JPH0486655A - Silver halide photographic color sensitive material - Google Patents

Abstract

PURPOSE:To enhance pressure resistance and color reproduction, performance by incorporating a specified silver halide photographic emulsion in at least one of emulsion layers and a specified compound or its precursor in at least one of photographic constituent layers. CONSTITUTION:At least one of the photosensitive silver halide emulsion layers has the silver halide emulsion comprising silver halide twin crystals having the ratio of a grain diameter to grain thickness of <5 in an amount of >=50% of the total projection area. At that time it contains the monodispersed emulsion having only one peak in the (420) X-ray diffraction signals using the CuKalpha ray as a beam source and a diffraction ray width of <1.5 deg. in the diffraction angle (2theta) in the highest peak height X 0.13. At least one of the photographic constituent layers contains the compound to be allowed to release a photographic useful reagent or its precursor by oxidation of the oxidized product of a developing agent and by attack of a nucleophilic agent, thus permitting pressure resistance to be improved without accompanying any desensitization and color reproduction performance to be enhanced.

Description

DETAILED DESCRIPTION OF THE INVENTION C. Industrial Application Field The present invention relates to a silver halide color photographic light-sensitive material, and more particularly to a silver halide color photographic light-sensitive material with improved pressure resistance and color reproducibility. It is.

[Background of the invention]

Silver halide photographic light-sensitive materials (hereinafter sometimes simply referred to as light-sensitive materials) have excellent photographic performance such as sensitivity and gradation, and storage stability of so-called raw samples, which are samples before exposure, and developed samples. In addition to this, the physical properties related to handling of the photosensitive material must also be excellent.

Photosensitive materials are usually subjected to pressure under various conditions during their manufacturing process, distribution process, exposure device, and development device. Silver halide, which is generally added to light-sensitive materials, loses its original photosensitivity properties when subjected to pressure, resulting in desensitization, sometimes sensitization, and fogging. For example P, Faelens et
al, ; J, P, S, 2.105 (1954), K
,B,Mather;J,Opt,Soc,A+m,3
81054 (194B), R. King et al.
;J, P, S, 4. 33, 127 (1985), etc.

Therefore, when the surface of the photosensitive material is pressed, scratched, rubbed, or bent, or due to the blade pressure when cutting, the nearby silver halide is subjected to pressure. This results in an image density that does not correspond to the image exposure, and may appear as defects on the finished image.

The support that forms the photosensitive material and the binder that holds the silver halide (gelatin, wood-philic polymer, etc.)
By devising the following, the above problem can be improved to some extent. However, this problem basically depends to a large extent on the characteristics of silver halide.

Conventionally, various studies have been made to improve this pressure resistance, such as the halide composition of silver halide, halide distribution, chemical ripening method, doping of metal ions, and selection of sensitizing dyes. This was accompanied by substantial desensitization and was unsatisfactory for practical use.

On the other hand, in recent years, there has been an increasing demand for higher image quality for silver halide color photographic materials.

For example, in order to improve color reproducibility, various improvement studies have been conducted regarding the development inhibiting effect (interimage effect; IIE) between layers having different color sensitivities.

In the case of reversal silver halide photographic materials, it is practically impossible to correct the secondary absorption of the coloring material using colored couplers, such as those used in color negative photographic materials.
Mainly uses the developing effect. That is, development of silver halide in one emulsion layer has been achieved by utilizing interimage effect (hereinafter referred to as IIE) which inhibits development of other layers. For example, the most common development inhibitor is iodide ion, and a technique is known in which the IIE is enhanced by controlling the normal content in each layer in a silver halide emulsion. JP 49-129536, U.S. Patent No. 3,379
, No. 529, No. 3,620,746, No. 4,332.
No. 878, No. 4,377.634 discloses hydroquinone derivatives that release organic inhibitors, and this technology attempts to further enhance IIE by releasing the inhibitor group during the first development. It is.

Further, JP-A No. 61-213847 discloses a type of compound as a redox compound that releases a photographically useful group while causing an oxidation-reduction reaction within the molecule.

However, even with these techniques, the improvement effect is not sufficient, and further improvements are desired.

[Purpose of the invention]

Accordingly, an object of the present invention is to provide a silver halide color photographic material which has good pressure resistance without desensitization and has improved brown color reproducibility.

[Structure of the invention]

The above object of the present invention is to provide a silver halide color photographic light-sensitive material having photographic constituent layers each comprising at least one red-sensitive, green-sensitive, and blue-sensitive light-sensitive silver halide emulsion layer on a support. A silver halide photographic emulsion in which at least one of the photosensitive silver halide emulsion layers comprises silver halide twin grains in which 50% or more of the projected area has a grain diameter/grain thickness ratio of less than 5. The silver halide emulsion was monodisperse, and CuKα radiation was used as the radiation source (
420) Contains a silver halide photographic emulsion in which the X-ray diffraction signal has a unique peak and the diffraction line width at the highest peak height X O,13 is less than 1.5 degrees at the diffraction angle (2θ), and At least one of the photographic constituent layers contains at least one compound or a precursor thereof that releases a photographically useful reagent upon attack by a nucleophile after being oxidized by an oxidation product of a developing agent. This was achieved using a silver halide color photographic light-sensitive material characterized by the following.

The photographic constituent layers mentioned in the present invention include, in addition to the silver halide emulsion layer, non-photosensitive layers such as an intermediate layer, a protective layer, a yellow filter layer, and an antihalation layer.

The present invention will be explained in more detail below.

First, the developing agent is oxidized by the oxidation product of the developing agent, which is a compound contained in at least one of the photographic constituent layers of the light-sensitive material of the present invention, and then a photographically useful reagent is released by attack with a nucleophile. The compound or its precursor (hereinafter referred to as a redox compound) will be described. The redox compound used in the present invention preferably has the following formulas (A) to [D
).

General formula [A) ED' -(Time), 1-PUG-formula CB) ED"(L)lI-A (Time), -PUG-formula (C) General formula [D) In the formula, ED' and ED2 is Kendall-Pelz
Represents a redox core or its precursor that follows the rules. ED
Examples of the redox nucleus represented by ' include hydroquinones, catechols, pyrogallols, aminophenols (e.g. p-aminophenols, 0-aminophenols), naphthalene diols (e.g. 1,
2-naphthalene diols,
．． 4-aminonaphthols, 2,6-aminonaphthols), etc.

