JPH03122636A - Reversal color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain natural hues and high saturations by controlling the gravity center sensitivity wavelength of the spectral sensitivity distribution of each silver halide emulsion layer containing yellow, magenta and cyan color within a specified wavelength region. CONSTITUTION:The silver halide emulsion layer containing the yellow coupler and spectrally sensitized so as to control the specified spectral sensitization region into 400 - 520 nm has a gravity center sensitization region within 430 - 480 nm, the silver halide emulsion layer containing the magenta coupler and spectrally sensitized so as to control the specified spectral sensitization region into 470 - 600 nm has a gravity center sensitization region within 520 - 580 nm, and the silver halide emulsion layer containing the cyan coupler and spectrally sensitized so as to control the specified spectral sensitization region into 540 - 700 nm has a gravity center sensitization region within 590 - 650 nm, thus, permitting a color picture having natural hues and high saturations to be obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a reversal color photographic material that provides an extremely natural hue and high chroma.

(Prior technology) Conventional color films have been developed by improving the three types of coloring dyes used, improving the spectral sensitivities of blue, green, and red, and by appropriately applying multilayer effects to reduce color mixture between each photosensitive layer. Its performance has been improved over time. However, these technologies themselves are still insufficient, and there has been insufficient comprehensive consideration of the spectral sensitivity characteristics of the human visual sense (for example, the human three-color stimulus value curve), and the saturation Conventional color photosensitive materials were still insufficient in expressing gradation of objects with high density and high density, or expressing differences in hue that change subtly.

For example, U.S. Pat. No. 3,672,898 describes the relative spectral sensitivity distribution of each photosensitive layer, which has particularly good color rendering properties for neutral colors and colors, obtained from a multilayer color photosensitive material photographed using various light sources. It is written about. However, this also lacks consideration of the details of Iruma's color sensing spectral characteristics, the spectral absorption characteristics of each coloring pigment, and the automatic compensation characteristics due to the mutual layering effect of each of the three layers. Satisfactory results cannot be obtained regarding the quality of color reproduction.

JP-A-54-118245 contains a DIR compound that couples with the oxidation product of a color developer to release a development inhibitor and produce a substantially colorless reaction product;
A method is disclosed for improving color reproducibility and sharpness by providing a silver halide emulsion layer that does not substantially contribute to color image formation.

However, the details of the spectral characteristics of the human color sense are not taken into account (and the image quality of the resulting color photographs is not satisfactory).

JP 62-136649 discloses that at least one of the dye image-forming units comprises a dye-forming coupler and a first silver halide emulsion layer spectrally sensitized to a certain spectral region;
a second silver halide emulsion layer spectrally sensitized to a different spectral region from that of the second silver halide emulsion layer and comprising means for producing an interlayer effect which forms during color development compounds which do not substantially contribute to color image formation. It has been disclosed that color reversal photosensitive materials for printing have improved interlayer effects.

Further, EP-0296,784A No. 2 discloses similar effects for reversal sensitive materials for printing and transmission.

However, both of the above two inventions are attempts to make the multilayer effect more effective by using DIR compounds during color development, and they are not sufficiently effective in color development at high pH and/or over a long period of time, such as in reversal color processing. cannot be obtained.

JP-A-61-34541 and JP-A-63-8985
Although No. 0 discloses a method for achieving spectral sensitivity that imitates the color-matching spectral sensitivity of the human eye and its effects, it does not disclose a reversal color photographic material. The reasons for this include, as mentioned above, that in reversal color photographic materials, it is not as easy to develop a multilayer effect during color development as in color negative photographic materials, and that color F couplers cannot be used.

JP-A No. 64-66644 discloses a reversal color photographic material containing an emulsion layer that produces an interlayer effect during black-and-white development and does not substantially form an image dye, but the spectral sensitivity has not been sufficiently studied. However, it had the drawback that the color reproduction was not faithful.

(Problems to be Solved by the Invention) An object of the present invention is to provide a reversal color photographic material that provides a natural hue and high saturation.

(Means for solving problems) The purpose of the present invention is to:

(1) each containing at least one layer of yellow couplers on a support, the specific spectral sensitivity range of which is from 400 nm to 5 nm;
A silver halide emulsion layer (BL) spectrally sensitized to have a specific sensitivity range between 20 nm and 20 nm, a silver halide emulsion layer (BL) that is spectrally sensitized to have a specific sensitivity range between 470 nm and 600 nm. In a reversal color photographic material having an emulsion layer (GL) and a silver halide emulsion layer (RL) containing a cyan coupler and spectrally sensitized so that the specific sensitivity range is between 540 nm and 700 nm, the GL The centroid sensitivity wavelength (λG) of the spectral sensitivity distribution of RL is between about 5200 m and 580 nm, and the centroid sensitivity wavelength (1,) of the spectral sensitivity distribution of RL is between about 590 nm and 650 nm.
nm, and the centroid sensitivity wavelength of the spectral sensitivity distribution of BL (
λR) is between about 430 nm and 480 nm, and has a silver halide grain-containing layer adjacent to at least GL or RL and covering the surface and/or inside thereof, ( 2) The reversal color photographic light-sensitive material according to item (1), which has at least one silver halide emulsion layer (ICL) that exhibits a multilayer effect during black-and-white negative development and does not substantially form an image dye; (3) The reversal color photographic light-sensitive material according to item (1) and item '(2), which contains a compound that exhibits a multilayer effect during color development and does not substantially form an image dye in ICL. , achieved by. Here, the "specific spectral sensitivity range" refers to the wavelength range sandwiched between the long wavelength side and the short wavelength side corresponding to the sensitivity of 1/10 of the maximum spectral sensitivity range of the spectral sensitivity spectrum curve, and is the "substantially does not form image pigments on
means that the maximum color density is 0.3 or less, preferably 0.
2 or less.

The present invention will be explained in detail below.

The centroid sensitivity wavelength of the spectral sensitivity distribution is described in, for example, Japanese Patent Laid-Open No. 61-34541. In the present invention, the centroid sensitivity wavelength λ for GL. is given by the following formula.

S here. (λ) is the spectral sensitivity distribution curve of GL. Similarly, J:::sm(λ)dλ Also, the interlayer effect donor layer (ICL) mainly for RL
) can be defined as R by looking at the centroid sensitivity wavelength. Other terms are also used accordingly.

The first object of the present invention is to provide natural color reproducibility that imitates human visual perception. About human vision, Color Science Handbook, Chapter 10 (Color Society of Japan, 1985, Chapter 5)
Wright's curve, which shows the spectral chromaticity values of the three colors red, green, and blue, is known. Also Pr1nciples of
Co1or Photography (R.

M. Evans et al. 1953 edition John W.H.
There is a description about color reproducibility in Chapter 18 of EY&5ONS Publishing Co., Ltd.). As shown in the visual isochromatic relative spectral sensitivity distribution using the current dye systems of yellow, magenta, and cyan, negative sensitivity appears in each of the blue, green, and red distributions, and there is a slight increase in the blue sensitivity region. An effect that gives a cyan image is required (Fig. 1).

The inventors of the present invention have repeatedly studied various means for providing this negative or positive sensitivity, and have found that, in order to obtain improved color reproducibility that is visually natural, the following multilayer effect is provided. I found that this is necessary.

That is, the spectral sensitivity of the interlayer effect donor layer mainly for RL is such that its centroid sensitivity wavelength ranges from approximately 490 nm to 56 nm.
The spectral sensitivity of the interlayer effect donor layer on GL is between approximately 400 nm and 5 nm.
00 nm and/or between about 570 nm and 670 nm, and the spectral sensitivity of the interlayer effect donor layer to BL is that its centroid sensitivity wavelength is between about 520 nm and 590 nm. Furthermore, it is also preferable to mix a small amount of cyan coupler into the BL in order to produce the effect of giving a slight cyan image to the BL.

The inventor of the present invention discovered that it is necessary to obtain a needle in the design of a color photosensitive material that has a large multilayer effect in order to achieve faithful color reproduction. We have discovered that the fidelity of color reproduction of wood can be measured quantitatively.This method uses spectral light mixed with white light, that is, spectral light with reduced stimulus purity (P,).The reason is that pure If spectral light is applied and only one of the blue, green, and red sensitive layers is exposed, the multilayer effect will not appear in the photograph, and the color photosensitive material for photographing will not absorb reflective objects with a certain degree of color turbidity. The reason is that it is often used as a photographic subject.

