JPH04177339A - Silver halogenide picture sensitive material - Google Patents

Abstract

PURPOSE:To reduce dependency on exposure illuminance, to achieve high sensitivity and gradation as well as color reproducibility, and to improve reciprocity, characteristic by including a specific coupler in at least one layer of halogenated silver emulsifier layers. CONSTITUTION:A coupler expressed by an expression I is included in at least one layer of halogenated silver emulsifier layers. At least two kinds of halogenated silver emulsifiers mixed together, which are different in sensitivity, are mixed together for the halogenated silver particle included in the halogenated silver emulsfier layer, while the illuminance dependency of the sensitivity of the halogenated silver emulsifier in the side of low sensitivity is lower than that of the halogenated silver emulsifier in the side of the high sensitivity. In the expression I, Z is a non-metallic atom group necessary for forming a heterocycle including nitrogen, while the cycle formed by Z may have substituent. X is a hydrogen atom or a group that can be removed through the reaction with oxide of coupling main chemical, while R is a hydrogen atom or substituent. The illuminance dependency of gradation can be improved without reducing the sensitivity, and a sensitive material of high sensitivity and of excellent gradation characteristic as well as color reproducibility can thus be obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a silver halide photographic light-sensitive material (hereinafter referred to as "photosensitive material"), and more specifically, the present invention relates to a silver halide photographic light-sensitive material (hereinafter referred to as "photosensitive material"), and more specifically, a silver halide photographic light-sensitive material (hereinafter referred to as "photosensitive material"). This results in excellent color reproducibility;
The present invention relates to a photosensitive material that allows high-quality photographs to be obtained more easily and stably.

[Background of the invention]

One of the characteristics of photosensitive materials is that even if the same amount of light is irradiated, photographic properties such as sensitivity may differ between high-intensity, short-time irradiation and low-intensity, long-term irradiation. Well known in the art, this phenomenon is called reciprocity failure.

In practical systems, countermeasures are taken to prevent changes in sensitivity due to increases in illuminance, such as changing the exposure amount in response to anticipated changes in sensitivity.
In practical terms, this is not a big obstacle.

However, if the variation in gradation due to exposure illuminance (hereinafter referred to as "illuminance dependence of gradation") is large, it becomes a fatal defect in terms of the quality of the photosensitive material.

Each photosensitive material has a desired gradation depending on the purpose of use, and each gradation is designed. When these photosensitive materials are actually exposed, the exposure conditions, for example, the brightness of the subject for photosensitive materials, and the difference in image density due to overexposure or underexposure of the original film for photosensitive materials for printing, the exposure illuminance naturally varies. changes.

In a photosensitive material whose gradation is highly dependent on illuminance, the actual gradation may deviate from the allowable range of the designed target gradation depending on the exposure illuminance.

As a result, depending on the scene, the contrast may be too high, resulting in a lack of depiction especially in low-density or high-density areas, or conversely, the contrast may be too soft, resulting in a dull, boring look. In the case of color photographs, if the gradation balance between each photosensitive layer is disrupted, the colors of the print may change in an unfavorable direction, and in any case, the quality of the photosensitive material will be significantly impaired.

Furthermore, in the case of photosensitive materials for printing, there are various print sizes, and the commonly used ones range from a small one called E size to full paper size, and depending on the purpose, there are prints that are more than twice the size of full paper. is sometimes created.

Typically, users first print several scenes in a small size, then select a preferred scene from among them and enlarge it to a large size. At this time, the original film is the same whether it is printed in a small size or large size, and it is difficult to significantly increase the light source intensity, so when enlarging it into a sky print, it is necessary to It is unavoidable that the exposure illuminance to the material will be reduced. As a result, when the dependence of gradation on illuminance is large, even if a desirable image quality is obtained in a small-sized print, the image quality deteriorates in a large-scale print, and the user cannot be satisfied.

As mentioned above, exposure equipment has been improved to deal with changes in sensitivity due to exposure illuminance, so it is no longer a problem in practice.However, changes in gradation need to be improved in equipment such as exposure equipment. However, it is difficult to deal with this problem, and it is desired to improve the illuminance dependence of the gradation of photosensitive materials.

Many techniques for improving the reciprocity law failure characteristics of photosensitive materials are known.

For example, JP-A-61-47941, JP-A-61-2314
No. 6, No. 61-97648, No. 61-112142, No. 62-7042, No. 63-316039, U.S. Pat. Ir, Cd, Pb
, Zn, Fe.

A technique for improving reciprocity law failure characteristics by doping with Rh etc. has been disclosed, but the effect is insufficient;
Furthermore, undesirable changes in photographic characteristics such as a decrease in sensitivity, an increase in fog, a large increase in contrast, or a change in gradation called softening are often accompanied, and the effects that can be obtained are limited.

Also, JP-A-63-212932, JP-A No. 63-3042
No. 53, JP-A No. 1-121847, JP-A No. 1-12184
No. δ, No. 1-167752, etc. also disclose improved techniques using silver halide grain formation methods, sensitization methods, etc., but the effects are insufficient.

Furthermore, as a gradation adjustment technique, the technique of mixing silver halide grains having the same color sensitivity but different sensitivities is well known in the art.
No. 542, JP-A-59-148049, JP-A No. 63-71
No. 838, etc., there is a description of using a mixture of silver halide emulsions with different sensitivities by changing the grain size, crystal habit, composition, etc. of silver halide grains, but there is no description suggesting improvement of reciprocity law failure. do not have.

JP-A-57-192942 discloses Ir-containing particles and Ir-containing particles.
Although a technique using mixed non-containing particles has been disclosed,
There is no description of the effect of improving reciprocity law failure characteristics, but rather, ``When two or more types of silver halide grains are used together, changing the exposure time will change the characteristics, especially contrast and gradation from low density areas to high density areas. "A uniform finish cannot be obtained," which not only does not suggest the effects of the present invention, but also indicates that the effects of the present invention are unexpected.

JP-A-1-131544 discloses a technique for chemical sensitization by mixing silver halide emulsions with different amounts of metal doping, but there is no mention of improvement in reciprocity law failure characteristics, which suggests the present invention. There is no description.

JP-A-63-71839, JP-A No. 62-5234, JP-A No. 6
No. 2-172348, etc., describes an example in which an emulsion doped with iridium is mixed, but there is no mention of reciprocity failure, and the conditions are outside the preferable range defined in the present invention. This does not imply the present invention.

As mentioned above, in the prior art, even if a silver halide emulsion, which is completely unknown in the art and whose gradations are highly dependent on illuminance when used alone, satisfies specific conditions. For example, by combining emulsion mixing and a pyrazoloazole magenta coupler, it is possible to obtain a photosensitive material that has excellent reciprocity law failure characteristics and also has excellent sensitivity, gradation, fog resistance, and color reproducibility. This finding led to the present invention.

[Purpose of the invention]

An object of the present invention is to provide a photosensitive material in which the dependence of gradation on exposure illuminance is extremely small by introducing a new technique for improving reciprocity law failure characteristics.

Another object of the present invention is to provide a photosensitive material that has high sensitivity, excellent gradation and color reproducibility, and excellent reciprocity law failure characteristics.

[Structure of the invention]

An object of the present invention is to provide a light-sensitive material having at least one silver halide emulsion layer on a support, in which at least one of the silver halide emulsion layers contains a coupler represented by the following general formula [M-I:l]. The silver halide grains contained in the silver halide emulsion layer are a mixture of at least two types of silver halide emulsions having different sensitivities, and the illuminance of the sensitivity of the silver halide emulsion on the lower sensitivity side This is achieved by a light-sensitive material characterized in that the dependence on illuminance is smaller than the dependence on illuminance of a silver halide emulsion on the high-speed side.