In addition, the redox nucleus indicated by ED' is ED'
In addition to those exemplified in , pyrazolidones, hydrazines, hydroxyamines, and reductones can be mentioned.

Examples of the redox core precursor represented by EDI or ED'' include those in which the hydroxyl group and/or amino group involved in the redox reaction are protected with a protecting group that is removed, for example, by hydrolysis during development. Examples of the protecting group include an acyl group, a carbonate ester group, a sulfonyl group, a cyanoethyl group, a sulfonylethyl group, an acylethyl group, and an imidomethyl group.

In addition, the amino group involved in the redox reaction has a substituent such as an alkyl group, a sulfonyl group (e.g., aliphatic sulfonyl group, aromatic sulfonyl group), or an acyl group (e.g., aliphatic acyl group, aromatic acyl group). Including ED”
In addition, (L)--A-(Time), -PU
Includes amino groups substituted with G.

The redox mother nucleus represented by ED' or ED2 is located at an appropriate position (e.g. 2 of the benzene nucleus in the hydroquinone nucleus).
．． It includes those having a substituent at the 3.5 or 6 position). Examples of these substituents include those having 25 or less carbon atoms, such as alkyl groups, aryl groups, alkylthio groups, arylthio groups, alkoxy groups, aryloxy groups, amino groups, amide groups, sulfonamido groups, and alkoxycarbonylamino groups. , ureido group, carbamoyl group, alkoxycarbonyl group, sulfamoyl group, sulfonyl group, cyano group, halogen atom, acyl group, carboxyl group, sulfo group, nitro group, heterocyclic group, and in ED', *T imeh P Examples of UG -, ED'' include -(L), -A-(Time), PUG, etc. Also, these substituents can be combined with each other or with the above-mentioned protecting group to form saturated or unsaturated The present invention also includes those forming a carbocyclic ring or a saturated or unsaturated heterocyclic ring.

Preferred examples of EDI include hydroquinones, catechols, pyrogallols, p-aminophenols, 0-aminophenols, 1,4-naphthalene diols, and 1,4-aminonaphthols; Preferred are hydroquinones, catechols, pyrogallols, p-aminophenols, and 0-aminophenols, and most preferred are hydroquinones.

R represents an alkyl group, an aryl group, or a heterocyclic group, and the polygroup includes those having substituents, and the substituents include:
Alkyl group, aryl group, hydroxy group, halogen atom, alkoxy group, aryloxy group, amino group, acylamino group, sulfonamido group, carbamoyl group, sulfamoyl group, alkylthio group, ureido group, thioureido group, acyl group, sulfonyl group, cyano group, nitro group,
Examples include heterocyclic groups.

R'' includes a hydrogen atom, an alkyl group, an aryl group, an acyl group, a carbamoyl group, an oxycarbonyl group, a sulfonyl group, a sulfamoyl group, and a heterocyclic group.

R represents a hydrogen atom or R (synonymous with R above).

Particularly preferred as A is -C-.

(synonymous with R12 described above).

B represents an acidic group, preferably a nitro group, a cyano group,
Represents a carboxy group, a sulfo group, or -A-X-R (A, X and R are as defined above).

L represents a divalent linking group, and preferably includes alkylene, alkenylene, arylene, oxyalkylene, oxyarylene, aminoalkyleneoxy, aminoalkenyleneoxy, aminoaryleneoxy, and an oxygen atom.

m and n each represent 0 or 1.

PIJG represents a photographically useful group, and preferable examples thereof include a development inhibitor, an antifogging agent, a development accelerator, a fogging agent, a silver halide solvent, a dye, and a color mixing inhibitor.

Time represents a timing group, specifically, a group that generates formalin or a derivative thereof and releases puc as described in JP-A No. 52-90932, and JP-A-541451.
Groups that release Pt1G by intramolecular nucleophilic reactions described in No. 35, No. 55-53330, etc., Japanese Patent Publication No. 54-397
No. 27, JP-A-57-136640, JP-A No. 57-154
p by electron transfer along the conjugated chain as described in No. 234, etc.
A group that releases uc, a group that generates PUG by generating carbon dioxide as described in JP-A-57-179842, etc., or JP-A-57-40245, JP-A-59-121328, JP-A-59-218439, etc. Examples include a group capable of releasing puc through an intramolecular nucleophilic reaction in which the oxygen atom of the carbonyl group forms a 5- to 7-membered ring.

The redox compound used in the present invention is oxidized by the oxidation product of the developing agent, and then oxidized by the nucleophile (e.g. hydroxyl ion,
PUG due to attack by sulfite ions, hydroxylamines, amines, hydroxamic acids, hydrazines, N-oximes, alkoxides, mercapto anions, etc.)
Particularly preferable ones are those that emit the above-mentioned -
It is expressed by formula (A) or [B].

Next, redox compounds used in the present invention will be illustrated. However, the invention is not limited to the following examples.

0■ UI'I UI'I drunkenness I4 R-14 11H I.J. ll しυN1IL++ztlzs ShiH3 H Below R-22~R 31 is expressed by the following formula.

R-41 R-43 The redox compound used in the present invention is disclosed in Japanese Unexamined Patent Application Publication No. 49-12
No. 9536, No. 52-57828, No. 60-2104
No. 4, No. 60-233642, No. 60-233648
No. 61-18946, No. 61-156043,
No. 61-213847, No. 61-230135, No. 61-236549, No. 62-62352, No. 62
-103639, U.S. Patent No. 3,379,529,
It can be synthesized according to the methods described in JP 3,620,746, JP 4,332,828, JP 4,377.634, JP JP 4,684,604, and the like.

The redox compound is added to the silver halide emulsion layer and/or the non-photosensitive hydrophilic colloid layer of the light-sensitive material of the present invention, and is preferably contained in the silver halide emulsion layer.

The amount added is generally 1X per mole of silver halide.
10-'mol-10-3 mol is preferred, especially lXl0
-6 moles -5X10-'' moles are preferred.