Next, a method for measuring the fidelity of color reproduction will be explained.

(Process 1) Apply equal energy spectrum light of 400 nm to color photosensitive materials with a constant stimulation purity specified by CIH in 1931.
and 700 nm at intervals of 10 nm. Further C
Exposure using the C light source defined in IE is also performed at the same time.

(Process 2) Perform color reversal development.

(Process 3) The chromaticity of the reproduced positive image was measured using a chromaticity meter SS color computer (manufactured by Suga Denki Co., Ltd.), and the chromaticity was measured using a 1931 CI
Plot on the EXY chromaticity diagram.

(Process 4) The dominant wavelength of the positive image reproduced by drawing on the chromaticity diagram is
The correlation with the wavelength of the spectral light obtained and exposed as shown in the figure is plotted as shown in FIG. 3.

In the graphs obtained in the above steps 1 to 4, the more the wavelength of the spectral light applied to the photosensitive material and the dominant wavelength of reproduction match, that is, the closer they are on a straight line, the better the color reproducibility.

The inventors of the present invention have conducted extensive studies on the above method, and have found that in order to faithfully obtain color reproducibility of spectral light over the entire range of visible light, the above-mentioned scope of the present invention must be satisfied.

In the present invention, the above-mentioned predetermined spectral sensitivity can be imparted to the multilayer effect donor layer preferably used by appropriately selecting and using commonly used silver halide spectral sensitizing materials.

One of the points of improving the color reproduction of reversal color photographic materials is how large the multilayer effect can be designed. U.S. Pat. No. 4,082,553 discloses that the interlayer effect is increased by including a silver halide emulsion with covered grain surfaces in a photosensitive emulsion layer.
U.S. Pat. No. 4,626,498 discloses the effect of fogging silver halide inside the grains. Furthermore, JP-A No. 60-305355 discloses that by placing a covered silver halide emulsion layer adjacent to the lowest sensitive layer of each color sensitive layer, the chromaticity of the highlight part of a positive image is improved. This is disclosed. When using the spectral sensitivity of the present invention,
Even if the multilayer effect is designed to be comparable to that of conventional light-sensitive materials, the chromaticity still deteriorates, and this difficulty can be overcome.

The fogged silver halide emulsion of the present invention means that the fogged silver halide emulsion of the present invention is applied uniformly (in a non-imagewise manner) to both unexposed and exposed areas of a photographic light-sensitive material.
A silver halide emulsion that can be developed.

The surface-fogged silver halide emulsion is prepared by preparing an emulsion capable of forming a surface latent image under appropriate conditions of pH and 1) Ag.
It can be prepared by a method of adding a reducing agent or a gold salt, a method of heating under low pAg, a method of providing -like exposure, or the like. As the reducing agent, stannous chloride, hydrazine compounds, ethanolamine, etc. can be used.

Silver halide grains whose interiors are fogged can be prepared by depositing silver halide on the surfaces of the silver halide grains whose surfaces are fogged to form an outer film.

ICL refers to a silver halide emulsion layer that exhibits an interlayer effect during black-and-white negative development and does not substantially form an image dye.

As the development inhibitor released in black-and-white development used in ICL, a development inhibitor released from iodide ions contained in silver halide grains or a so-called DIR compound can be used.

It is necessary to appropriately select the iodine content of the photosensitive silver halide grains used as the iodide ion release material in ICL, but it is preferably 40 mol% or less, more preferably 2
It is 0 mol% or less and 2 mol% or more.

As the DIR compound, those represented by the following general formula (I) are preferred.

When using the above DIR compound, the above ICL is divided into an ICL (1) containing a photosensitive silver halide emulsion and an ICL (2) which is a non-photosensitive hydrophilic colloid layer containing a DIR compound.
Particularly preferred is separation into two.

General formula (I) A-(T L me) t represents.

Time represents a timing group linked to A via a sulfur atom, nitrogen atom, oxygen atom or selenium atom, t
is an integer of 0 or 1.

X means a development inhibitor.

A will be explained below. Examples of the redox nucleus represented by A include hydroquinone, catechol, p-aminophenol, 0-aminophenol, 1,2-naphthalenediol, 1,4-naphthalenediol, ■, 6-
Naphthalene diol, 1,2-aminonaphthol, 1.
Examples include 4-aminonaphthol and 1.6-aminonaphthol. At this time, the amino group is preferably substituted with a sulfonyl group having 1 to 25 carbon atoms or an acyl group having 1 to 25 carbon atoms.

Examples of the sulfonyl group include substituted or unsubstituted aliphatic sulfonyl groups and aromatic sulfonyl groups. Examples of the acyl group include substituted or unsubstituted aliphatic acyl groups and aromatic acyl groups.

The hydroxyl group or amino group forming the redox core of A is
It may be protected with a protecting group that can be removed during development.

Examples of protective groups include those having 1 to 25 carbon atoms, such as acyl group, alkoxycarbonyl group, carbamoyl group,
Furthermore, JP-A-59-197037, JP-A-59-20
Protecting groups described in No. 1057 may be mentioned.

Furthermore, if possible, this protecting group may be bonded to the substituents of A described below to form a 5.6- or 7-membered ring.

The redox nucleus represented by A may be substituted with an appropriate substituent at an appropriate position. Examples of these substituents include those having 25 or less carbon atoms, such as alkyl groups, aryl groups,
Alkylthio group, arylthio group, alkoxy group, aryloxy group, amino group, amido group, sulfonamido group, alkoxycarbonylamino group, ureido group, carbamoyl group, alkoxycarbonyl group, sulfamoyl group, sulfonyl group, cyan group, halogen atom, acyl group,
carboxyl group, sulfo group, nitro group, heterocyclic residue,
can be given. These substituents may be further substituted with the substituents described above. Further, these substituents may be bonded to each other to form a saturated or unsaturated carbocycle or a saturated or unsaturated heterocycle, if possible.

Preferred examples of A include hydroquinone, catechol, p-aminophenol, and 0-aminophenol% 1
, 4-naphthalenediol, and 1°4-aminonaphthol. More preferred examples of A include hydroquinone, catechol, p-aminophenol, and 0-aminophenol. Most preferred as A is hydroquinone.

Preferred examples of A are shown below.

The pain is +T i me 9-t Indicates the bonding position of X.

υH M H H H H 0H Blue H (Jl-1 QC141-12, (n) fT I me +t X is A in general formula (1)
It is a group that is released as "+Time+x" only when the acid and the reducing mother nucleus, which is commonly known in the art, undergo a cross-oxidation reaction during development and become an oxidized product.

Time is a timing group that is linked to humans through a sulfur atom, nitrogen atom, oxygen atom, or selenium atom. Examples include groups that cause release. As for Time, for example, U.S. patent ig, 24
LJ', No. 5'6.2, U.S. Patent Law 7. riOri, 313
No. 2,004, 71rJ, U.S. Patent No. V/411. , No. 3, Japanese Patent Publication No. 37
-7 Ko4, Ir, No. 21, Japanese Patent Publication Publication Ratio! 7-
Examples include those described in JJ, No. 137. Time may be a combination of two or more selected from those listed above.

X means a development inhibitor. Examples of development inhibitors include:
Examples include compounds having a mercapto group bonded to a heterocycle or heterocyclic compounds capable of producing iminosilver. Examples of compounds having a mercapto group bonded to a heterocycle include ff, substituted or unsubstituted mercaptoazoles (e.g. /-phenyl-3-mercaptotetrazole, /-probyl-3-mercaptotetrazole, l
-Butyl-J-mercaptotetrazole, cortacylthio-3-mercapto-i, 3. a-deadiazole, 3
-Methyl-4t-phenyl-! -Mercapto1. Ko,
gutriazole, /-(4t-ethylcarbamoylphenyl)-komelkabutoimidazole, -monomerkabutobenzooxazole, -monomerkabutobenzimidazole, komelkabutobenzothiazole, komelkabutobe/zooxazole, -monophenyl! -Merkaf)-/.