In the formula, 2 represents a group of nonmetallic atoms necessary to form a nitrogen-containing heterocycle, and the ring formed by Z may have a substituent. X represents a hydrogen atom or a group that can be separated by reaction with an oxidized product of a color developing agent, and R represents a hydrogen atom or a substituent.

The present invention will be explained in detail below.

First, the magenta coupler represented by the general formula [M-I] used in the present invention will be explained.

In the general formula [M-I], there are no particular restrictions on the substituent represented by R, but typically there are six groups such as alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl, and cycloalkyl. In addition, halogen Jll [child and hycycloalganyl, alkynyl, heterocycle, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyan, alkoxy, aryloxy, heterocycleoxy, siloxy, acyloxy , carbamoyloxy, amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl,
Also included are aryloxycarbonyl, six heterocyclic thio groups, spiro compound residues, bridged hydrocarbon compound residues, and the like.

The alkyl group represented by R preferably has 1 to 32 carbon atoms, and may be linear or branched.

The aryl group represented by R is preferably a phenyl group.

Examples of the acylamino group represented by R include an alkylcarbonylamino group and an arylcarbonylamino group.

Examples of the sulfonamide group represented by R include an alkylsulfonylamino group and an arylsulfonylamino group.

Examples of the alkyl component and aryl component in the alkylthio group and arylthio group represented by R include the alkyl group and aryl group represented by R above.

The alkenyl group represented by R preferably has 2 to 32 carbon atoms, and the cycloalkyl group preferably has 3 to 12 carbon atoms, especially 5 to 7 carbon atoms, and the alkenyl group may be linear or branched.

The cycloalkenyl group represented by R has 3 to 3 carbon atoms.
12, especially those of 5 to 7 are preferred.

Sulfonyl groups represented by R include alkylsulfonyl groups, arylsulfonyl groups, etc.; sulfinyl groups include alkylsulfinyl groups, arylsulfinyl groups, etc.; phosphonyl groups include alkylphosphonyl groups, alkoxyphosphonyl groups, and aryloxyphosphonyl groups. , arylphosphonyl group, etc.; As an acyl group, an alkylcarbonyl group, an arylcarbonyl group, etc.; As a carbamoyl group, an alkylcarbamoyl group, an arylcarbamoyl group, etc.; As a sulfamoyl group, an alkylsulfamoyl group,
Arylsulfamoyl, etc.; As an acyloxy group, an alkylcarbonyloxy group, an arylcarbonyloxy group, etc.; As a carbamoyloxy group, an alkylcarbamoyloxy group, an arylcarbamoyloxy group, etc.; As an ureido group, an alkylureido group, an arylureido group, etc. ; As the sulfamoylamino group, an alkylsulfamoylamino group, an arylsulfamoylamino group, etc.; As the heterocyclic group, a 5- to 7-membered one is preferable, and specifically, a 2-furyl group, a 2-thienyl group, a 2- Pyrimidinyl group, 2-benzothiazolyl group, etc.; as the heterocyclic oxy group, those having a 5- to 7-membered heterocycle are preferred, such as 3.
4.5.6-tetrahydropyranyl-2-oxy group, l
-Phenyltetrazole-5-oxy refinishing; The heterocyclic thio group is preferably a 5- to 7-membered heterocyclic thio group, such as 2-pyridylthio group, 2-benzothiazolylthio group, 2.4-diphenoxy-1, 3,5-triazole-6-thio group; As a siloxy group, a trimethylsiloxy group, a triethylsiloxy group, a dimethylbutylsiloxy group; As an imide group, a succinimide group, a 3-heptadecylsuccinimide group, a 7-talimide group. and glutarimide groups, such as spiro [3,3] heptan-1-yl; examples of bridged hydrocarbon compound residues include bicyclo [2゜2.
1] Hebutan-1-yl, tricyclo [3,3,1
, l''·7]decane-1-yl, 7,7-dimethyl-bicyclo[2,2,1]heptane-1-yl, and the like.

Groups that can be separated by reaction with the oxidized product of the color developing agent represented by X include, for example, halogen atoms (chlorine atom, bromine atom, fluorine atom, etc.), alkoxy, aryloxy, heterocyclic oxy, acyloxy, sulfonyloxy, alkoxy Carbonyloxy, aryloxycarbonyl, alkyloxalyloxy, alkoxyoxalyloxy, alkylthio, arylthio, heterocyclic thio, alkyloxythiocarbonylthioamide, NJlj [nitrogen-containing heterocycle bonded with child, alkyloxycarbonylamino, aryloxycarbonyl Amino, carboxyl, (R1' is the same as the above R, 2' is the same as the above Z, and R,/and R3' represent a hydrogen atom, an aryl group, an alkyl group, or a heterocyclic group), etc. Among them, a halogen atom, particularly a chlorine atom is preferred. Examples of the nitrogen-containing heterocycle formed by Z or Z' include a pyrazole ring, imidazole ring, triazole ring, or tetrazole ring, and examples of the substituents that the ring may have include those described for R above. can be mentioned.

More specifically, what is represented by the general formula [M-I] is represented by, for example, the following general formulas [M-II) to [M-■].

General formula [M-I[) General formula [M-I[1] -N-N General formula [M-IV] General formula [M-V] General formula [M-Vl] General formula [M-■] - N-N In the general formulas [M-11) to [M-■], R1 to R
, and X have the same meanings as R and X above.

Also, preferred among the general formulas [M-1] are those represented by the following general formula [M-■].

General formula [M-■] In the formula, R, , X and Z have the same meanings as R, X and Z in general formula [M-I) 1:.

Among the magenta couplers represented by the general formulas [M-n) to [M-■], those of the general formula [M-
This is a magenta coupler represented by 11).

The most preferred substituents R and R1 on the heterocycle are those represented by the following general formula [M-II)j:.

General formula [M-11:I R.

(2) In the formula, Rs, R+o and R++ each have the same meaning as R above.

Also, two of the above R=, R+- and R11 are 1fR.
9 and R1° may be combined to form a saturated or unsaturated ring (e.g., cycloalkane, cycloalkene, heterocycle), and R11 is further combined to the ring to form a bridged hydrocarbon compound residue. You may.

Among the general formula [M-II), (i) R9
When at least two of ~R1□ are alkyl groups, (
ii) One of Re-R11, for example, R1□, is a hydrogen atom, and the other two R9 and RIG combine to form a cycloalkyl together with the root carbon atom.

Furthermore, in (1), it is preferable that two of R1 to R11 are alkyl groups and the other one is a hydrogen atom or an alkyl group.

In addition, substituents that the ring formed by Z in general formula [M-I] and the ring formed by Zl in general formula [M-■] may have, and general formulas [M-n) to ( M
-Vl), ~R, and the following general formula [
Those represented by M-X) are preferred.

General formula [M-X) -R'-3Q, -R'' In the formula, RJ represents an alkylene group, and R1 represents an alkyl group, a cycloalkyl group, or an aryl group.

In the alkylene group represented by R1, the linear moiety preferably has a degree prime of 2 or more, more preferably 3 to 6, and does not matter whether the linear chain is bibranched or not.

The cycloalkyl group represented by R8 is preferably a 5- to 6-membered one.