Conventional methods can be used to add the redox compound to the silver halide emulsion layer and/or other hydrophilic colloid layers. That is, compounds soluble in water may be dissolved in water or added as they are to an aqueous gelatin solution. Compounds that are insoluble or sparingly soluble in water may be dissolved in a water-miscible solvent and mixed with an aqueous gelatin solution, or the method described in, for example, US Pat. No. 2,322,027 may be used.

Next, the emulsion contained in at least one of the light-sensitive silver halide emulsion layers of the light-sensitive material of the present invention will be described.

This emulsion is a silver halide photographic emulsion in which 50% or more of the projected area consists of silver halide twin grains with a grain diameter/grain thickness ratio of less than 5, and the silver halide emulsion is monodispersed. and CuKα radiation was used as the radiation source (420)
The X-ray diffraction signal has only one peak, and the diffraction line width at the highest peak height x 0.13 is 1 at the diffraction angle (2θ).
．． It is a silver halide photographic emulsion (hereinafter also referred to as "the emulsion of the present invention" as appropriate) having a particle diameter of less than 5 degrees.

This emulsion consists of twinned grains as described above, and the term "twinned" here means a silver halide crystal having one or more twin planes within one grain. The classification of the morphology of twins is based on the paper by Klein and Moyser.
ondenz) Vol. 99, p. 99, Vol. 100, p. 57. Two or more twin planes of a twin may or may not be parallel to each other. Twin planes can be observed directly with an electron microscope, but they can also be observed from a cross section by dispersing silver halide grains in a resin and solidifying them as an ultrathin section sample.

The silver halide twin crystal grains constituting the emulsion of the present invention preferably have two or more parallel twin planes, more preferably an even number of twin planes, and particularly preferably two twin planes. It is something that you have.

Here, "consisting mainly of twins having two or more parallel twin planes" means that the number of twin grains having two or more parallel twin planes is 50 when counted from large grain size particles. % or more, preferably 60% or more, particularly preferably 70% or more.

The silver halide emulsion of the present invention is composed of silver halide twin grains in which 50% or more of the projected area has a grain diameter/grain thickness ratio of less than 5, preferably 70% of the projected area.
% or more, particularly preferably 90% or more. Further, the ratio of particle diameter/particle thickness is preferably 1.0 to 4.5, particularly preferably 1.1 to 4.0. The particle size here is the diameter when the projected image of the particle is converted into a circular image with the same area.

The projected area of a particle can be determined from the sum of the particle areas. Both can be obtained by observing with an electron microscope a silver halide crystal sample scattered on a sample stage to such an extent that grains do not overlap. The thickness of the particles can be measured by obliquely observing the sample using an electron microscope.

When the emulsion of the present invention is composed of twin grains, it means that the emulsion is mainly composed of twin crystals, and when it is said that the emulsion is mainly composed of twin crystals, the ratio of twin grains to the whole grains is 6.
0% or more, preferably 80% or more, particularly preferably 95
~100%.

The emulsion of the present invention is preferably a silver iodobromide emulsion mainly composed of twin crystals.

The emulsions of the present invention are monodisperse.

In the present invention, a monodisperse silver halide emulsion is one in which the weight of silver halide contained within a grain size range of ±20% around the average grain size a is 70% or more of the total weight of silver halide. Good, preferably 80% or more, more preferably 90%
% or more.

Here, the average particle size d is the frequency n of particles having particle size d,
The product n of and d, 3, the particle size d when Xd43 is maximum
Define as 1. (3 digits of significant digits, the lowest digit is 4 to 5.) The particle size referred to here is the diameter when the projected image of the particle is converted into a circular image of the same area.

The particle size can be obtained, for example, by magnifying the particles 10,000 to 50,000 times using an electron microscope, projecting the particles, and actually measuring the particle diameter or area at the time of projection on the print. (
It is assumed that the number of particles to be measured is indiscriminately 1000 or more. ) In the present invention, preferred highly monodisperse emulsions have a distribution width defined by 20% or less, more preferably 15% or less, particularly preferably 12% or less.

Here, the particle size measurement method shall follow the measurement method described above,
The average particle size is a simple average.

X-ray diffraction is known as a method for investigating the structure of silver halide crystals.

Various characteristic X-rays can be used as the X-ray source. Among them, CuKα rays targeting Cu are the most widely used.

Silver halides, such as silver iodobromide, have a rock salt structure, and Cu
The (420) diffraction line in the Kcr line is observed at 2θ; 71 to 74 degrees. Since the signal intensity is relatively strong and the angle is wide, the resolution is good and it is ideal for investigating crystal structures.

When measuring the X-ray diffraction of a photographic emulsion, it is necessary to remove gelatin, mix a standard sample such as silicon, and measure using a powder method.

Regarding the measurement method, reference can be made to Basic Analytical Chemistry Course 24 "X-ray Analysis" (Benmuro Publishing).

The emulsion of the present invention uses (420)X using CuKα radiation as a radiation source.
At the maximum peak height of the line diffraction signal x 0.13,
It is characterized in that the diffraction line width is less than 1.5 degrees at a diffraction angle (2θ). More preferably, the diffraction line width is less than 1.0 degrees, particularly preferably 0.90 degrees or less.

The emulsion of the present invention has only one peak in the diffraction signal. When counting the number of peaks, measurement noise and peaks less than 4% of the highest peak height shall not be counted.

The emulsion of the present invention uses (420)X using CuKα radiation as a radiation source.
The line segment where a horizontal line is cut by the signal at the highest peak height xo, 13 of the line diffraction signal is A
When A' is the intersection with a line drawn perpendicularly from the highest peak position and B is the intersection point, the segment shall be divided so that the ratio of the length of line segment AB to the length of line segment BA' is 1.0 or less. is preferred. Here, the line segment AA' is drawn from the narrow angle side of the diffraction angle to the wide angle conversion side. Further, the ratio of the length of line segment AB to the length of line segment BA' is more preferably 0.95 or less, particularly preferably 0.60 to 0.90.

The silver halide twin grains constituting the emulsion of the present invention are (1
11) It is preferable to have both a plane and a (100) plane.
It is preferable that 20% or more of the particle surface is a (100) plane, more preferably 30% or more, particularly preferably a 40
This is the case where ~70% of the surfaces are (100) planes. (100)
It is preferable that the other planes are mainly (111) planes.