3, goooxadiazole, /-(j-(J-methylureido)phenyl 1-J-mercaptotetrazole, /
-(4t-nitrophenyl)-j-mercaptotetrazole,! -(-monoethylhexanoylamino)-comelcabutobenzimidazole), substituted or unsubstituted mercaptoazaindenes (e.g. t-methyl-Hiro-mercapto/, J, Ja, 7-titrazaindene, G,
J-dimethyl-comercapto/, J,3a,7-titrazainde/), substituted or unsubstituted mercaptopyrimidines (e.g. -1-mercaptopyrimidine/, -1-mercapto-goo-methyl-t-human tetraxypyrimidine) and so on.

Examples of the heterocyclic compound capable of forming iminosilver include substituted or unsubstituted triazoles (for example, 2.
4t-) Riazole, benzotriazole,! -Methylbe/sotriazole,! - nitrobenzotriazole,
! -bromobenztriazole, j-n-butylbe/citriazole, 4ft-dimethylbenzotriazole)
, substituted or unsubstituted indazoles (e.g.
Taso-k,! -nitroindazole, 3-nitrointazole, 3-chloro-! -nitrointasole), substituted or unsubstituted benzimidazole ff4C e.g.!
-Nitrobenzimidazole! , t-dichlorotetrabenzimidazole).

In addition, after X separates from Time in general formula (I) and once becomes a compound that has development inhibiting properties, it further causes a certain chemical reaction with the developer components and essentially does not have development inhibiting properties. Alternatively, it may be significantly reduced and converted into the following compound. Examples of functional groups that undergo such chemical reactions include ester groups, carbonyl groups,
Examples include an imino group, an immonic group, a Michael addition acceptor group, and an imide group. An example of such a deactivated development inhibitor is /-(j-7dinoxycaldznylphenyl)-! -Mercaptotetrazok, /-(4
t-phenoxylphenyl)-! -Mercaptotetrazole, /-(j-maleinimidophenyl)-
! -Mercaptotetrazole, j-phenoxycarbonylbenzotriazole, r (≠-cyanophenoxycarbonyl)benzotriazole, cophenoxycarbonylmethylthio, monomercapto 7,3. ≠-thiadiazole, j-nitro-3-phenoxycarbonylintersol, t-(j,j-dicroprobyloxycarbonyl)benzotriazole, 1-(4t-benzoyloxyphenyl)-t-mercaptotetrazole,
! -(-1methanesulfonylethoxycarbonyl)-komelkasotobe/zoteazole,! -cinnamoylaminobenzotriazole, /-(J-vinylcarbonylphenyl)-! -Mercaptotetrazole,! -succinimidomethylbenzotriazole, co-11-succi/
imidophenyl j-j-mercap) −/, J.

Gooki-cho diazole, 6-fethoxycarbonyl-comel-kabutobenzoxazole is produced.

In order to more specifically describe the content of the present invention, specific examples of compounds represented by the general formula CI) are shown below.

(I-/) (I-J) (I-,2) (1-1) C3H7 (1-A) (■-7) (x-r> ()-/ko) (I-/) (1 -/F) H (I-2) (■-10) (1-//) (I-/j) (1-/j) (I-77) (I-ノ?) 1-/ri] l -20) ■--≠) ■-One ( ■-27 ) (I-, 2-2) ( 1-, 2J) The compound represented by the general formula (I) can generally be prepared by the following two methods. It can be synthesized with First, Time is just a bond (1
= 0), the first is in chloroform, 1,2-dichloroethane, carbon tetrachloride, or tetrahydrofuran without catalyst or in the presence of an acid catalyst such as p-toluenesulfonic acid, benzenesulfonic acid, trifluoromethanesulfonic acid, or methanesulfonic acid. The method below involves reacting benzoquinone, orthoquinone, quinone monoimine, or quinone diimine derivative with a development inhibitor at a temperature between room temperature and 100°C. Second
is a benzoquinone, orthoquinone, or quinone monosubstituted with chlorine, bromine, or iodine in an aprotic polar solvent such as acetone, tetrahydrofuran, or dimethylformamide in the presence of a base such as potassium carbonate, sodium bicarbonate, sodium hydroxide, or triethylamine. Imin,
The quinone diimine derivative and the development inhibitor were heated from -20°C to 10°C.
This is a method in which the quinone compound obtained by reacting at 0° C. is reduced with a reducing agent such as diethylhydroxylamine or sodium hydrosulfide.

[Reference: Re5earch Disclosure
e 18227 (1979) ; Liebigs An
n, Chem, 764. 131 (1972)
] Then the type (t
=1), it can be synthesized in substantially the same manner as above.

That is, Time-
This is a method in which X is used or Time having a group that can be substituted for X (e.g., a halogen atom, a hydroxyl group, or a precursor thereof) is first introduced into the redox core, and then X is linked by a substitution reaction. .

The compounds represented by the general formula of the present invention may be used alone or in combination of two or more.

The compound represented by the general formula may be added as an emulsion obtained by dissolving in high-boiling oil and stirring at high speed, or dissolved in a water-soluble organic solvent such as alcohol or cellosolve, added to a gelatin solution, and finely divided by stirring. It may be added after being dispersed in.

The so-called DIR coupler is preferable as the "compound that exhibits a multilayer effect during color development and does not substantially form an image dye" in item (3) of the present invention.

As the DIR coupler used in ICL in the present invention, a compound represented by the following general formula (II) is used.

B+ (L+), -t-z (tr) In the formula, B represents a coupler component (including a colorless coupler and a hydroquinone residue), and Z represents the basis of a compound that exhibits a development inhibitory effect (development inhibitor). A bone-like expression, a represents 0 or l, when a=O, Z is directly bonded to B, when a=1, Z is directly bonded to A via a linking group L+, L is a linking group represents.

As the coupler component B in general formula (II), for example, U.S. Pat.
No. 91, No. 3,632,345, No. 3,958,99
Specification No. 3, JP-A-51-64927, JP-A-55-
Coupler components that react with oxidation products of developing agents but do not form coloring dyes, such as those described in Japanese Patent No. 161237, are also preferably used. Compounds of the above general formula (ff) having this type of coupler component B can be widely used in the ICL in the present invention.

Next, the compound represented by general formula (n) will be explained in detail.

The yellow image-forming coupler residue (yellow coupler component) represented by B in the above general formula (II) includes pivaloylacetanilide type, benzoylacetanilide type, malondiester type, malondiamine type, dibenzoylmethane type, benzothia Zolylacetamide type, malone ester monoamide type, benzothiazolylacetate type, benzoxacylylacetamide type, benzoxacylylacetate type, benzimidazolylacetamide type or benzimidazolylacetate type coupler residue, U.S. Pat. No. 3,841, Coupler residues derived from petrocyclic-substituted acetamides or heterocyclic-substituted acetates contained in No. 880 or U.S. Patent No. 3,770,4
No. 46, British Patent No. 1,459,171, West German Patent (
OLS) No. 2.503,099, Japanese Published Patent No. 50
-139738 or Research Disclosure No. 15737, or a coupler residue derived from the acylacetamides described in US Patent No. 4,046,574.
The heterocyclic coupler residues described in the above are preferred. Coupler residues derived from heterocyclic substituted acetates or U.S. Pat. No. 3,770.446, British Patent No. 1,459,1
No. 71, West German Patent (OLS) No. 2,503,099,
Coupler residues derived from acylacetamides described in Japanese Publication No. 50-139738 or Research Disclosure No. 15737, or heterocyclic coupler residues described in US Pat. No. 4,046,574 are preferred.

The magenta image-forming coupler residue (magenta coupler component) represented by B includes a 5-year-old xo-2-pyrazoline nucleus, a pyrazolo-[1,5-al benzimidazole nucleus, a cyanoacetophenone type coupler residue, or a pyrazolotriazole nucleus. Coupler residues having .

The cyan image-forming coupler residue (cyan coupler component) represented by B is preferably a coupler residue having a phenol nucleus or an α-naphthol nucleus.

In the present invention, the ICL with spectral sensitivity in the range of about 490 nm to 560 nm has little cyan coloring (and magenta coloring).
is an ICL with spectral sensitivity in the range of approximately 400 nm to 500 nm.
For ICL, B has less magenta coloring and preferably cyan or yellow coloring, and ICL has spectral sensitivity for about 570 nm to 670 nm, and ICL has less magenta coloring and cyan coloring, and B has spectral sensitivity for about 520 nm to 590 nm. It is particularly preferable to use B, which has less yellow (preferably magenta color) in ICL.