The following number 2 shows typical specific examples of the compounds according to the present invention.
'11 CH.

11m * BesH++(t) Ushi@H+y c+sl'lss N -N -NH x:y-50:5Q In addition to the above typical examples of the compounds according to the present invention, there are For example, JP-A-62-1663
Among the compounds described on pages (18) to (32) of Specification No. 39, No. 1-4, 6, 8-17.19-
24.26~43.45~59.61~104.106
-121.123-162.164-223 can be mentioned.

Also, the coupler is described in the Journal of the Chemical
Society (Journal of the Che)
micalSociety) + Perki
n) I (1977), 2047-2052, U.S. Pat. No. 60
-43659, 60-172982, 60-1
No. 90779, No. 62-209457 and No. 63-30
It can be synthesized by referring to No. 7453 and the like.

The coupler expressed by the -fi formula [M-1] is usually Hao1f
The coupler can be used in the range of lXl0-' mol-1 mole per 1M11 mole of magenta compound, preferably in the range of l X 10-' mole to 8 X to-' mole.The coupler may also be used in combination with other types of magenta couplers. You can also do it.

Next, the silver halide emulsion layer according to the present invention will be explained.

In the present invention, the silver halide grains contained in the silver halide emulsion layer containing the pyrazoloazole magenta coupler represented by the general formula [M-I] have substantially the same color sensitivity (preferably green sensitivity). It is a mixture of at least two types of silver halide emulsions having different sensitivities.

In this case, at least one of the silver halide emulsions to be mixed
In the two combinations, the sensitivity dependence of the silver halide emulsion on the lower sensitivity side must be smaller than the illuminance dependence of the sensitivity of the silver halide emulsion on the high sensitivity side. Here, the illuminance dependence of sensitivity is determined by the exposure time being 0.0
It is expressed as the variation range of sensitivity when changing from 2 seconds to 10 seconds.

The above sensitivity is expressed as the reciprocal of the exposure amount required to obtain a reflection density of 0.8, and is evaluated based on its relative value. In addition, the illuminance dependence can be determined by exposing each sample to wedge light with an exposure time of 0.02 seconds (high illuminance condition) and an exposure time of 10 seconds (low illuminance condition) so that the exposure amount is the same. Dependency (△S)
Find out.

△S is the ratio of the sensitivity obtained when exposed under high illuminance conditions and the sensitivity obtained when exposed under low illuminance conditions, and is expressed by the following formula. The smaller the value of △S, the lower the sensitivity. This is a silver halide photographic material with low illuminance dependence.

In the present invention, there is no particular restriction on the method of making the illuminance dependence of the sensitivity of the silver halide emulsion on the low-speed side smaller than the illuminance dependence of the sensitivity of the silver halide emulsion on the high-sensitivity side, such as chemical sensitization conditions. When adding a water-soluble iridium compound at the time of forming silver halide grains, this can be done by changing the amount of addition.

Preferably, at least part of the means for adjusting the illuminance dependence of sensitivity is carried out by adjusting the amount of a water-soluble iridium compound added during silver halide grain formation or growth. In this case, the amount of the water-soluble iridium compound added is expressed as the average amount added per grain of silver halide, and the amount added per grain of the silver halide emulsion on the low-speed side is higher than that of the silver halide emulsion on the high-speed side. It is preferable that the average amount of the water-soluble iridium compound added is large.

Here, the average addition amount per silver halide grain [1r
],, are expressed by the following formula.

[1r],, = [1r]/N [1r]: Average amount of water-soluble iridium compound added per grain [1r]: Total amount of water-soluble iridium compound added N: Number of silver halide grains (N is the amount added) (Calculated from the amount of silver and average grain size.) When using an iridium compound as a means to adjust the illuminance dependence of sensitivity, the copper halide emulsion on the high-sensitivity side may or may not be used with a water-soluble iridium compound. Good, but
It is preferable that the average amount added per silver halide grain is smaller than that of the lower-speed emulsion.

The amount of the water-soluble iridium compound to be added may satisfy the above relationship, but preferably, the amount of the low-speed emulsion is 2X 10
-"~5X 10-"mol/1 grain, high-speed side emulsion is 2
There is a range of
3-5×lO-molar 1 grain, high-speed side emulsion is 2X
It ranges from 10-'' to 2X 10-'' moles/particle.

The water-soluble iridium compound used in the present invention is not particularly limited, but from the viewpoint of compound stability, safety, economic efficiency, etc., industrially possible and preferable compounds include halogenated iridium (I[l) compounds, halogenated iridium Iridium chloride (
TV) compounds, iridium complex salts having halogens, amines, oxalates, etc. as ligands.

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

Iridium trichloride, iridium tribromide, hexachloroiridium (I[[) potassium, iridium sulfate (I[[
) ammonium, iridium ternary acid (I[I) potassium, iridium ternary acid (I[[) tripotassium, iridium sulfate (I[[), trioxalate iridium (III
), iridium tetrachloride, iridium tetrabromide, potassium hexachloroiridium (IV), ammonium hexachloroiridium (IV), potassium iridium (rV), iridium (IV) trioxalate.

In the present invention, any of these compounds can be selected, and they can also be used in combination as necessary.

These iridium compounds are used after being dissolved in water or a water-miscible solvent, and methods commonly used to stabilize solutions of iridium compounds, such as hydrogen halides (e.g. hydrochloric acid, hydrobromic acid, etc.) or A method of adding an alkali halide (eg, potassium chloride, sodium chloride, potassium bromide, etc.) can be used.

There are no particular restrictions on the method of adding the water-soluble iridium compound;
For example, there are methods such as adding an iridium compound to the mother liquor before nucleation, adding the iridium compound in a rush during the growth of silver halide, adding it to the halide solution, and adding the iridium compound to the halide solution after growth, just before physical ripening. Can be mentioned. Preferably, the method is one in which one halide solution is added. Further, the iridium metal may be added in different stages.

As the iridium compound to be added, a mixed solution of two or more different iridium compounds may be used.

Alternatively, two or more different solutions of iridium compounds may be added at different stages.

The halide composition of the silver halide grains used in the silver halide emulsion layer according to the present invention is preferably silver chloride or silver chlorobromide containing substantially no silver iodide. Here, if silver iodide is not substantially contained, the silver iodide content is 0.
It represents 1 mol% or less. Preferably, silver chloride or silver chlorobromide having a silver chloride composition of 90 mol % or more is used, and more preferably silver chloride or silver chlorobromide having a silver chloride composition of 95 mol % or more.

Any shape of silver halide grains in the silver halide emulsion layer according to the present invention can be used. One preferred example is a cube having a (100) plane as a crystal surface. Also, U.S. Pat. No. 4,183゜756, U.S. Pat.
No. 25,666, JP-A No. 55-26589, JP-A No. 5
5-42737, etc., and The Journal of Photographic Size S-7 (J, Photo, 5ci)
Particles having shapes such as octahedrons, tetradecahedrons, and dodecahedrons can be prepared by the method described in literature such as 21゜39 (1973) and used. Furthermore, particles having twin planes or irregularly shaped particles may be used.

There is no particular restriction on the grain size of the silver halide grains used in the silver halide emulsion layer according to the present invention, but it is on the low sensitivity side (if the silver halide emulsions to be mixed are three or more types with different sensitivities, the lowest sensitivity The average grain size of the silver halide grains (hereinafter referred to as "grains A") contained in the silver halide emulsion (side) is suitably in the range of 0.2 to 1.6 .mu.m. In addition, the silver halide grains (hereinafter referred to as "grain B") contained in the silver halide emulsion on the high sensitivity side (the highest sensitivity side if the silver halide emulsions to be mixed are three or more types with different sensitivities) The average particle diameter is suitably in the range of 0.3 to 1.7 μm.