The ratio of the (100) plane to the (111) plane is the signal of the (200) plane, (222) plane, and (220) plane of a sample in which silver halide grains are distributed so as not to overlap on a flat sample stage. Intensity ratio and (200) in powder samples
It can be determined by comparing the signal ratios of the plane, (222) plane, and (220) plane.

The silver halide emulsion of the present invention has an average silver iodide content of 6.
It is preferable that the silver iodobromide emulsion contains less than mol %, more preferably 0 to 5 mol %, particularly preferably 1 to 4 mol %. Further, in that case, silver chloride may be contained within a range that does not impair the effects of the present invention.

The silver halide emulsion of the present invention can be obtained, for example, by localizing silver iodide within grains. A preferred embodiment is one in which silver iodobromide having a lower silver iodide content is deposited in a layered structure on an inner core having a higher silver iodide content.

In this case, the silver iodide content of the inner core is preferably 18 to 45 mol%. Particularly preferably 25 to 40 mol%.

It is preferable that the difference in silver iodide content between the outermost shell and the inner core is 10 mol% or more, and particularly preferably,
The difference is 20 mol% or more, particularly preferably 30 to 40 mol% or more.

In the above embodiment, another silver halide phase may be present at the center of the inner core or between the inner core and the outermost shell.

The volume of the outermost shell is preferably 10 to 90 mol%, more preferably 50 to 80 mol%, of the entire particle. The inner core, the outermost shell, and other silver halide phases may have a uniform composition, or may be a phase group consisting of multiple phases with a uniform composition and whose composition changes in a stepwise manner, Alternatively, it may be a continuous phase in which the composition changes continuously within the phase, or a combination of these may be used.

In another aspect of the invention, the silver iodide within the grain is not localized forming a substantially uniform phase, but the silver iodide content varies continuously from the center of the grain to the outside. Examples include aspects. In this case, it is preferable that the silver iodide content decreases monotonically from the point where the silver iodide content within the grain is maximum toward the outer side of the grain.

The silver iodide content at the point where the silver iodide content is maximum is preferably 15 to 45 mol%, more preferably 2
It is 5 to 40 mol%.

Further, the silver iodide content on the grain surface is preferably 3 mol% or less, more preferably 0 to 2 mol%, particularly preferably 0.1 to 1.0 mol% of silver iodobromide. .

As a method for obtaining the silver halide emulsion of the present invention, a method in which silver iodobromide or a silver bromide-containing phase is precipitated on monodisperse seed crystals is preferably used. Particularly preferably, the method described in JP-A No. 61-6643, which includes a growth step for enlarging a monodisperse spherical twin seed emulsion, can be used.

Specifically, when using a method for producing a silver halide photographic emulsion in which a water-soluble silver salt solution and a water-soluble halide solution are supplied in the presence of a protective colloid, (a) the silver iodide content is 0 to 0; A core particle generation step is provided to maintain the pBr of the mother liquor at 2.0 to -0.7 for two or more periods from the beginning of the formation of 5 mol % silver halide precipitate, and (b) following the core particle generation step, Add a silver halide solvent to the mother liquor at 10% per mole of silver halide.
- A seed particle forming step is provided to form silver halide seed particles containing 5 to 2.0 moles and are substantially monodisperse spherical twins (c) Next, a water-soluble silver salt solution and a water-soluble halogen Preferably used is a method that includes a growth step in which the seed grains are enlarged by adding a compound solution and/or fine silver halide grains.

Here, the mother liquor is a liquid (also containing a silver halide emulsion) used for preparing a silver halide emulsion to produce a finished photographic emulsion.

The silver halide grains formed in the grain forming step (a) above are twin grains made of silver iodobromide containing 0 to 5 mol % of silver iodide.

The twin crystal mentioned here has the above-mentioned requirements, but in addition, the outer wall of the crystal is composed of (111) planes, and (100
) or both sides.

When the above production method is adopted, the twin core particles are produced by reducing the bromide ion concentration in the protective colloid aqueous solution to 0.01 to 5 mo) L, /l, or p
B r =2.0 to -0.7, preferably 0
．． 03~5 mol/i, (pBr=1.5~-
0.7) and adding a water-soluble silver salt or a water-soluble silver salt and a water-soluble halide.

Here, the nucleation particle generation process refers not only to the period from the time when the water-soluble silver salt is added to the protective colloid solution until the time when new crystal nuclei are substantially no longer generated, but also the period after which the particles grow. It is defined as a step before the seed particle forming step.

In this method, the size distribution of the core particles is not limited and may be monodisperse or polydisperse. Polydispersity here refers to particles having a coefficient of variation (synonymous with the above-mentioned width of distribution) of 25% or more. In this case, the core particles preferably contain at least 50% of twin grains, more preferably 70% or more, and 90% of the total number of core particles.
Most preferably.

Next, in the case of the above production method, the core grains obtained in the core grain generation step (b) above are ripened in the presence of a silver halide solvent to obtain seed grains consisting of monodisperse spherical grains. The particle forming step will be explained.

Ripening in the presence of a silver halide solvent (hereinafter simply referred to as ripening) is thought to generally lead to a broader grain size distribution, with the small grains dissolving and the larger grains growing when large and small grains coexist. This seems to be different from the Ostwald ripening that has been described. The conditions for ripening the seed grains from the core grains obtained in the core grain generation step include the core grain generation step in which twin core grains are produced using silver halide with a silver iodide content of 0 to 5 mol%. Substantially monodisperse spherical seed grains are obtained by ripening the emulsion mother liquor that has gone through the process in the presence of a silver halide solvent of 10-5 to 2.0 mol/silver mol. Substantially monodisperse means that the width of the distribution as defined above is less than 25%.

Substantially spherical grains herein refer to (111) or (111) planes or (111) planes or (
100) When a surface such as a plane is rounded to the extent that it cannot be clearly distinguished, and three-dimensional axes that are perpendicular to each other are set at one point near the center of gravity within the particle, the vertical, horizontal, and height of the plane image of the particle Maximum particle size L and minimum particle size in the direction! The ratio C=
is 1.0~2.0,! Preferably, it refers to particles in the range of 1.0 to 1.5.