The basic moiety of the development inhibitor represented by Z in the above general formula includes a divalent nitrogen-containing heterocyclic group or a nitrogen-containing heterocyclic thio group, and examples of the heterocyclic thio group include a tetrazolylthio group and a benzthiazolylthio group. Examples include a ruthio group, a benzimidazolylthio group, a triazolylthio group, and an imidazolylthio group. Specific examples are 113-(L+)- and -(L2-Y). The substituent positions of the groups are shown below.

In the above formula, the substituent X is included in the part Z of general formula (I), and is a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkanamide group, an alkenamide group, an alkoxy group, a sulfonamide group, or an aryl group. represents.

Examples of the linking group represented by Ll include the following. B and Z-(L, -Y). Shown with

B-(-OCH2Z-(Lz-Y)b)p (linking group described in U.S. Patent No. 4.146.396) Bmo5CH2-
Z-(Lz-Y)b:] p1 B(-QC-Z-(Lz Y)b)p (linking group described in West German Published Patent Application No. 2.626.315) (West German Published Patent Application No. 2.855 (C represents an integer of 0 to 2.) In the above formula, R□ is a hydrogen atom, a halogen atom, an alkyl group,
Alkenyl group, aralkyl group, alkoxy group, alkoxycarbonyl group, anilino group, acylamino group, ureido group, cyano group, nitro group, sulfonamide group, sulfamoyl group, carbamoyl group, aryl group, carboxy group, sulfo group, cycloalkyl group , represents an alkanesulfonyl group, an arylsulfonyl group or an acyl group.

Rzi represents a hydrogen atom, an alkyl group, an alkenyl group, an aralkyl group, a cycloalkyl group, or an aryl group, and p and q each represent 1 or 2. When q is 2, RZI may form a condensed ring.

These DIR couplers (in general formula (II) a=
In case 1), the leaving group released after reacting with the oxidized form of the developing agent immediately decomposes and forms the development inhibitor (H-Z-(
L, -Y), ) is released. Therefore, the effect of the present invention is the same as that of a DIR coupler having no group represented by (when a=O in general formula (II)).

In each of the above formulas, the linking group represented by L2 includes a chemical bond that is cleaved in a developer.

Such chemical bonds include the examples listed in the table below. Since these are cleaved by nucleophilic reagents such as hydroxy ions or hydroxylamine, which are components of the color developer, the effects of the present invention can be obtained.

The divalent linking group shown in the preceding table is linked to Z directly or via an alkylene group or (and) a phenylene group, and directly linked to Y. When connecting to Z through an alkylene group or a phenylene group, the intervening divalent group has an ether bond, an amide bond, a carbonyl group,
It may contain thioether bonds, sulfone groups, sulfonamide bonds and urea bonds.

As the linking group represented by L2, the following examples are preferable. The substitution positions of Z and Y are shown below.

-Z-(CH2)-Coo-Y -z -(cH2)7-NHcoo-yZ-NCOO-
Y W and d represent an integer of 0 to 10, preferably 0 to 5. Wl is a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, an alkanamide group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, and an alkanamide group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms. alkoxy group, alkoxycarbonyl group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, aryloxycarbonyl group, alkanesulfonamide group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, aryl group, carbamoyl group, carbon number 1 to 10, preferably 1 to 5 N-alkylcarbamoyl groups, nitro groups, cyano groups, arylsulfonamide groups, sulfamoyl groups, imido groups, and the like. W2 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms,
It represents an aryl group or an alkenyl group, W represents a hydrogen atom, a halogen atom, a nitro group, an alkoxy group having 1 to 6 carbon atoms, or an alkyl group, and e represents an integer of 0 to 6.

The alkyl group or alkenyl group represented by Substituents include halogen atoms, nitro groups, alkoxy groups having 1 to 4 carbon atoms, aryloxy groups having 6 to 10 carbon atoms, alkaninosulfonyl groups having 1 to 4 carbon atoms, and 6 to 10 carbon atoms. Arylsulfonyl group, C1-5 alkanamide group, anilino group, benzamide group, C1-6 alkyl-substituted carbamoyl group, carbamoyl group, C6-5
10 aryl-substituted carbamoyl group, an alkylsulfonamide group having 1 to 4 carbon atoms, an arylsulfonamide group having 6 to 10 carbon atoms, an alkylthio group having 1 to 4 carbon atoms, an arylthio group having 6 to 10 carbon atoms, a phthalimide group, Succinimide group, imidazolyl group, 1,2.4-triazolyl group, pyrazolyl group, benztriazolyl group, furyl group, benzthiazolyl group, alkylamino group having 1 to 4 carbon atoms, alkanoyl group having 1 to 4 carbon atoms, benzoyl basis,
Alkanoyloxy group having 1 to 4 carbon atoms, benzoyloxy group, perfluoroalkyl group having 1 to 4 carbon atoms, cyano group, tetrazolyl group, hydroxy group, carboxyl group,
Mercapto group, sulfo group, amino group, alkylsulfamoyl group having 1 to 4 carbon atoms, arylsulfamoyl group having 6 to 10 carbon atoms, morpholino group, aryl group having 6 to 10 carbon atoms, pyrrolidinyl group, ureido group , urethane group, alkoxy-substituted carbonyl group having 1 to 6 carbon atoms, 6 to 6 carbon atoms
It is selected from an aryloxy-substituted carbonyl group of IO, an imidazolidinyl group, an alkylidene amino group having 1 to 6 carbon atoms, and the like.

Specifically, the alkanamide group or alkenamide group represented by X and Y has 1 to 1 carbon atoms, preferably 1 to 5 carbon atoms.
represents a straight chain, branched chain or cyclic alkanamide group or alkenamide group, and may have a substituent (the substituent is selected from the substituents listed above for the alkyl group and alkenyl group).

The alkoxy group represented by X specifically has 1 to 1 carbon atoms.
0, preferably represents a straight chain, branched chain or cyclic alkoxy group having 1 to 5 carbon atoms, and may have a substituent (,
The substituent is selected from the substituents listed above for the alkyl group or alkenyl group.

The aryl group represented by Y represents a phenyl group or a naphthyl group, and examples of the substituent include the substituents listed above for the alkyl group or alkenyl group or those having 1 to 1 carbon atoms.
4 alkyl groups, etc.

The heterocyclic group represented by Y includes a diazolyl group (2-imidazolyl group, 4-pyrazolyl group, etc.), a triazolyl group (1,2,4-triazol-3-yl group, etc.), a thiazolyl group (2-benzothiazolyl group, etc.) ), oxacylyl group (l,3-oxazol-2-yl group, etc.), pyrrolyl group, pyridyl group, diazonyl group (1,4-diazin-2-yl group, etc.), triazinyl group (1°2.4-yl group)
(such as a riazin-5-yl group), a furyl group, a diazolinyl group (such as an imidacillin-2-yl group), a pyronyl group, and a thienyl group.

More detailed examples of compounds are described in JP-A-63-89850.

The amount of the compound of general formula (I) added is preferably 10-4 to 1 mol, more preferably 10-'' to 10-1 mol, per 1 mol of silver halide in ICL. per mole of silver halide in ICL,
Preferably 10-4 to 1, more preferably 10-3 to 1
Contain 0-1 mol.

Further, the coating amount of silver halide grains whose surfaces and/or interiors are covered is preferably 1 mg to 100 mg/rr.
r, more preferably 5 mg to 80 mg/go.

The silver halide photographic emulsion used in the present invention may contain any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, and silver chloride. Excluding the silver halide used in the ICL, the preferred silver halide is about 3
Silver iodobromide or silver iodochlorobromide containing 0 mol% or less of silver iodide. Particularly preferred is about 0.5 mol% to about 1
Silver iodobromide containing up to 5 mole percent silver iodide.

Silver halide grains may be so-called regular grains having regular crystal shapes such as cubes, octahedrons, and tetradecahedrons, or grains having irregular crystal shapes such as tabular, spherical, etc. It may be one with crystal defects such as crystal planes or a composite form thereof. Also, mixtures of various crystal forms may be used.

The grain size of the silver halide may be fine grains of about 0.1 μm or less, or large grains with a projected area diameter of about 10 μm. Preferably it is 0.05 μm or more and 2 μm or less.