The above grain size is expressed by the diameter of the grain when the silver halide grain is spherical or nearly spherical, and otherwise by the diameter of a circle obtained by converting the projected area into a circle with the same area.

There is no particular restriction on the difference in particle size between particles A and B, but the smaller the difference in particle size, the more preferable it is, and the most preferable is that there is no difference in particle size.

Although the grain size distribution of the silver halide grains contained in the silver halide emulsion before mixing used in the silver halide emulsion layer according to the present invention may be polydisperse, it is preferably monodisperse.

Preferably, the silver halide grains are monodisperse silver halide grains having a coefficient of variation in particle size distribution of 0.22 or less, more preferably 0.15 or less.

The coefficient of variation is a coefficient indicating the breadth of the particle size distribution, and is expressed as (standard deviation of particle size distribution/average particle size).

The silver halide emulsion according to the present invention can be subjected to total sulfur sensitization, and can also be chemically sensitized with at least one selected from sulfur sensitization, selenium sensitization, noble metal sensitization, and reduction sensitization. I can do it. At that time, it is preferable to chemically sensitize the silver halide emulsions to be mixed separately.

When the present invention is applied to color photographic materials, usually
A yellow dye-forming coupler is used in the blue-sensitive emulsion layer, a magenta dye-forming coupler is used in the green-sensitive emulsion layer, and a cyan dye-forming coupler is used in the red-sensitive emulsion layer. However, depending on the purpose, silver halide color photographic materials may be produced using different combinations from the above.

These dye-forming couplers preferably have a group called a ballast group in the molecule, which makes the coupler non-diffusive and has 8 or more carbon atoms. In addition, even if these dye-forming couplers are 4-equivalent, in which 4 molecules of silver ions need to be reduced in order to form 1 molecule of dye, only 2 molecules of silver ions need to be reduced. Either bi-isomerism is acceptable.

As the yellow dye-forming coupler, various acylacetanilide couplers can be preferably used.

Among these, benzoylacetanilide and pivaloylacetanilide compounds are advantageous.

As the cyan dye-forming coupler, naphthol couplers and phenol couplers can be preferably used.

The dye-forming properties of the light-sensitive material of the present invention are usually obtained by using a high boiling point organic solvent with a freezing point of about 150°C or higher, a water-insoluble polymer, and a low boiling point and/or water-soluble organic solvent as necessary. After dissolving and emulsifying and dispersing it in a hydrophilic binder such as an aqueous gelatin solution using a surfactant, it is added to the desired hydrophilic colloid layer. A step of removing the low boiling point organic solvent may be included simultaneously with the dispersion or dispersion.

The high boiling point organic solvent is preferably a compound with a dielectric constant of 6.5 or less, such as esters such as phthalates and phosphoric esters, organic acid amides, ketones, hydrocarbon compounds, etc. with a dielectric constant of 6.5 or less. be.

More preferably, the dielectric constant is 6.5 or less and 1.9 or more and 100
It is a high boiling point organic solvent with a vapor pressure of 0.5 mmHg or less at °C. Among these, phthalate esters and phosphoric esters are more preferred.

Most preferred is a dialkyl heptatalate having an alkyl group having 9 or more carbon atoms. Furthermore, the high boiling point organic solvent may be a mixture of two or more kinds. Note that the dielectric constant indicates the dielectric constant at 30°C.

These high-boiling organic solvents generally have a low
It is used in a proportion of ~400% by weight. Preferably it is 10-100% by weight, based on the coupler.

The photosensitive material of the present invention can be, for example, color negative and positive films, color photographic paper, etc., but the effects of the present invention are particularly effective when color photographic paper used for direct viewing is used. Demonstrated.

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

The silver halide emulsion used in the present invention can be optically sensitized to a desired wavelength range using a dye known as a sensitizing dye in the photographic industry.

As the binder used in the silver halide photographic material of the present invention, gelatin is preferably used.

Gelatin commonly used in the photographic industry includes alkali-treated gelatin, which is treated with lime during the production process from collagen, and acid-treated gelatin, which is treated with hydrochloric acid. Manufactured as a raw material.

For details on the manufacturing method and properties of these gelatins, see, for example, The Macro by Arthur Veis.
Olecular Chemistry of Ge1a
tinj, Academic Press, 13
pp. 7-217 (1964), T. Hlames: Th
e Theory of thePhotograph
ic Process 4th, ed, 1977, (M
acmillan) 55 pages, Scientific Photography Handbook (top) 72~
75 pages (Maruzen), Basics of Photographic Engineering - Silver Salt Photography Edition 119~
It is described on page 124 (Corona Publishing), etc.

The gelatin used in the light-sensitive material of the present invention may be lime-treated gelatin, acid-treated gelatin, or gelatin produced from cow bone, cow skin, pig skin, etc., but Lime-treated gelatin produced from bovine bone is preferred.

The photographic emulsion layer and other hydrophilic colloid layers of the light-sensitive material of the present invention are hardened by using alone or in combination with a hardening agent that crosslinks binder (or protective colloid) molecules and increases film strength.

It is desirable to add the hardening agent in an amount that can harden the photosensitive material to such an extent that it is not necessary to add the hardening agent to the processing solution, but it is also possible to add the hardening agent to the processing solution.

In the photosensitive material of the present invention, an ultraviolet absorber is added to the hydrophilic colloid layer such as the protective layer and the intermediate layer to prevent fogging due to discharge caused by charging of the photosensitive material due to friction, etc., and to prevent image deterioration due to ultraviolet light. May contain.

The photosensitive material of the present invention can be provided with auxiliary layers such as a filter layer, a haleysilane prevention layer and/or an irradiation prevention layer. These layers and/or the emulsion layer may contain dyes that are leached from the color light-sensitive material or bleached during development.

A matting agent can be added to the silver halide emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material of the present invention for the purpose of reducing the gloss of the light-sensitive material, increasing the ease of writing, preventing the light-sensitive materials from sticking to each other, and the like.

A lubricant can be added to the photosensitive material of the present invention in order to reduce sliding friction.

In the present invention, an antistatic agent for the purpose of preventing static electricity can be added to the photosensitive material. Antistatic agents are sometimes used in the antistatic layer on the side of the support on which the emulsion is not laminated, or they are used to protect the emulsion layer and/or the side other than the emulsion layer on which the emulsion layer is laminated with respect to the support. A colloid layer I may also be used.

In the photographic material of the present invention, the photographic emulsion layer and/or other hydrophilic colloid layer may be used to improve coating properties, prevent static electricity, improve slipperiness, emulsification and dispersion, prevent adhesion, and (promote development, harden the film, sensitize the film, etc.). )
Various surfactants can be used for the purpose of improving photographic properties and the like.

The photographic emulsion layer and other layers of the light-sensitive material of the present invention are made of baryta paper or non-laminated paper such as σ-olefin polymer, filter paper support, or synthetic paper on which the σ-olefin layer can be easily peeled off from the paper support. Flexible reflective supports such as cellulose acetate, cellulose nitrate, polystyrene, polyvinyl chloride, etc.
It can be applied to films made of semi-synthetic or synthetic polymers such as polyethylene terephthalate, polycarbonate, and polyamide, reflective supports coated with white pigments, and rigid bodies such as glass, metal, and ceramics. or 120-160μm
It is also possible to use a thin reflective support.

