dye and coupler DIR compound per mole of silver halide is the same as Sample No. 203.) Sample No. 205 to Sample No. 208 are the same as Sample No. 2.
The emulsion contained in 04 was changed as shown in Table 5, and YC
Except for changing the yellow dye contained in as shown in Table 5,
It was produced in the same manner as sample No. 204.

Sample No. 201 to Sample No. thus obtained.

The contents of 208 are shown in Table-5.

The samples thus prepared were evaluated for storage stability of l@l tone in storage of photosensitive materials and storage of latent images in the same manner as in Example 1.

In addition, the sample was divided into two parts, and one part was subjected to wedge exposure in the same manner as in Example 1.The sample was processed in the same manner as in Example 1, except that the p)I of the developer in the processing step was changed to 9.8. The storage stability of gradation during fluctuation was evaluated in the same manner as in Example 1.

The results for the blue sensitive layer are shown in Table 6.

Margin Table 6 below As is clear from Table 6, the samples of the present invention are excellent in the storage stability of photosensitive materials and latent image storage, and are also extremely excellent in gradation storage against processing variations.

The effect of the yellow dye according to the present invention on gradation preservation is greater when the photosensitive emulsion layer is a single layer than when it is a multilayer, and the processing stability is more effective when the photosensitive emulsion layer is a single layer. I understand.

Comparing among the samples of the present invention, among the photosensitive emulsion layers,
A single layer consisting of a blue-sensitive emulsion layer and a green-sensitive emulsion layer is
It is preferable because it has a large improvement effect on storage stability and processing stability, and it is preferable that all photosensitive emulsion layers are made into a single layer.
This is preferable because the improvement effect is even greater.

Sample No. 205 to Sample No. 208 contain an emulsion doped with Rh inside the grains, the grain size distribution of the silver halide grains in each photosensitive layer is narrow, and the improvement effect is even greater. It has been found to be a preferred embodiment of the invention.

In this example, an emulsion with a variation coefficient of 19 to 20% was used, but the effect of the present invention was also observed even when an emulsion with a variation coefficient of 29% was used.

In addition, each sample used D-4, D-2, and D-29 in place of DIR compound D-23 in B-1 of sample 208, and D-6 and D-2 in place of D-23 in G-1. , each sample using D-10, D-17, D-19 in place of D-42 of R-1,
The effects of the present invention were also observed for each sample using D-21.

Also, RhcI! , instead of RuCj! , , 05
A seed emulsion prepared by adding CRs, Pb (NO3) 2 was used instead of NE-2 to prepare an emulsion as sample N.
o, 205 EM-3 and sample No. 206 to sample No.
, 208 for each sample used instead of EM-4,
The effects of the present invention were obtained.

[Effects of the Invention] The photosensitive material obtained by the present invention has excellent storage stability and latent image storage stability, as well as excellent stability against fluctuations in processing conditions.

[Brief explanation of the drawing]

FIG. 1 is a graph showing a reference characteristic curve (broken line) and a characteristic curve to be evaluated (solid line) of a photographic light-sensitive material. FIG. 2 is a graph showing the point gamma of a photographic light-sensitive material between a reference characteristic curve (broken line) and a characteristic curve to be evaluated (solid line).

Claims (1)

[Claims] A silver halide color photographic light-sensitive material comprising at least blue-sensitive, green-sensitive and red-sensitive silver halide emulsion layers and a yellow filter layer on a support.
A silver halide color photograph comprising an R compound, wherein the yellow filter layer contains a yellow dye, and at least one of the blue, green and red color-sensitive layers has a single layer structure. photosensitive material.