Further, a monodisperse emulsion having a narrow distribution or a polydisperse emulsion having a wide distribution may be used, but a monodisperse emulsion is preferable in terms of improving graininess and gradation.

Monodispersed emulsions are typically those in which at least 95% by weight of the emulsions are within ±40% of the average grain diameter. Emulsions used in the present invention have an average grain diameter of 0.05 to 2 microns and at least 95% by weight or at least 95% (by number of grains) of silver halide grains within a range of ±20% of the average grain diameter. can. Methods for making such emulsions are described in U.S. Pat. No. 3,574,628, U.S. Pat.

Also, Japanese Patent Application Publication No. 59-133542 and Japanese Patent Application No. 61-306
An internal latent image type emulsion as disclosed in No. 029 can also be preferably used.

In order to give the internal latent image type emulsion a preferable latent image distribution,
The degree of chemical sensitization, the amount of silver halide to be precipitated after chemical sensitization, and the conditions for precipitation must be adjusted.

Specifically, after optimally chemically sensitizing the core, the thickness is 0.
01 gm or less, preferably 0.001 to 0.009 μm
Thereafter, a shell with a thickness of preferably 0.002 to 0.008 μm is formed, and the surface of the shell is further chemically sensitized. The degree of chemical sensitization to be applied to the core surface and the shell surface is such that the ratio of the latent coefficients of the shell surface and the core surface when exposed to light is 115 or more and less than 1, preferably 1/4 to 9/10.
There is a way to make it so.

The silver halide emulsion described above has pAg and pH during grain formation.
obtained by controlling the For more information, see Photographic Science and Engineering (Photograp)lieScience an
d Engineering) Volume 6, 159-165
Page (1962); Journal of Photographic Science
aphic 5science), Volume 12, 242~
251 pages (1964), U.S. Patent No. 3,665°394
No. 1,413,748 and British Patent No. 1,413,748.

In addition, known silver halide solvents (for example, ammonia, rhodankali, or Showa 54-100717
Physical ripening can also be carried out in the presence of thioethers and thione compounds (described in No. 2003 or JP-A-54-155828).

Further, tabular grains having an aspect ratio of 5 or more can also be used in the present invention. Tabular grains are described by Gatoff, Photographic Science and Engineering (
Gutoff, Photographic Sciences
14, pp. 248-257 (1970); U.S. Patent No. 4.4
34.226, 4,414,310, 4゜43
3.048, 4,439,520, and British Patent No. 2,112,157. When tabular grains are used, there are advantages such as increased covering power and increased color sensitization efficiency by sensitizing dyes, and the above-cited US Pat. No. 4,43
4.226 describes in detail.

In the present invention, the following monodisperse hexagonal tabular grains can be used. The emulsion is a silver halide emulsion consisting of a dispersion medium and silver halide grains, in which 70% or more of the total projected area of the silver halide grains has a maximum area of 70% or more relative to the length of the side having the minimum length. The ratio of the lengths of the sides with length is
2 or less and is occupied by tabular silver halide grains having two parallel surfaces as outer surfaces, and furthermore, the coefficient of variation of the grain size distribution of the hexagonal tabular silver halide grains (its projection) is The particle size variation (standard deviation) expressed by the circular diameter of the area divided by the average particle size) is monodisperse of 20% or less, and the aspect ratio is 2.5 or more and the particle size is is 0.2μ
m or more.

The composition of the hexagonal tabular grains includes silver bromide, silver iodobromide,
It may be either silver chlorobromide or silver chloroiodobromide. When containing legal ions, the content is 0 to 30 mol%,
The crystal structure may be --like, or it may be composed of different halogen compositions on the inside and outside (or may have a layered structure.Also, it is preferable that the grains contain reduction-sensitized silver nuclei. .

The silver halide grains can be produced by undergoing the formation-Ostwald ripening and grain growth,
The details are as described in Japanese Patent Application No. 61-299155.

These emulsion grains are described in British Patent No. 1,027°146, U.S. Pat.
No. 877 and Japanese Unexamined Patent Publication No. 143331/1984. Further, silver halides of different compositions may be bonded by epitaxial bonding, or compounds other than silver halide such as silver rhodan or lead oxide may be bonded, and these emulsion grains are disclosed in US Pat. No. 4.094,684, No. 4,142,900, No. 4
, 459,353, British Patent No. 2.038.792, U.S. Patent No. 4,349,622, British Patent No. 4,395,4
No. 78, No. 4,4.33,501, No. 4,463,0
No. 87, No. 3,656.962, No. 3,852,06
No. 7, JP-A-59-162540, etc.

Additives used in the manufacturing process of silver halide emulsions are Research Disclosure No. 17643 and Research Disclosure No.
o, 18716, and the relevant parts are summarized in the table below.

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

■ Chemical sensitizers 2 Sensitivity enhancers Spectral sensitizers, supersensitizers Brighteners Antifoggants and stabilizers Light absorbers, filter dyes UV absorbers Anti-stain agents 3 Dye image stabilizers Hardeners Binder plasticizers agent, lubricant coating aid, surfactant static prevention agent RD 17643 23 pages 23-24 pages 24 pages 24-25 pages 25-26 pages 25 right column 25 pages 26 pages 26 pages 27 pages 26-27 pages 27 RD 18716 Page 648 Right column Same as above Page 648 Right column - Page 649 Right column Page 649 Right column Page 649 Right column - Page 650 Left column Page 650 Left - Right column Page 651 Left column Same as above Page 650 Right column Same as above Same as above The present invention Various color couplers can be used, specific examples of which include the aforementioned RD% No. l 7643, ■
- Described in the patents listed in Sections CG. As dye-forming couplers, couplers that give the three primary colors (i.e., yellow, magenta, and cyan) in subtractive color development are important, and specific examples of diffusion-resistant, hydrophobic, 4-equivalent or 2-equivalent couplers are mentioned above. RD, No. 17
In addition to the couplers described in Patent No. 643, ■-C and Section 0, the following can be preferably used in the present invention.

A representative example of the yellow coupler that can be used in the present invention is a hydrophobic acylacetamide coupler having a ballast group. A specific example is U.S. Pat.
No. 407,210, No. 2,875,057, and No. 3,265,506. The use of two-equivalent yellow couplers is preferred for the present invention, and U.S. Pat.
No. 3,933.501 and No. 4゜022.
Oxygen atom separation type yellow couplers described in Japanese Patent Publication No. 58-10739, U.S. Pat. No. 4,401,752, U.S. Pat.
D18053 (April 1979), British patent cylinder 1,42
No. 5,020, West German Application Publication No. 2,219,917,
Typical examples include the nitrogen atom separation type yellow couplers described in Japanese Patent Nos. 2,261,361, 2,329,587, and 2,433,812. α-pivaloylacetanilide couplers have excellent color fastness, especially light fastness, while α-
Benzoylacetanilide couplers provide high color density.

Magenta couplers that can be used in the present invention include hydrophobic indacylon- or cyanoacetyl-based couplers, preferably 5-pyrazolone- and pyrazoloazole-based couplers, which have a ballast group. The 5-pyrazolone coupler is preferably a coupler in which the 3-position is substituted with an arylamino group or an acylamino group from the viewpoint of the hue and color density of the coloring dye, and a representative example thereof is disclosed in US Pat.
311.082, 2,343.703, 2
, No. 600,788, No. 2,908.573, No. 3,062,653, No. 3,152,896, and No. 3,936.015. Particularly preferred as the leaving group for the two-equivalent 5-pyrazolone coupler are the nitrogen atom leaving group described in U.S. Pat. No. 4,310,619 or the arylthio group described in U.S. Pat. No. 4,351,897. Also, European Patent No. 73.
The 5-pyrazolone coupler having a ballast group described in No. 636 provides high color density. Examples of pyrazoloazole couplers include pyrazolobenzimidazoles described in U.S. Pat. No. 3,016,432, preferably pyrazolo[5] described in U.S. Pat. No. 3,725,067.
, 1-cl [1,2,4] Triazoles, Research Disclosure No. 24220 (198
pyrazolotetrazoles described in Research Disclosure No. 24230 (June 1984) and JP-A No. 60-33552 and pyrazolopyrazoles described in JP-A No. 60-43659 (June 1984). It will be done. The imidazo[1,2-bl pyrazoles described in U.S. Pat. No. 4,500,630 are preferred from the viewpoint of low yellow side absorption and light fastness of coloring dyes, and the imidazo[1,2-bl pyrazoles described in European Patent No. 119,860A Pyrazolo [1,5-
bl[1,2,4])-lyazole is particularly preferred.