The support used in the light-sensitive material of the present invention may be either a reflective support or a transparent support, and in order to have reflective properties, a white pigment may be contained in the support, or a white pigment may be added to the support. A hydrophilic colloid layer containing .

As the white pigment, inorganic and/or organic white pigments can be used, preferably inorganic white pigments, such as alkaline earth metal sulfates such as barium sulfate, calcium carbonate, etc. Carbonates of alkaline earth metals, finely divided silicic acid, silicas of synthetic silicates, calcium silicate,
Examples include alumina, alumina hydrate, titanium oxide, zinc oxide, talc, clay, and the like. The white pigment is preferably barium sulfate or titanium oxide.

The photosensitive material of the present invention can be prepared by subjecting the surface of the support to corona discharge, ultraviolet irradiation, flame treatment, etc., if necessary, and then directly or applying an undercoat layer (adhesiveness, antistatic property, and dimensional stability of the support surface). ,
The coating may be coated via one or more subbing layers to improve abrasion resistance, hardness, anti-ration properties, frictional properties and/or other properties.

When coating the silver halide emulsion of the present invention, a thickener may be used to improve coating properties. The application method is 2.
Particularly useful are extrusion coatings and curtain coatings in which more than one layer can be applied simultaneously.

In the processing of the light-sensitive material of the present invention, the color developing agent used in the color developing solution includes known color developing agents that are widely used in various color photographic processes.

These developers include aminophenol and p-phenylezineamine derivatives. These compounds are generally used in the form of salts, such as hydrochlorides or sulfates, since they are more stable than in the free state. Additionally, these compounds are generally present in a concentration of preferably 0.1 to 30 g for color developer IQ, preferably about 1 g to about 15 g for color developer IQ.
Use at a concentration of

Examples of aminophenol-based developers include 0-aminophenol, p-aminophenol, and 5-amino-2-
Oxytoluene, 2-amino-3-oxytoluene, 2
-oxy-3-amino-1,4-dimethyl-benzene and the like.

Particularly useful primary aromatic amine color developers include N, N-
A dialkyl-p-7z nylene diamine compound,
The alkyl group and phenyl group may be substituted with any substituent. Among them, an example of a particularly useful compound is N
-N-diethyl-p-phenylenediamine hydrochloride, N
-Methyl-p-7 22-diamine hydrochloride, N,N-dimethyl-p-22-diamine hydrochloride, 2-amino-
5-(N-ethyl-N-dodecylamino)-toluene,
N-ethyl-N-β-methanesulfonamidoethyl-3
-Methyl-4-aminoaniline sulfate group, N-ethyl-N
-β-hydroxyethylaminoaniline, 4-amino-
3-methyl-N,N-diethylaniline, 4-amino-
Examples include N-(2-methoxyethyl)-N-ethyl-3-methylaniline-p-toluenesulfonate.

The color developing solution applied to the processing of the light-sensitive material of the present invention includes:
In addition to the above-mentioned primary aromatic amine color developer, known developer component compounds can be added. For example, alkaline agents such as sodium hydroxide, sodium carbonate, potassium carbonate, alkali metal sulfites, alkali metal bisulfites, alkali metal thiocyanates, alkali metal halides, benzyl alcohol, water softeners and thickeners, etc. can also be optionally included.

The color developer usually has a PU value of 7 or higher, most commonly about 10-13.

The color development temperature is usually 15°C or higher;
It is in the range of °C to 50 °C. For quick development, 30℃
It is preferable to carry out the above. Further, the color development time is generally preferably carried out within a range of 20 seconds to 60 seconds, more preferably within a range of 30 seconds to 50 seconds.

The light-sensitive material of the present invention may contain these color developing agents in the hydrophilic colloid layer, either as the color developing agent itself or as its precursor, and may be processed in an alkaline activation bath. The color developing agent precursor is a compound that can generate a color developing agent under alkaline conditions, and includes a Schiff base type precursor with an aromatic aldehyde derivative, a polyvalent metal ion complex precursor, a phthalic acid imide derivative precursor, a phosphoric acid amide derivative precursor, Examples include sugar amine reactant precursors and urethane type precursors.

Precursors for these aromatic primary amine color developing agents are, for example, U.S. Pat.
7゜114, 2,695,234, 3,719
, No. 492, specifications of British Patent No. 803,783, Japanese Unexamined Patent Publications No. 53-185628 and No. 54-79035, Research Disclosure Magazine No. 15159, No. 1
No. 2146 and No. 13924. These aromatic primary amine color developing agents or their precursors need to be added in such an amount that sufficient color development can be obtained upon activation treatment. This amount varies depending on the type of photosensitive material, but is generally between 0.1 mol and 5 mol, preferably between 0.5 mol and 3 mol, per mol of silver halide. These color developing agents or their precursors can be used alone or in combination.

Water, methanol, ethanol,
It can also be added after being dissolved in a suitable solvent such as acetone.
It can also be added as an emulsified dispersion using a high boiling point organic solvent such as dibutyl phthalate, dioctyl phthalate, or tricresyl phosphate, or added by impregnating it into a latex polymer as described in Research Disclosure No. 14850. You can also.

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

Many compounds are used as bleaching agents, but iron (
■), polyvalent metal compounds such as cobalt (■) and copper (It), especially complex salts of these polyvalent metal cations and organic acids,
For example, ethylenediaminetetraacetic acid, nitriloacetic acid, N-
Aminopolycarboxylic acids such as hydroxyethylethylenediaminediacetic acid, metal complex salts such as malonic acid, tartaric acid, malic acid, diglycolic acid, dithioglycolic acid, or ferricyanates, dichromic acid, etc. may be used alone or in appropriate combinations. It will be done.

As the fixing agent, a soluble complexing agent that solubilizes silver halide as a complex salt is used. Examples of the soluble complexing agent include sodium thiosulfate, ammonium thiosulfate, potassium thiocyanate, thiourea, and thioether.

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

Further, as an alternative to the water washing treatment, a stabilization treatment may be performed, or both may be used in combination. The stabilizing liquid used in the stabilization treatment can contain a pH adjuster, a chelating agent, an anti-spill agent, and the like.

For these specific conditions, reference may be made to JP-A-58-134636 and the like.

〔Example〕

Example 1 On a paper support laminated with polyethylene on one side and polyethylene containing titanium oxide on the other side, each layer having the structure shown below was coated on the side of the polyethylene layer containing titanium oxide. Multilayer silver halide color photographic light-sensitive material samples (Sample No. 101- No. 107)
was created. The coating solution was prepared as follows.

First layer coating liquid Yellow coupler (Y-1) 26.7g, dye image stabilizer (ST-1) 10.0g, (ST
-2) 6.67g.

Add 60 ml (l) of ethyl acetate to 0.67 g of additive (HQ-1) and 6.67 g of high boiling point organic solvent (DNP) and dissolve. This solution is mixed with 7 ml (20% surfactant (SU-1)) of 20% surfactant (SU-1).
A yellow coupler dispersion was prepared by emulsifying and dispersing the yellow coupler into 220 mQ of a 10% aqueous gelatin solution containing 10% by using an ultrasonic homogenizer. This dispersion was mixed with a blue-sensitive silver halide emulsion (containing 10 g of silver) prepared under the following conditions to prepare a first layer coating solution-2.