In this method, it is preferred that the spherical particles account for 60% or more, preferably 80% or more, and more preferably most of the total number of seed particles.

Silver halide solvents used in the seed grain forming step of this method include (a) U.S. Pat. No. 3,271,157, U.S. Pat. Organic thioethers described in No. 1019, No. 54-158917, and Japanese Patent Publication No. 58-30571, (b) JP-A-53-82408, No. 55-2982
9 and 55-77737, etc.; (c) a solvent having a thiocarbonyl group sandwiched between an oxygen or sulfur atom and a nitrogen atom, which is described in JP-A-53-144319; (d) Japanese Patent Publication No. 54-10071
Imidazole described in No. 7, (e) sulfite, (
f) Thiocyanates, (g) ammonia, (h) ethylenediamines substituted with hydroxyalkyl described in JP-A-57-196228, (i) JP-A-57-196228.
Substituted mercaptotetrazoles described in No. 202531, (j) water-soluble bromide, (k) JP-A-58-543
Examples include benzimidazole derivatives described in No. 33.

Next, specific examples of these silver halide solvents (a) to (k) will be given.

HOCHzC)IzSCHzCHzSCHzCHzOH
(e) KzSOs l azSOs (f) NH4SCN, KSCN (g) NH.

(h) (FIOCI(2CH2) ZNC)12c)12N(
CFl, CI(,OR) ZCHzCHJ(CH:+)
3 (j) NaBr 1 NHJr + Br (k) (CzHsCHCHz) zNCHzCHzN(C)I
zCt(CzHs) zOH0H CHzGHzN(CHs) t GHzGHzN)It These solvents can be used in combination of two or more types. Preferred solvents include thioethers, thiocyanates, thioureas, ammonia, and bromides, and particularly preferred is a combination of ammonia and bromide.

These solvents contain from 10-5 to 1 mole of silver halide.
It is preferable to use it in a range of 2 moles.

In addition, the pH is 3 to 13, and the temperature is 30 to 70.
°C is preferred, particularly preferably pH 6-12, temperature 3
It is in the range of 5 to 50°C.

One example of a preferred embodiment when the above manufacturing method is adopted is that the pH is 10.8 to 11.2, the temperature is 35 to 45°
C, using a combination of 0.4 to 1.0 mol/l of ammonia and 0.03 to 0.5 mol/i of potassium bromide, 30
An emulsion containing suitable seed particles was obtained by ripening for 10 seconds to 10 minutes.

A water-soluble silver salt may be added for the purpose of adjusting ripening during the seed particle forming step.

The seed grain growth step (c) for enlarging silver halide seed grains includes T'Ag, pH1 temperature, silver halide solvent concentration, and silver halide composition during silver halide precipitation and Ostwald ripening. This is accomplished by controlling the rate of addition of silver salt and halide solutions.

The conditions for enlarging the seed particles are as described in JP-A-51-390.
No. 27, No. 55-142329, No. 58-11392
No. 8, No. 54-48521, and No. 58-49938, a water-soluble silver salt solution and a water-soluble halide solution are added by the double jet method, and the addition rate is adjusted according to the enlargement of the particles to increase the number of new nuclei. One example is a method in which the temperature is gradually changed within a range where formation does not occur and Ostwald ripening does not occur. As another condition for enlarging the seed grains, a method of enlarging the seed grains by adding silver halide fine grains, dissolving and recrystallizing can be used, as shown in the Proceedings of the 1988 Annual Conference of the Photographic Society of Japan, page 88, but the former The method is preferred.

In producing the emulsion of the present invention, growth conditions for silver halide grains include pAg of 5 to 11 and temperature of 40 to 8.
5'C and pH 15 to 5.8 are preferred. The pH is 1
．． 8 to 3.5 is particularly preferred. PAg is 6.0~
9.5 is particularly preferred, and the temperature is particularly preferably 60-80''C.

During growth, it is preferable to add a silver nitrate aqueous solution and a halide aqueous solution by a double jet method. Further, the modified state can also be supplied into the system as silver iodide. The addition rate should be such that new nuclei are not generated and the size distribution does not widen due to Ostwald ripening.
That is, it is preferable to add at a rate of 30 to 100% of the rate at which new nuclei are generated.

The emulsion of the present invention has a high silver iodide content phase (inner core) in the center.
The concentration of the aqueous silver nitrate solution used during the growth of the high silver iodide content phase is preferably IN or less, particularly preferably 0.3 to 0.8N.

In producing the emulsion of the present invention, stirring conditions during production may be extremely important. As a stirring device, a device shown in JP-A-62-160128, in which the additive liquid nozzle is installed near the mother liquor inlet of the stirrer (inside the liquid), is particularly preferably used. 1
Preferably, the speed is 200 rpm.

The emulsion of the present invention used to constitute the light-sensitive material of the present invention and other silver halide emulsions used in combination as appropriate are as follows:
Chemical sensitization can be carried out by conventional methods, or optical sensitization can be carried out 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 hydrophilic colloid layers can be hardened and can contain a plasticizer and a dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer.

The photosensitive material of the present invention can be preferably used as a color photosensitive material such as a color negative or a color reversal.

In particular, it is preferably used in color reversal light-sensitive materials having at least one blue-sensitive layer, one green-sensitive layer, and one red-sensitive layer on a support.

When the present invention is applied to a color reversal light-sensitive material, it is preferable that the emulsion of the present invention has a red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer in this order from the support side.
It may be used in any of the red-sensitive layer, green-sensitive layer, and blue-sensitive layer. When these color-sensitive layers consist of two or more photosensitive layers, they are added to the layer furthest from the support, and the core layer is the same.
It is preferable that the photosensitive medium also has high sensitivity.

Furthermore, the emulsion of the present invention is preferably added to a blue-sensitive layer. If the blue-sensitive layer consists of two or more layers with different sensitivities, it is preferable to add it to the layer furthest from the support, and the core layer is the blue-sensitive layer with the highest sensitivity, and Most preferably, the emulsion of the present invention is added to the high speed blue sensitive layer.