Cyan couplers that can be used in the present invention include hydrophobic, diffusion-resistant naphthol and phenolic couplers, preferably the naphthol couplers described in U.S. Pat. 052,
No. 212, No. 4゜146.396, No. 4,228
Typical examples include two-equivalent naphthol couplers of the oxygen atom dissociation type described in No. 233 and No. 4,296,200. Further, specific examples of phenolic couplers are given in U.S. Patent Nos. 2,369,929 and 2,80.
No. 1,171, No. 2,772,162, No. 2,8
No. 95,826, etc.

Cyan couplers that are stable against humidity and temperature are preferably used in the present invention, and a typical example thereof is as described in U.S. Pat. Phenolic cyan coupler having U.S. Pat. No. 2,772,162;
Same No. 3.758.308, Same No. 4.126.396, Same No. 4,334,011, Same No. 4.327.173
2,5-diacylamino substituted phenolic couplers described in German Patent Publication No. 3,329,729 and European Patent No. 121,365, and U.S. Pat.
, No. 446.622, No. 4,333,999, No. 4,451.559 and No. 4,427,767, etc., having a phenylureido group at the 2-position,
These include phenolic couplers having an acylamino group in the wig position.

Granularity can be improved by using a coupler in which the coloring dye has an appropriate diffusibility. Such a coupler is
U.S. Patent No. 4,366.237 and British Patent No. 2,
No. 125,670 contains specific examples of magenta couplers, and European Patent No. 96,570 and West German Application No. 3,2
No. 34,533 describes specific examples of yellow, magenta or cyan couplers.

The dye-forming couplers and the special couplers described above may form dimers or more polymers. A typical example of a polymerized dye-forming coupler is U.S. Pat. No. 3,451,82.
No. 0 and No. 4,080.211. Specific examples of polymerized magenta couplers are described in British Patent No. 2,102.173 and U.S. Patent No. 4.367.2.
It is described in No. 82.

The coupler used in the present invention can be introduced into the photosensitive material by various known dispersion methods, such as a solid dispersion method, an alkali dispersion method, preferably a latex dispersion method, and more preferably an oil-in-water dispersion method. be able to. In the oil-in-water dispersion method, after dissolving either a high-boiling organic solvent with a boiling point of 175°C or higher and a so-called auxiliary solvent with a low boiling point, either alone or in a mixture of both, water or gelatin is dissolved in the presence of a surfactant. Finely dispersed in aqueous media such as aqueous solutions. Examples of high boiling point organic solvents are U.S. Pat.
, No. 027, etc.

Dispersion may be accompanied by phase inversion, and if necessary, the auxiliary solvent may be removed or reduced by distillation, noodle washing, ultrafiltration, or the like before use for coating.

Specific examples of latex dispersion processes, effects, and latex for impregnation include U.S. Pat. It is described in.

The light-sensitive materials produced using the present invention contain hydroquinone derivatives, aminophenol derivatives, amines, gallic acid derivatives, catechol derivatives, ascorbic acid derivatives, colorless couplers, and sulfonamide phenols as color-fogging inhibitors or color-mixing inhibitors. It may also contain derivatives and the like.

Various anti-fading agents can be used in the light-sensitive material of the present invention. Organic anti-fading agents include hydroquinones,
Hindered phenols, mainly 6-hydroxychromans, 5-hydroxycoumarans, spirochromans, p-alkoxyphenols, and bisphenols;
Representative examples include gallic acid derivatives, methylenedioxybenzenes, aminophenols, hindered amines, and ether or ester derivatives obtained by silylating or alkylating the phenolic hydroxyl group of each of these compounds. Further, metal complexes represented by (bissalicylaldoximado)nickel complex and (bis-N,N-dialkyldithiocarbamado)nickel complex can also be used.

The invention is also applicable to multilayer, multicolor photographic materials having at least two different spectral sensitivities on the support. Multilayer natural color photographic materials usually have at least one each of a red-sensitive emulsion layer, a green-sensitive emulsion layer and a blue-sensitive emulsion layer on a support. The arrangement of these layers can be arbitrarily selected as required. The preferred order of layer arrangement is red sensitivity, green sensitivity, and blue sensitivity from the support side, or blue sensitivity, red sensitivity, and green sensitivity from the support side.

Further, each of the above-mentioned emulsion layers may be composed of two or more emulsion layers having different sensitivities, or a non-photosensitive layer may be present between two or more emulsion layers having the same sensitivity. Usually, the red-sensitive emulsion layer contains a cyan-forming coupler, the green-sensitive emulsion layer contains a magenta-forming coupler, and the blue-sensitive emulsion layer contains a yellow-forming coupler, but different combinations may be used depending on the case.

The light-sensitive material according to the present invention includes, in addition to the silver halide emulsion layer,
Protective layer, intermediate layer, filter layer, antihalation layer,
It is preferable to appropriately provide an auxiliary layer such as a back layer.

In the photographic material of the present invention, the photographic emulsion layer and other layers are coated on a flexible support such as plastic film, paper, or cloth, or a rigid support such as glass, ceramic, or metal that is commonly used in photographic materials. be done. Useful flexible supports include cellulose derivatives (cellulose nitrate,
cellulose acetate, cellulose acetate butyrate, etc.), films made of synthetic polymers (polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, etc.), baryta layers or α-olefin polymers (e.g. polyethylene, polypropylene, ethylene/butene copolymers), etc. Paper coated or laminated with The support may be colored using dyes or pigments. It may be made black for the purpose of blocking light. The surface of these supports is generally treated with an undercoat to improve adhesion with photographic emulsion layers and the like.

When processing a color reversal photosensitive material, black and white development is performed and then color development is performed. This black and white developer contains dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, or N
Known black and white developing agents such as aminophenols such as -methyl-p-aminophenol can be used alone or in combination.

The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. Aminophenol compounds are also useful as color developing agents, but p-phenylenediamine compounds are preferably used, representative examples of which include 3-methyl-4-amino-N, N-diethylaniline, 3- Methyl-4-amino-N-ethyl-N
-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N
-β-methoxyethylaniline and their sulfates, hydrochlorides or p-toluenesulfonates.

Two or more of these compounds can be used in combination depending on the purpose.

The pH of these color developing solutions and black and white developing solutions is generally 9 to 12. The color developing solution of the present invention has a pH of 1
It is desirable that it be in the range of 1 to 12. The amount of replenishment of these developing solutions depends on the color photographic light-sensitive material being processed, but is generally less than 3ρ per square meter of light-sensitive material, and can be reduced to less than 500ml by reducing the bromide ion concentration in the replenisher. You can also do that. When reducing the amount of replenishment, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the area of contact with the air in the processing tank. Furthermore, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developer.

After color development, the photographic emulsion layer is usually bleached. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed separately. Furthermore, in order to speed up the processing, a processing method may be used in which a bleaching treatment is followed by a bleach-fixing treatment.

Furthermore, treatment with two consecutive bleach-fixing baths, fixing treatment before bleach-fixing treatment, or bleaching treatment after bleach-fixing treatment can be carried out as desired depending on the purpose. Examples of bleaching agents that can be used include compounds of polyvalent metals such as iron (■), cobalt (m), chromium (VI), and copper (II), peracids, quinones, and nitro compounds. Typical bleaching agents include ferricyanide; dichromate; iron (II);
I) or organic complex salts of cobalt (III), such as aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, glycol etherdiaminetetraacetic acid, or Complex salts of citric acid, tartaric acid, malic acid, etc.: persulfates; bromates; permanganates; nitrobenzenes, etc. can be used. Among these, aminopolycarboxylic acid iron (Ill) complex salts including ethylenediaminetetraacetic acid iron (Ill) complex salts and persulfates are preferred from the viewpoint of rapid processing and prevention of environmental pollution.

A bleach accelerator may be used in the bleaching solution, bleach-fixing solution, and their prebaths, if necessary.

Examples of fixing agents include thiosulfates, thiocyanates, thioether compounds, thioureas, and large amounts of iodide salts, but thiosulfates are commonly used, with ammonium thiosulfate being the most widely used. Can be used for As the preservative for the bleach-fix solution, sulfites, bisulfites, or carbonyl bisulfite adducts are preferred.