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

Further, as a hardening agent, (H-1) was added to the second layer and the fourth layer, and (H-2) was added to the seventh layer. As coating aids, surfactants (SU-2) and (SU-3) were added to adjust the surface tension.

The structures of the first to seventh layers are shown in Table 1 below.

CsHs(t) CsH+ +(t)T-4 T-5 CH.

HQ-IR
Q-2DOP Dioctyl phthalate DNP Dinonyl phthalate DIDP Diisodecyl phthalate PvP Polyvinylpyrrolidone I-1 I-2 l-3 U-2 C2H.

U-3C(CH2SO2CH= CHz)4Na (Preparation method of blue-sensitive silver halide emulsion) 40°C! i
: Keep warm; 1 m in 2% gelatin aqueous solution 10100O
The following (liquid A) and (liquid B) were mixed with l) Ag-6,5, pH=
3.0 over 30 minutes, and further added the following (solution C) and (solution D) to pAg = 7.3, pH -5,
5] over a period of 80 minutes. At this time,
The pAg was controlled by the method described in JP-A-59-45437, and the pH was controlled using an aqueous solution of sulfuric acid or sodium hydroxide.

(Liquid A) Sodium chloride 3.42g Potassium bromide 0.03g Add water 200mFF (Liquid B) Add silver nitrate 10g water 200mQ (Liquid C) Sodium chloride 102.7g Potassium bromide Add 1.0g water 600 mff (solution D) Add 300 g of silver nitrate and add 600 m of water. average grain size 0.85 μm, coefficient of variation of grain size distribution (σ/r) = 0.07, silver chloride content 99
．． A 5 mol % monodisperse cubic emulsion EMP-1 was obtained.

The above emulsion EMP-1 was chemically ripened for 90 minutes at 50°C using the following compound, and a stomach-sensitive lambda silver halide emulsion (
Em-B) was obtained.

Sodium thiosulfate 0.8 mg 1 mol 1 mol A
Kakin @ 0.5 mg 1 mol 1 mol A
Fixer 5TAB-16xlO-' mol 1 mol AgX Sensitizing dye B S -14x 10-' mol/mol Agx
Sensitizing dye B5-2 1xto-' mol 1 mol AgX (
Preparation method of red-sensitive silver halide emulsion) The average grain Diameter 0.50
Coefficient of variation of μm1 particle size distribution (σ/r) = 0.08
, a monodispersed cubic emulsion EM with a silver chloride content of 99.5 mol%
P-2 was obtained.

90°C at 60°C using the following compound for EMP-2.
A red-sensitive silver halide emulsion (Em-R
) was obtained.

Sodium thiosulfate 1.8 mg 1 mol 1 mol A Auric acid 2.0 mg 1 mol 1 mol A fixer 5TAB-15XIQ-' mol 1 mol AgX sensitizing dye R5-11XIO-' mol 1 mol AgxS-1 S-2 TAB- 1 (Preparation of Silver Halide Emulsion (Em-■)) The amounts of additives used in the preparation of the emulsion below are per mole of silver halide unless otherwise specified.

Silver nitrate solution and IJium chloride solution were added to an inert aqueous gelatin solution in a double jet method over 120 minutes.

The temperature at this time was 40°C, the pAg was maintained at -7.3, and IrCQ was added to 9.3 during silver halide grain formation.
X 10-'' mole/AgX mole was added.

Next, desalting and washing with water are carried out in a conventional manner to reduce the average particle size to 0.5.
Em-■ consisting of cubic silver chloride grains with a variation coefficient of 0.09 in particle size distribution of 0 μm was obtained.

=IrCI2= added to this emulsion is 4.5X 1
0-'' mole/1 particle.

(Preparation of silver halide emulsion (Em-■)) It was prepared under the same conditions as Em-■, except that 2.5X 10-' mol/AgX mol of IrCQ was added during the formation of silver halide grains, and the average Particle size 0.50 μm 1 Coefficient of variation of particle size distribution 0°08
Em-■ consisting of cubic silver chloride grains was obtained.

The IrCQ added to the emulsion was 1.2X 10
-" 71 particles per mol.

(Preparation of silver halide emulsion (Em-■)) During the formation of silver halide grains, J! rc12a was added at 1.2X 10-' mol/AgX mol, and the addition time was increased by 2 times compared to the case of Em-■.
Em-
I got ■.

The amount of 2IrCI2s added to this emulsion was 4.2X 1
0-'' mole/1 particle.

For each of the above emulsions, the following compounds were used at 120°C at 55°C.
A green-sensitive/10-gen silver emulsion (Em-
G■~Em-G■) were obtained.

Sodium thiosulfate 1.5 mg 1 mol 1 mol A Auric acid 1.0 mg 1 mol 1 mol A fixative 5TAB
-16X 10-' mol 1 mol AgX sensitizing dye GS
-14X 10-' mol 1 mol Ag
o, 101- No. 107 were produced.

At this time, samples No. 101-No. 103 are samples in which single emulsions were evaluated before mixing two types of silver decogenide emulsions, and the illuminance dependence of the sensitivity of the single emulsions was also the same as that of the samples of the present invention. Measured at the same time.

The sensitivity, gradation, illuminance dependence, and color reproducibility of the samples No. 101 to No. 107 obtained using this comparative magenta coupler A were evaluated using the following methods.

(Evaluation of Sensitivity and Gradation) After the above sample was exposed to light as usual, it was subjected to the following treatments and its sensitometry was performed.

Processing process Temperature Time Development color development 35.0±0.3°C 45 seconds bleach fixing
35.0±0.5°C 45 seconds stabilization 30~34°C
Dry for 90 seconds 60-80°c 60
Second color developer Pure water 800ml Triethanolamine 10gN,N-diethylhydroxylamine 5g Potassium bromide
0.02g potassium chloride 2
g Potassium sulfite 0.3 g 1-Hydroxylethylidene-1,1-diphosphonic acid 1.0 g Ethylenediamine quaternary acid 1.0 g Catechol-3,5
-Disodium diphosphonate 1.0gN-ethyl-
N-β-methanesulfonamidoethyl-3-methyl-4
-Amine aniline sulfate 4.5g Fluorescent brightener (4,4'-diaminostilbene sulfonic acid derivative) 1.0g Potassium carbonate 27g Add water to bring the total volume to 1+2
and adjust the pH to -10.10.

Bleach-fix solution ethylenediaminetetraacetic acid ferric ammonium dihydrate
60g ethylenediaminetetraacetic acid
3g ammonium thiosulfate (70% aqueous solution) 0
0ml Ammonium sulfite (40% aqueous solution) 27.5ml Add water to bring the total volume to lff, and adjust the pH to -5.7 with potassium carbonate or glacial acetic acid.

Stabilizing liquid 5-chloro-2-methyl-4-inchazolon-3-one Ethylene glycol 1.0 g 1-hydroxyethylidene-1,1-diphosphonic acid 2.0 g Ethylenediaminetetraacetic acid 1.0 g Ammonium hydroxide (20% aqueous solution) 3.0g optical brightener (4
,4-diaminostilbenesulfonic acid derivative)
Add 1.5 g of water to bring the total volume to 1Q, and adjust the pH to 7.0 with sulfuric acid or potassium hydroxide.

Note that the sensitivity (S) was expressed as the reciprocal of the exposure amount required to obtain a reflection density of 0.8, and evaluated based on its relative value. The gradation (γ) is indicated by a slope of reflection density from 0.8 to 1.8.