When the emulsion of the present invention is used in a blue-sensitive layer, it is preferably spectrally sensitized with a known blue sensitizing dye.

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

It is preferable to provide one or more non-photosensitive layers further away from the support than the layer to which the emulsion of the present invention is added.

In the present invention, a development accelerator, a bleach accelerator, a developer, a silver halide solvent, a toning agent, a hardening agent, a fogging agent, a color toning agent, a hardening agent, a fogging agent, etc. are prepared by coupling with a colored coupler, a competitive coupler, and an oxidized form of a developing agent as necessary. Compounds that release photographically useful fragments can be used, such as agents, antifoggants, chemical sensitizers, spectral sensitizers, and desensitizers.

The photosensitive material can be provided with auxiliary layers such as a filter layer, an antihalation layer, an antiirradiation layer, and the like.

These layers and/or the emulsion layer may contain dyes that are washed out of the light-sensitive material or bleached 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 retarder, and a bleach accelerator can be added to the photosensitive material.

As a support, paper laminated with polyethylene, etc.
Polyethylene terephthalate film, baryta paper, cellulose triacetate film, etc. can be used.

[Example] Examples of the present invention will be described below. However, it goes without saying that the present invention is not limited to the examples described below.

Example 1 (Preparation of spherical seed emulsion) The following A1 to D
A monodisperse spherical seed emulsion was prepared using this solution.

/l, and the ammonia concentration was 0.63 mol/1.

Thereafter, the pH was adjusted to 6.0, and the solution was immediately desalted and washed with water. When this seed emulsion was observed under an electron microscope, the average grain size was 0.
．． It was a monodisperse spherical emulsion with a diameter of 36 μm and a distribution width of 18%.

Comparative Example 1 Using the seed emulsion of Example 1, a tabular comparative emulsion Em-A having an average silver iodide content of 1.93 mol % was prepared.

D. Ammonia water (28%) 705
d Stir vigorously at 40°C.A, liquid, B, liquid and C.

The liquid was added in 30 seconds using a double jet method to generate nuclei. The pBr at this time was 1.09 to 1.15.

After 1 minute and 30 seconds, liquid D was added over 20 seconds, and the mixture was aged for 5 minutes. The KBr concentration during ripening is 0.071 mol L. Adjust to 41 with water.

Liquid B2 and liquid 02 were added over 40.5 minutes to liquid A2, which was vigorously stirred at 65°C, by a double jet method.

During this time, the pH was maintained at 2.0 with nitric acid, and the pAg was maintained at 9.0 throughout. The addition speed of B2 liquid and 02 liquid is 2 at the initial and final stage.
．． It was increased linearly by a factor of 95.

After the addition was completed, the pH was adjusted to 6.0, and in order to remove excess salts, precipitation desalination was performed using an aqueous solution of Demol (manufactured by Kao Atlas Co., Ltd.) and an aqueous solution of magnesium sulfate.
g8.5. An emulsion with pH 5.85 at 40°C was obtained. When the obtained emulsion was observed with an electron microscope, the average grain size was 0.92 μm, the distribution width was 14%, and the projected area was 8.
8% of the grains were tabular silver halide grains consisting of 100% (111) planes.

Further, the average grain diameter/grain thickness ratio of the tabular silver halide grains was 3.6. The CuKα of this emulsion consisted of two sharp peaks with a peak interval of 0.27 degrees (2θ) (see Figure 2).

All measurements of the emulsion samples on each side were carried out using a JDX-11 model manufactured by JEOL Ltd., a graphite monochromator as a monochromator for diffraction lines, and the measurement conditions were a tube voltage of 40 kV, a tube current of 50 n+A, and a step angle. The angle was 0.02 degrees (2θ). Under these measurement conditions, the half-width of the (331) diffraction signal of the silicon powder used as a standard sample was 0.33 degrees (2θ) (see FIG. 4).

Comparative Example 2 The seed emulsion of Example 1 was used, the average grain volume was the same as Em-A, and the average silver iodide content was 8.0 mol%.
A comparative emulsion Em-B, which is a monodisperse twin emulsion having a high silver iodide content phase inside the grains, was prepared.

Liquid 83-1 and liquid C8-1 were added to liquid A, which was vigorously stirred at 75°C, by a double jet method. At this time, the pH was maintained at 2.0 with nitric acid and the PAg was maintained at 8.0. The addition time was 45 minutes, and the addition rate was increased linearly by a factor of 1.9 between the initial and final times. Next, add B5-2 solution and C to the same solution.
3-z solution was added by double jet method.

At this time, the pH was maintained at 2.0 and the pAg at 8.0. The addition time was 28 minutes, and the addition rate was increased linearly by a factor of 1.75 between the initial and final times. After the addition was completed, the pH was adjusted to 6.0, and in order to remove excess salts, precipitation desalting was carried out using an aqueous Demol solution and an aqueous magnesium sulfate solution to obtain an emulsion with a PAg of 8.5 at 40°C.

When the obtained emulsion was observed with an electron microscope, the average grain size was 0.75 μm, the distribution width was 15%, and the (100) plane and (1
11) It was a monodisperse tabular silver halogen emulsion with a plane.

The (420) diffraction line of this emulsion using CuKα radiation as a radiation source was a wide signal consisting of two peaks with a peak interval of 1.32 degrees (see Figure 3).

Example 2 The seed emulsion of Example 1 was used, and the average grain volumes were Em-A, E
Same volume as m-B and average silver iodide content of 2.25
Emulsion Em-1 of the present invention was prepared in mol %.

Liquid B4-1 and Liquid 04-1 were added by a double jet method to Liquid A4 (manufactured by 542) (Company) 1, which was vigorously stirred at 75°C. At this time, the pH was maintained at 2.0 and p and Ag at 8.0 with nitric acid. The addition time was 16 minutes, and the addition rate was increased linearly by a factor of 1.27 between the initial and final times. Next, in the same liquid, add 13m-'z
Liquid and 04-2 liquid were added by double jet method. At this time, the pH was adjusted to 2.0 and the PAg was adjusted to 8.0.