The silver halide color photographic light-sensitive material of the present invention is generally subjected to water washing and/or stabilization steps after desilvering treatment.

The amount of water used in the washing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the application, the temperature of the washing water, the number of washing tanks (the number of stages), the replenishment method such as countercurrent or forward flow, and various other conditions. Can be set over a wide range. this house,
The relationship between the number of washing tanks and the amount of water in the multistage countercurrent method is J
our own of the 5ociety
of Motion Picture and
Television Engineers Volume 64,
9.248-253 (May 1955 issue).

The pH of the washing water in the processing of the photosensitive material of the present invention is 4 to 9.
and preferably 5 to 8. The washing water temperature and washing time can be set variously depending on the characteristics of the photosensitive material, its use, etc., but generally it is 20 seconds to 10 minutes at 15 to 45°C, preferably 25 to 45°C.
A range of 30 seconds to 5 minutes at ~40°C is selected. moreover,
The light-sensitive material of the present invention can also be directly processed with a stabilizing solution instead of washing with water. In such stabilization treatment, Japanese Patent Application Laid-Open Nos. 57-8543 and 58-14834
All of the methods such as multistage countercurrent stabilization treatment, low replenishment thereof, and ion exchange treatment described in No. 60-220345 can be used.

Furthermore, following the water washing process, a further stabilization process may be performed, such as a stabilizing bath containing formalin and a surfactant, which is used as a final bath for color photosensitive materials for photography. . Various chelating agents and antifungal agents can also be added to this stabilizing bath.

Various treatment liquids in the present invention are used at 10°C to 50°C. Normally, the standard temperature is 33°C to 38°C, but higher temperatures can be used to accelerate processing and shorten processing time, or lower temperatures can be used to improve image quality and stability of the processing solution. be able to.

(Effects of the Invention) The reversal color photographic material of the present invention exhibits the excellent effect of providing color images with extremely natural hues and high saturation.

(Example) The present invention will be explained in more detail below using examples.

Example 1 Sample 101 was prepared by coating an emulsion layer with the following composition on an undercoated cellulose triacetate support (note that the layer number in this example is the number of sample 101)
.

Color reproducibility was also evaluated using the following process.

Rolling plate process time Temperature first development 6 minutes 38℃ Water washing 2 minutes 7 inversions
2 minutes Color development 6 minutes
〃 Adjustment 2 minutes 〃 Bleaching
6 minutes 〃Fixing 4 minutes 〃Washing 4 minutes
〃Stable 1 minute Drying at room temperature
The composition of the drying treatment liquid used is as follows.

East 2 current game water Nitrilo-N,N,N-tri Methylenephosphonic acid thorium salt sodium sulfite Hydroquinone monosulfate A00 Makoto g 0g Onate Sodium carbonate (-water salt) 1-phenyl-4-methyl- 4-hydroxymethyl-3 Pyrazolidone potassium bromide potassium thiocyanate Potassium iodide (0.1% solution) liquid) add water Inverted Yomogi water Nitrilo-N,N,N-tri Methylenephosphonic acid thorium salt Stannous chloride (trihydrate) 3.6-Sithiaoctane- 1.8-diol add water Kokkyouyogi 0g 0g g 2.5g 1, 2g m1 000m1 00m1 g g g 000ml water sodium sulfite Sodium ethylenediaminetetraacetate Rium (trihydrate salt) thioglycerin glacial acetic acid add water Ontan Koshiki water Sodium ethylenediaminetetraacetate Rium (trihydrate salt) Iron ethylenediaminetetraacetate (III) Ammonium (trishydride) salt) potassium bromide add water Dingzu precept water sodium thiosulfate sodium sulfite 00m1 2g g 0.4m1 S invitation 1000m [! 00m1 g 120g 00g 000d 800Trllll! 80.0g 5.0g sodium bisulfite add water fixed lid water Formalin (37% by weight) Fuji Drywell (Fuji film surfactant) add water 1st layer: anti-halation layer Black colloidal silver.

-1 -2 11-1 Gelatin 2nd layer: Intermediate layer PD-D 11-3 Gelatin 3rd layer: Intermediate layer gelatin 5, 0g 1000mf (800 units 5, 0m1 1000 units 0.25g/I 0.1g/r+1 ' 0.1g/resistance 0.1cc/resistance 1.9g/rrI1 10mg/rri' 40mg/rri 0.4g/rd 0.4g/a 4th layer: 1st red-sensitive emulsion layer sensitizing dye S-1 and Silver iodobromide emulsion spectrally sensitized with S-2 (monodispersed chamber cubic with average grain size 0.4μ, AgI content 4.5mol% and average grain size 0.3μ, AgI content 4.5mol%) A 1:1 mixture of monodispersed cubes) Amount of silver: 0.4 g/A fine grained silver iodobromide emulsion (average grain size: 0.06 μm, 0.1 mol% of AgI content) Amount of silver: 0.02 g/ rr? Coupler C-10,,2g/I C-2 0.05g/rrl'0il-1
0.1cc/I Oi 1-2 0.05cc/Gogelatin 0.8g/rrf 5th layer:
Second red-sensitive emulsion layer Silver iodobromide emulsion spectrally sensitized with sensitizing dyes S-1 and S-2 (average grain size 0.5μ, monodisperse cubic with AgI content 4 mol%) Silver amount 0.4g /rrr Coupler C-10,2g/r11' G-30,2g/I C-2 0.05g/rrItOi 1-
1 0. 1cc/rr? Oil
-20,05cc/rr? Gelatin 0.8g/rrr No. 6
Layer: Third red-sensitive emulsion layer Silver iodobromide emulsion spectrally sensitized with sensitizing dyes S-1 and S-2 (average grain size 0.7 μm, AgI content 2 mol %, monodisperse cubic particles) Silver amount 0.4g/rrr Coupler C-30, 7g1rd Coupler C-10, 3g/Saki Oi 1-2 0. lee/i
Gelatin 1.1g/a 7th layer:
Intermediate layer dye D-1 0.02g/Igelatin 0.6g/A 8th layer: Intermediate layer compound Cpd-A 0.2g/rr1''
g/chin 1. og/i 9th layer:
1st green-sensitive emulsion layer Silver iodobromide emulsion spectrally sensitized with sensitizing dyes S-3 and S-4 (average grain size 0.4μ, AgI content 4.5 mol%, monodisperse chamber cubic and average A 1:1 mixture of monodisperse cubes with a grain size of 0.2 μm and an AgI content of 4.5 mol %) Amount of silver 0.5 g/rrr A fogged fine grain silver iodobromide emulsion (average grain size of 0.06 μm and an AgI content of 0.5 g/rrr) (0.1 mol% of) Silver amount 0.02 g/rrf Coupler C-40, 10 g/Ikabra C-70.10 g/Coupler resistant C-80, lOg/Compound resistant Cpd-B 0.03 g/I Cpd
-E O,Ig/ICpd-F
O,Ig/BaCpd-G
O,05g/rrrCpd-H0,05g/GoOi 1-2 0. 1
cc/rr? Gelatin 0.5g
/ 10th resistant layer: 2nd green-sensitive emulsion layer Silver iodobromide emulsion containing sensitizing dyes S-3 and S-4 (monodisperse cubic with average grain size 0.5 μm and AgI content 3 mol%) Silver amount 0.4g/rri' coupler C-40, lOg/resistance coupler C-70, log/rrl' coupler C-80, 10g/A compound Cpd-8 0.03g/I Cpd-
E O,Ig/rrrCpd-F
O, Ig/rr? c, p d -G Cpd-H 11-2 Gelatin 0.05g/resistant 0.05g/r & 0.1cc/resistant 0.6g/a 11th layer: 3rd green-sensitive emulsion layer sensitizing dye S-3 and Silver iodobromide emulsion contained in S-4 (monodispersed flat plate with an average grain size of 0.6μ in terms of spheres, AgI content 0.6μ, and an average diameter/thickness value of 7) Silver amount 0.5g/Coupler resistance C -40.4g/rr? Coupler C-70, 2g/rd g/Lar C-80, 2g/Compound resistant Cpd-B O, 08g/rdCp
d-E O,Ig/rrrCpd-F
O, Ig/rr+”Cpd-G
O,Ig/GoCpd-HO,Ig/Go0il-20,1cc/Igelatin 12th layer: Intermediate layer dye D-2 Gelatin 1.0g/rd 0.05g/Resistance 0.6g/I 13th layer: Yellow Filter layer Yellow colloidal silver compound Cpd-A Gelatin 14th layer: Intermediate gelatin 15th layer: First blue emulsion layer Silver iodobromide emulsion containing sensitizing dyes S-5 and S-6 (average grain size 0) (1:1 mixture of monodisperse cubes with an average particle size of 0.2μ and 3 mol% AgI content and monodisperse cubes with an average particle size of 0.2μ and 3 mol% AgI content) Silver amount 0.6g/resistant cuff coupler C-50,5 Ikablur C-90,3g/i0.1g/rr? 0.01g/1.1g/0.6g/rrr 0i 1-2 0. 02
cclrd gelatin 0.8g/
A 16th layer: 2nd blue-sensitive emulsion layer Silver iodobromide emulsion containing sensitizing dyes S-5 and S-6 (monodisperse cubic with average grain size 0.5μ and AgI content 2 mol%) Silver amount 0 .4g/Ikabura C
-50,3g/Ikabura-C-60,3g/Oi resistance 1-2 0.01cc/rrr
Gelatin 0.9g/i 17th layer: 3rd blue-sensitive emulsion layer Silver iodobromide emulsion containing sensitizing dyes S-5 and S-6 (average grain size in terms of spheres 0.7μ, AgI content i, s Mol%, flat plate with average diameter/thickness of 7) Silver amount 0.4 g/rrr Coupler C-13o, 7 g/Il-2 resistance 0.01 cc/Igelatin t, 2 g/rn' 18th layer:
First protective layer U-'1 0.04g/Go U-30
．． 03g/Bo U-40,03g/I U-50,05g/Go U-60,05g/rrf Compound Cpd-C0,8g/rr? Dye D-30.05g/rr? Gelatin O, '7g1rd 1st
9th layer: Silver iodobromide emulsion covered with second protective layer (average grain size 0.06 um, AgT content 1 mol%) Silver amount 0.1 g/Igelatin
O,,4g/rri 20th layer: 3rd protective layer polymethyl methacrylate (average particle size 1.5μm) 0.1g/4=6 copolymer of gomethyl methacrylate and acrylic acid (average particle size 1.5μm) ) O, 1g1rd silicone oil 0.03g/IW-13gZr
d Gelatin 0.4 g/rd In addition to the above composition, gelatin hardener H-1 and a surfactant were added to each layer.