(Evaluation of illuminance dependence) Illuminance dependence was determined after each sample was wedge-exposed with an exposure time of 0.02 seconds (high illuminance condition) and an exposure time of 10 seconds (low illuminance condition) with the same exposure amount. The illuminance dependence of sensitivity (ΔS) and the illuminance dependence of gradation (Δγ) were investigated.

△S is the ratio of the sensitivity obtained when exposed under high illuminance conditions to the sensitivity obtained when exposed under low illuminance conditions, and the smaller this value is, the less the illuminance dependence of sensitivity is. It is a silver photographic material.

Also, △γ is the γ obtained when exposed under low illumination conditions.
and γ obtained when exposed under high illuminance conditions, and the smaller the absolute value of this value, the less the dependence of gradation on illuminance, and the better the silver halide photographic light-sensitive material is.

(Evaluation of color reproducibility) Next, each sample was subjected to wedge exposure with green light, and then processed in the same manner as in the sensitivity and gradation evaluation described above. Absorption) is measured and I
;.

(Spectral absorption characteristic test) The spectral reflection spectrum of the magenta colored sample was measured using Color Analyzer Model 607 (manufactured by Hitachi Seisakusho). At this time, the maximum concentration of the absorption spectrum in the visible region of each sample was set to 1
．． The measurement was normalized to 0.

Next, the absorbance at 440 nm in the visible region (magenta) of each sample was read, and this value was used as a measure of unnecessary absorption in the yellow region, which was taken as secondary absorption.

A light-sensitive material with low secondary absorption can be said to be a silver halide photographic light-sensitive material with excellent color reproducibility.

In order to make it easier to understand the structure of the present invention, Table 3 shows the effects of the illuminance dependence on the sensitivity of the emulsions before mixing.

Next, Table 4 shows the results of sensitivity, illuminance dependence (ΔS, Δγ), and spectral absorption characteristics.

As is clear from Table 4, (1) Compared to the comparative coupler, the coupler of the present invention had smaller secondary absorption and a clearer image was obtained, but the illuminance dependence of the gradation deteriorated.

■When two types of silver halide emulsions with different sensitivities are mixed, the illuminance dependence of the sensitivity of the silver halide emulsion on the lower sensitivity side is
If the comparative coupler is smaller than that on the high-speed side, the illuminance dependence of gradation is improved compared to a single emulsion, but the degree of improvement is not sufficient. At this time, the general formula of the present invention [M-I:
When the coupler shown by l is used, the dependence of gradation on illuminance is further improved and the color reproducibility is also good.

Example 2 Each layer having the structure shown in Table 5 was coated on a paper support laminated with polyethylene on one side and polyethylene containing titanium oxide on the first layer side of the other side, and a multilayer silver halide layer was formed. A color photographic material was produced. The coating solution was prepared as follows.

First layer coating liquid Yellow coupler (Y-2) 26.5g, dye image stabilizer (ST-1) 10.0g, additives (HQ-
1) 0.46g and high boiling point organic solvent (DNP) lO
Add and dissolve 60 ml of ethyl acetate to
A yellow coupler dispersion was prepared by emulsifying and dispersing the yellow coupler in 220 ml of a 10% gelatin aqueous solution containing 7 ml of % surfactant (SU-1) using an ultrasonic homogenizer. This dispersion was mixed with a blue-sensitive silver halide emulsion (containing 10 g of silver) prepared under the following conditions to prepare a first layer coating solution.

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

Table 5 (!ki) In addition, as a coating aid, 5O-4, 5U-5, T-6 T-7 T-8 UUBth+ Q-3 0)I tl I-4 U-4 U-5 CA-1 0H Each color-sensitive emulsion was prepared as follows.

(Sensitized silver chlorobromide emulsion) A silver chlorobromide emulsion with an average grain size of 0.7 μm and a silver bromide content of 90 mol% was optimally sensitized at 57°C using sodium thiosulfate. Z as sensitizing dye (BS-2) and stabilizer
-1 was added.

(Red-sensitive silver chlorobromide emulsion) A silver chlorobromide emulsion with an average grain size of 0-0-4u and a silver bromide content of 60 mol%, sodium thiosulfate, and a sensitizing dye (R5-2).
and optimally sensitized at 60℃ using phenolic resin,
Z-1 was added as a stabilizer.

(Preparation of silver halide emulsion (Em-■)) A silver nitrate solution and a mixed solution of potassium bromide and sodium chloride were added to an inert aqueous gelatin solution over a period of 140 minutes by a double die-nod method. The temperature at this time was maintained at 50°C and pAg = 7-5, and IrCQ was added at 5.5% during particle formation. lx
IQ-” mol/AgX mol addition L f:.

Next, silver halide emulsion E was desalted and washed with water by a conventional method.
m−■ was obtained. Em-■ has an average grain size of 0.522 m1, silver bromide content of 70 mol%, and a coefficient of variation of grain size distribution of 0.1 O11.
It consists of tetrahedral silver chlorobromide grains.

Added to this emulsion was Ir(4, 3.3X 10
-"mol/1 particle.

(Preparation of silver halide emulsions (Em-■ to Em-■))K
11rC (Em-
Emulsions Em-■ to Em-■ were obtained in the same manner as in (2).

Table 6 shows the contents, average grain size, coefficient of variation of grain size distribution, and average amount of 21rC12m added per silver halide grain.

Table 6 (Preparation of silver halide emulsion (Em-■)) Silver nitrate aqueous solution and 7) Ride aqueous solution (mixed aqueous solution of potassium bromide and potassium iodide) were added to an inert gelatin aqueous solution by double jet method over 120 minutes. . At this time, the temperature was 60℃,
The pAg should be kept at 9.0 and the temperature should be kept at 21rC during particle formation.
Qa was added at 9.3X 10-' moles/AgX moles.

Then, desalination and water washing were carried out in a conventional manner to obtain emulsion Em-■. Em-■ is an emulsion consisting of silver iodobromide grains with an average grain size of 0.5 μm, a silver iodide content of 2 mol%, and a coefficient of variation of grain size distribution of 0.13. ，
is 4.5×10-”/1 particle.

(Preparation of silver halide emulsion (Em-[phase])) Silver nitrate aqueous solution and halide aqueous solution (mixed aqueous solution of potassium bromide and potassium iodide) were added to an inert gelatin aqueous solution by a double jet method over 120 minutes. At this time, the temperature was 60℃,
The pAg was maintained at 9.0, and IrC was added during particle formation.
Q, was added in an amount of 2.5X 10-' mole/AgX mole.

Next, desalting and washing with water are carried out by a conventional method to obtain an emulsion E m −
(FjJ was obtained. Em-@ has an average particle size of 0.50 μm.

Silver iodide content 2.5 mol%, coefficient of variation of grain size distribution 0.1
This is an emulsion consisting of silver iodobromide grains of No. 4, and KtlrC4i added to this emulsion is 1.2X 10-22 mol/1
It is a particle.

Each of the above emulsions was optimally chemically sensitized at 59°C using the following compound to create a green-sensitive silver halide emulsion (E m -
G■-Em-G@) was obtained.

Sodium thiosulfate 4.5 mg 1 mol 1 mol A-sensitive dye G5-2 4XlO-' mol 1 mol AgX stabilizer
Z-12g 1 mol Ag
1 to No. 218 were produced.