The addition time was 38 minutes, and the addition rate was increased linearly by a factor of 1.80 between the initial and final times. Comparative example 1 after completion of addition.
Desalting and precipitation were performed in the same manner as in 2, and the PAg was 8.5 at 40°C.
An emulsion with a pH of 5.85 was obtained.

When the obtained emulsion was observed with an electron microscope, it was found that 100
The silver halide emulsion consisted of % twin grains, had an average grain size of 0.73 μm, and had a distribution width of 11%. In addition, 100% of the projected area has a particle diameter/particle thickness ratio of 160 to 1.
5 and had (100) and (111) planes, with a ratio of 64:36.

The (420) diffraction line using CuKα radiation as the radiation source of this emulsion has only one peak, and the maximum peak height x 0. The diffraction width at X3 was 0.816 degrees (2θ).

Also, a line drawn perpendicularly from the highest peak and peak height x 0
．． Let B be the point where the lines drawn horizontally at 13 intersect, and let AA' be the line segment where the lines drawn horizontally at peak height x 0.13 are cut by the signal, then AA' is determined by B AB: BA' =0.85: Divided into 1 (see Figure 1).

Example 3 An emulsion Em-2 of the present invention having an average silver iodide content of 2.02 mol % was prepared in the same manner as in Example 2 except that the solution B4-2 was replaced with the following solution. .

A5 Same as solution A4 of Example 2 B5-1 Same as solution B4-1 of Example 2 C5-1
C5-Z same as solution C4-1 of Example 2 Example 2
When the obtained emulsion, which was the same as solution C4-2, was observed using an electron microscope, it was found that it consisted of 100% twinned grains, with an average grain size of 0.
．． It was a silver halide emulsion with a diameter of 73 μm and a distribution width of 11%. In addition, 100% of the projected area has a ratio of particle diameter/particle thickness of 1.0 to 1.5, and (100) plane and (11
1) The ratio was 65:35.

The (420) diffraction line of this emulsion using CuKα radiation as the radiation source had only one peak, and the diffraction width at the maximum peak height x 0.13 was 0.820 degrees (2θ).

Also, a line drawn perpendicularly from the highest peak and peak height x 0
．． 13, the point where the horizontal lines intersect is B, and the line segment where the horizontal lines cut the signal at peak height x 0.13 is AA', then AA' is AB by B.
: BA'=o, a6: Divided into 1.

Example 4 The silver halide emulsions Em-A, Em-B, Em-1, and Em-2 obtained in Comparative Examples, 1 to 2, and Examples 2 to 3 were treated with sodium thiosulfate, chloroauric acid, and An appropriate amount of ammonium thiocyanate was added and chemical ripening was performed at 50°C. After chemical ripening, a sensitizing dye and 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene were added as a stabilizer.

Using these emulsions, the following multilayer color light-sensitive materials were prepared. The types and amounts of the sensitizing dyes are shown below.

Sample 101 was prepared as a comparative sample of a multilayer color light-sensitive material by sequentially coating each layer having the composition shown below from the support side onto a subbed triacetyl cellulose film support.

The coating amount of each component is expressed in g/rrf. However, for silver halide, the coating amount is expressed in terms of silver.

1st layer (antihalation layer) Ultraviolet absorber U-10,3 Ultraviolet absorber U-20,4 High boiling point solvent 0-1 1.0 Black colloidal silver 0.24 Gelatin
2.0 Second layer (intermediate layer) 25-di-t-octylhydroquinone 0.1 High boiling point solvent 0-1 0.2 Gelatin 1.0 Third layer (low sensitivity red-sensitive silver halide emulsion layer) Red enhancement Sensitive dye (S-1,5-
AgBrI emulsion spectrally sensitized by 2) (Agl content 4.0 mol% average grain size 0.25 μm)
0.5 Coupler C-10,3 High boiling point solvent 0-2 0.6 Gelatin 1.3 4th layer (high sensitivity red-sensitive silver halide emulsion layer) Red sensitizing dye (S-1,5-
2) AgBrI emulsion spectrally sensitized (Em-A)
0.8 Coupler C-11,0 High boiling point solvent 0-2 1.2 Gelatin 1.8 5th layer (intermediate layer) 2.5-di-t-octylhydroquinone 0.1 High boiling point solvent 0-1 0. 2 Gelatin 0.9 6th layer (low sensitivity green-sensitive silver halide emulsion layer) Green sensitizing dye (S-3,5-4
) spectrally sensitized AgBrI emulsion (AgI content 3.5 mol%).

Average particle size 0.25 am) 0.
6 Coupler M-10,15 Coupler M-20,04 High boiling point solvent 0-3 0.5 Gelatin 1.4 7th layer (high sensitivity green-sensitive silver halide emulsion layer) Green sensitizing dye (S-3,5 −
4) AgBr1 emulsion spectrally sensitized (Em-A)
0.9 coupler M-10,56 coupler M-20,12 High boiling point solvent 0-3 1.0 gelatin 1.5 8th layer (intermediate layer) 9 layers same as 5th layer (yellow filter layer) Yellow colloidal silver 0.1 Gelatin 0.92.5-di-octylhydroquinone 0.1 High boiling point solvent 0-10.2 10th layer (low sensitivity blue-sensitive silver halide opalescent layer) Blue sensitizing dye (S-5) AgBrI emulsion spectrally sensitized by (
AgI content 2.5 mol%, average particle size 0.35 μm)
0.6 coupler Y-
11,4 High boiling point solvent 0-3 0.6 Gelatin 1.3 Eleventh layer (high sensitivity blue-sensitive silver halide emulsion layer) AgBrI emulsion spectrally sensitized with blue sensitizing dye (S-5) (E m -A)
0.9 Coupler Y-13,5 High boiling point solvent 0-3 1.4 Gelatin 2.1 12th layer (first protective layer) Ultraviolet absorber U-10,3 Ultraviolet absorber U -20,4 2,5 -di-t-octylhydroquinone 0.1 High boiling point solvent 0-3 0.6 Gelatin 1.2 13th layer (second protective layer) Average particle size (F) 0.08 μm, contains 1 mol% silver iodide Non-photosensitive fine-grain silver halide emulsion made of silver iodobromide
0.3 Polymethyl methacrylate particles (diameter 1.5 μm) 0.06 Surfactant 5A-10,004 Gelatin 0.7 In addition to the above composition, each layer contains gelatin hardening agent H-1 and an interface. Activator was added.

Ultraviolet absorber U-1 Ultraviolet absorber U-2 Sensitizing dye S-1 Sensitizing dye S-2 ('DI Sensitizing dye S-3 Sensitizing dye-enhancing dye N (CzHsh Coupler Gelatin Hardener Surfactant A -1 Coupler H Coupler Next, in contrast to Comparative Sample 1, Samples 2 to 9 were prepared as shown in Table 1.

These samples were exposed to red light (Eastman Kodak CC).
-9OR filter) was used to perform wedge exposure, and then the development process described later was performed.

In addition, for each sample, the following (1) scratch test,
and (2) a bending test was conducted.

(1) Scratch test A sample is fixed on a steel plate with the photosensitive layer side up, and a diamond needle with a tip diameter of 0.01 mm is used to move the diamond needle over the sample for 1.5 seconds while applying a load of 10 g. 0c
It was pressed and moved at a speed of m7 seconds.

(2) Bending test The sample was bent along the direction of change in exposure amount with a radius of curvature of 3 degrees and a bending angle of 20 degrees and left standing for 5 seconds.

This was carried out for the case where the photosensitive layer was on the inside.

For this bending test, after wedge exposure using white light, the development process described below was performed.

There is some blank space below...

table In addition, the amount of compounds added in Table 1 is It was set to 0.001 mol/AgX mol.

Processing process Processing time Processing temperature First development
6 minutes 38°C water washing 2 minutes
38°C inversion 2 minutes
38°C color development 6 minutes 38°C adjustment 2 minutes 38°C bleaching 6 minutes 38°C fixing
4 minutes Wash with water at 38°C 4 minutes Stable at 38°C 1 minute
Dry at room temperature The composition of the treatment liquid used in the above treatment step is as follows.

(First developer) Sodium tetrapolyphosphate 2g Sodium sulfite 20g Hydroquinone
Monosulfonate 30g Sodium carbonate (monohydrate) 30
g 1-phenyl-4-methyl-4-dihydroxymethyl-3-pyrazolidone 2g Potassium bromide Potassium thiocyanate Potassium iodide (0.1% solution) Add water and invert solution> Nitrilotrimethylenephosphonic acid 6-sodium salt chloride Stannous (dihydrate) Sodium p-aminophenol hydroxide Add glacial acetic acid water Color developer Sodium tetrapolyphosphate Sodium sulfite Tertiary sodium phosphate (dihydrate) Potassium bromide Potassium iodide (0.1% Solution) Sodium hydroxide citrazine acid 2.5g 1.2g 1d 000d g g 0.1g g 5d 1000 relativesg g 6g g 90ai! g 1.5g N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 11g2.2-ethylenedithiogetanol 1g Add water
1000d〈Adjustment solution〉 Sodium sulfite 12g Sodium ethylenediaminetetraacetate (dihydrate) g O,4d 3-relative000d Add thioglycerin glacial acetic acid water〈Bleach solution〉 Sodium ethylenediaminetetraacetate (dihydrate) Iron ethylenediaminetetraacetate ( I[r] Ammonium (dihydrate) Add ammonium bromide water <Fixer> g 20g 00g Ammonium thiosulfate 80g Sodium sulfite 5g Sodium bisulfite 5g Add water
1,000 liters (stabilizing solution) Formalin (37% by weight) 5-III Conidax (manufactured by Konica Corporation) Add 5-III water and measure the concentration of the 1,000-unit developed sample using an X-Lite densitometer model 310 using a Status A filter. were measured to determine the yellow and cyan densities when the cyan density of the red image was 1.0. The obtained results are summarized in Table-2.

For scratch testing, use Microdensitometer P
Density 1.0 by blue light photometry using DM-5 (manufactured by Konica)
The density difference (ΔD1..) between the pressed area and the pressed area is shown.

Regarding the bending test, the density change in the folded part relative to the unfolded part was visually evaluated relative to that in the following manner.

◎...No change in concentration is observed.

○: Slightly observed.

△...Difference in concentration is observed.

×: There is a significant difference in concentration.

The above results are shown in Table-2.

As is clear from Table 2, the samples of the present invention have excellent pressure resistance and red color reproducibility.

Moreover, instead of redox compound R-35 of sample 9, redox compound R-1, R-7, R-9 or R-48
When similar tests were conducted on samples using the same molar amount of , the effects of the present invention were obtained.

〔Effect of the invention〕

As described above, the silver halide color photographic light-sensitive material of the present invention has the effects of being able to have good pressure resistance without desensitization and having improved color reproducibility.

[Brief explanation of drawings]

FIGS. 1, 2, and 3 are graphs showing X-ray diffraction signals of emulsion grains of emulsion Em-1, emulsion Em-A, and emulsion Em-B, respectively. Figure 4 shows silicon powder (33
1) Powder X-ray diffraction pattern. Em-A times 1 & l Natsume (2e) Em-1 times-vr chromaticity size of IEm-1 x 1 instantaneous square J sheet Figure 1 x 103 Em-8 11'r1111i (2e) Em-B11X! Dam? ``711'' Figure 3

Claims (1)

[Scope of Claims] 1. A silver halide color photographic light-sensitive material having photographic constituent layers each including at least one red-sensitive, green-sensitive, and blue-sensitive light-sensitive silver halide emulsion layer on a support. , a silver halide photograph in which at least one of the light-sensitive silver halide emulsion layers comprises silver halide twin grains in which 50% or more of the projected area has a grain diameter/grain thickness ratio of less than 5; an emulsion, the silver halide emulsion is monodisperse, the (420) X-ray diffraction signal using CuKα radiation as a radiation source has a unique peak, and the maximum peak height x 0.1
A silver halide photographic emulsion having a diffraction linewidth of less than 1.5 degrees at a diffraction angle (2θ) in No. 3 is contained, and at least one of the photographic constituent layers is oxidized by an oxidation product of a developing agent. 1. A silver halide color photographic light-sensitive material comprising at least one compound or a precursor thereof that releases a photographically useful reagent upon attack by a nucleophile.