At this time, samples No. 201-No. 207 were single emulsions before mixing two types of silver halide emulsions, and the illuminance dependence of the sensitivity of the single emulsions was also measured at the same time as the samples of the present invention.

After exposing samples No. 201 to No. 218 in the same manner as in Example 1, they were processed according to the following processing steps to improve sensitivity, gradation,
Evaluate illuminance dependence and color reproducibility.

Extracted results of the illumination dependence of the sensitivity of the emulsions before mixing are shown in Table 8, and Table 9 shows the overall results.

Processing process Time Temperature color development 3 minutes 30 seconds 33°C bleach fixing
1 minute 30 seconds Wash with water at 33℃ 3 minutes
Mixed at 33°C, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 4.9g Hydroxylamine sulfate 2.0g Potassium carbonate
25.0g sodium bromide
0.6g anhydrous sodium iLite
2.0g benzyl alcohol 13m
1 diethylenetriamine pentavinegar rll 3.0
g triethanolamine IO, 0 g diethylene glycol 10.0 g Water was added to make the solution 112, and the pH was adjusted to IO20 with sodium hydroxide.

Bleach-fix solution Iron (I[[) ethylenediaminetetraacetate] Sodium salt 60g Ammonium thiosulfate 100g Sodium bisulfite 10g Sodium metabisulfite
Add 3g of water to make 1g, and adjust the pH to 7.0I:T14 with aqueous ammonia.

Table 9 Table 9 shows that when the average amount of iridium added per grain of the silver halide emulsion on the low-speed side is larger than that of the silver halide emulsion on the high-speed side, the illuminance dependence of gradation can be improved. Recognize.

When the silver halide grains of the present invention are silver iodobromide, the illuminance dependence of gradation is improved, but compared to silver chloride or silver chlorobromide,
Sensitivity is slightly lower, even if the same coupler is used, 440n
The absorption near m is high, and the color reproducibility is slightly inferior.

For this reason, it is preferable that the silver halide grains contained in the silver halide emulsion of the present invention do not substantially contain silver iodide.

Example 3 (Preparation of silver halide emulsion (Em-a)) A silver nitrate aqueous solution and a halide aqueous solution (mixed aqueous solution of potassium bromide and sodium chloride) were added over 100 minutes by a double jet method. At this time, the temperature was maintained at 50'O, pAg = 7.8, and 21rCQa was added at 1.3X 10 during particle formation.
-”mol/Agx% 4 additions.

Then, Em-a was obtained by desalting and washing with water by a conventional method. E
m-a is an average particle size of 0.40 μm and a silver bromide content of 0.1
It was a monodisperse emulsion consisting of cubic silver chlorobromide grains with a particle size distribution coefficient of variation of 0.12 and 0 mol %.

The IrCQ6 added to this emulsion was 3.3X 10
−”−!−le/1 particle.

(Preparation of silver halide emulsion (Em-b)) A silver nitrate aqueous solution and a halide aqueous solution (mixed aqueous solution of potassium bromide and sodium chloride) were added over 100 minutes by a double jet method. At this time, the temperature was maintained at 50° C. and pAg was maintained at 7-8, and 21rC4a was added at 3.3×10 −” mol/AgX mol during particle formation.

Next, the emulsion Em-b was obtained by desalting and washing with water in a conventional manner. Em-b has an average grain size of 0.40 μm and a silver bromide content of 0.
It was a monodisperse emulsion consisting of cubic silver chlorobromide grains of 10 mol % and a coefficient of variation of grain size distribution of 0.11.

JIrC<l= added to this emulsion is 8.3X 1
It was 0-'' mole/1 particle.

(Silver halide emulsion (E m -c)) Silver nitrate aqueous solution and halide aqueous solution (mixed aqueous solution of potassium bromide and sodium chloride) were added in 90 minutes using a double jet method. At this time, the temperature was 50°C. pAg = 7.8 and 21rCI2 = 6.6X 1 during particle formation.
0-'' mole/AgX mole was added.

Next, the emulsion Em-C was obtained by desalting and washing with water in a conventional manner. Em-c has an average grain size of 0.50 pm and a silver bromide content of 0.
．． The emulsion was a monodisperse emulsion consisting of cubic silver chlorobromide grains having a particle size distribution of 1θ mol% and a coefficient of variation of 0.11.

The 21ri added to this emulsion is 3.2X 10-
"Mole/1 particle.

Each of the above emulsions was optimally chemically sensitized at 60°C under the following conditions to produce green-sensitive silver halide emulsions (Em-G■ to E
m-G4φ).

In the same manner as in Example 1, a multilayer silver halide color photographic light-sensitive material (Sample No. 3
01-No. 311) was produced.

Samples No. 301 to No. 306 are single emulsions before being mixed with two types of silver halide emulsions, and the illuminance dependence of the sensitivity of the single emulsions was also measured at the same time as the samples of the present invention.

Samples No. 301-No. 311 were exposed and processed in the same manner as in Example 1, and evaluated.

Extracting the results of the illuminance dependence of the sensitivity of the emulsion before mixing,
Table 12 shows the overall results, and Table 13 shows the overall results.

Table 13 From Table 13, in the present invention, the method of making the illuminance dependence of the sensitivity of the silver halide emulsion on the low sensitivity side smaller than the illuminance dependence of the sensitivity of the silver halide emulsion on the high sensitivity side is to use a water-soluble iridium compound. In addition to changing the amount of water-soluble iridium compound added, this can also be done by changing the chemical sensitization conditions, such as extending the chemical ripening time or increasing the amount of sodium thiosulfate. It turns out to be the best.

Cargo flow side 4 Magenta coupler M-2 of sample No. 311 of Example 3
2 to Exemplary Compounds 1, 4, 10.20.35.59.
When similar samples were prepared and evaluated in the same manner except that 61.63 was used, the effects of the present invention were obtained.

〔Effect of the invention〕

According to the present invention, a new technique for improving the reciprocity law failure characteristics of a photosensitive material is provided, thereby improving the illuminance dependence of gradation without reducing sensitivity.

Therefore, the present invention provides a photosensitive material with high sensitivity and excellent gradation and color reproducibility.

Claims (3)

[Claims] (1) In a silver halide photographic material having at least one silver halide emulsion layer on a support, at least one of the silver halide emulsion layers has the following general formula [M-
The silver halide grains containing the coupler represented by I] and contained in the silver halide emulsion layer are a mixture of at least two types of silver halide emulsions having different sensitivities, and the halogen grains on the low sensitivity side A silver halide photographic light-sensitive material characterized in that the illuminance dependence of the sensitivity of the silver halide emulsion is smaller than the illuminance dependence of the silver halide emulsion on the high-sensitivity side. General formula [M-I] ▲ Numerical formulas, chemical formulas, tables, etc. It may have. X represents a hydrogen atom or a group that can be separated by reaction with an oxidized product of a color developing agent, and R represents a hydrogen atom or a substituent. ] (2) Claim (1) characterized in that the silver halide grains contained in the at least two types of silver halide emulsions having different sensitivities are made of silver chloride or silver chlorobromide that does not substantially contain silver iodide. ) The silver halide photographic material described in ). (3) In at least one combination of the at least two types of silver halide emulsions having different sensitivities, the silver halide emulsion on the lower sensitivity side is a photosensitive silver halide to which iridium is added at the time of grain formation. The silver halide photographic sensitizer according to claim (2), wherein the silver halide emulsion contains grains, and the average amount of iridium added per silver halide grain is larger than that of a silver halide emulsion on the high-sensitivity side. material.