-1 H C-CoHC C-gC-t -t -10 -11 Oil-/ CHI -,2 COOC3H, (iso) dibutyl 7-talate etR tricresyl-7 Coupler C-r Coupler C-2 Cpd-Person Q p d -B Cpd-C α Cl) d -E Cpd-H U-G-j U- & S-/ Cpd-D TJ-/ U-CoTJ-J -J -3 S-Hiroshi8-z S-+ -7- 2H5 -10 -11 -1 Example 2 for S03 Color photographic material 2 in which the following 1st to 12th layers were coated in multiple layers on a paper support laminated on both sides with polyethylene.
01 was created. The first layer coating side of the polyethylene contains titanium white as a white pigment and a trace amount of ultramarine as a bluish dye.

(Photosensitive layer composition) The components and coating amounts in g/rrr units are shown below. Regarding silver halide, the coating amount is shown in terms of silver.

1st layer (gelatin layer) Gelatin...1.30 2nd layer
Layer (antihalation layer) Black colloidal silver,...0.10 Gelatin...0.70 Third layer (low sensitivity red sensitive layer) Spectrally sensitized with red sensitizing dye (ExS-1, 2) Silver chloroiodobromide EMI (silver chloride 1 mol%, silver iodide 4 mol%, average grain size 0.3μ, grain size distribution 10%, cubic,
Core tolerance type core shell)...0.06 Silver iodobromide EM2 spectrally sensitized with red sensitizing dye (ExS-1, 2) (silver iodide 5 mol%, average grain size 0.4
5μ, particle size distribution 20%, flat plate (aspect ratio = 5
)) ...0. lO gelatin
...1.00 cyan coupler (ExC-1) ...0.14 cyan coupler (ExC-2) ...0.07
Antifading agent (Cpd-2, 3, 4, 9 equivalent)...
0.12 force puller dispersion medium (Cpd-5)
...0.03 coupler solvent (Solv-1,2,3
) -0,06 4th layer (high sensitivity red-sensitive layer) Silver iodobromide EM3 spectrally sensitized with red sensitizing dye (ExS-1,2) (silver iodide 6 mol%, average grain size 0. 7
5μ, particle size distribution 25%, flat plate (aspect ratio = 8
), core tolerance)) ...0.15 gelatin
...1.00 cyan coupler (ExC-1) ...0,20 cyan coupler (ExC-2) -0,10 antifading agent (Cpd-2, 3, 4, 9 equivalent) ...0 .1
Five force puller dispersion medium (Cpd-5)...
0.03 coupler solvent (Solv-1, 2, 3) 5th
Layer (intermediate layer) Magenta colloid silver gelatin color mixture inhibitor (Cpd-6, 7) Color mixture inhibitor solvent (Solv-4, 5) Polymer latex ((1:PD-8) 6th layer (low sensitivity green sensitive layer) Silver chloroiodobromide EM4 spectrally sensitized with a green sensitizing dye (ExS-4) (1 mol% silver chloride to 2.5 mol% silver iodide, average grain size 0.28μ, grain size distribution 12%, Cubic, core density type core shell) green sensitized color (ExS-3)
Emulsion A spectrally sensitized with 0.04 Silver iodobromide EMS (silver iodide 2.8 mol%, average grain size 0.4) spectrally sensitized with green sensitizing dye (ExS-4)
5μ, particle size distribution 12%, flat plate (aspect ratio = 5
)) ...0.06 gelatin ...0.80 magenta coupler (ExM-1) ...-0,10...
・0.02 ...1.00 ...0.08 ...0.16 ...0.10 ...0.10 Anti-fading agent (Cpd-9) Anti-stinting agent (Cpd-10) Stain inhibitor (Cpd-11) Stain inhibitor (Cpd-12) Coupler dispersion medium (Cpd-5) Coupler solvent (Solv-4, 6) 7th layer (high sensitivity green sensitive layer) Green sensitizing dye (εxS- Silver iodobromide EMS spectrally sensitized with 4) (silver iodide 3.5 mol%, average grain size 0.9
μ, particle size distribution 23%, flat plate (aspect ratio = 9,
0.10 gelatin
...0.80 magenta coupler (ExM-1) -0.10 anti-fading agent (
Cpd-9) ...0. IO stain inhibitor (Cpd-1o) ・0.01 stain inhibitor (Cpd-11) -0°001
Stain inhibitor (Cpd-12)...0
．． 01 force puller dispersion medium (Cpd-5) ・
・・0.05 coupler solvent (Solv-4,6)
・0.15 8th layer (yellow filter layer) ...0. IO...0. Ol...0.001...0.01...0.05...0.15 Yellow colloidal silver gelatin color mixing inhibitor (Cpd-7) Color mixing inhibitor solvent (Solv-4, 5) Polymer latex (Cpd-ill) 9th layer (low sensitivity blue sensitive layer) Silver chloroiodobromide EM7 spectrally sensitized with blue sensitizing dye (ExS-5) (silver chloride 2 mol%, silver iodide 2.5 mol %, average grain size 0.35μ, grain size distribution 8%, cubic, core density type (core shell))...0.07 Silver iodobromide EMS spectrally sensitized with blue sensitizing dye (ExS-5) ( Silver iodide 2.5 mol%, average grain size 0.4
5μ, grain size distribution 16%, flat plate (aspect ratio = 6
)) ...o, i.

Gelatin...0.5゜Yellow coupler (ExY-1) ・=0.
20 Stain inhibitor (Cpd-11) ・0
．． 001 Anti-fading agent (Cpd-6)
・0.10 coupler dispersion medium (Cpd-51-0,05・
...0.20 ...1.00 ...0.06 ...0.15 ...0.10 Coupler solvent (Solv-2) -0,0
5 10th layer (high sensitivity blue sensitive layer) Silver iodobromide EM9 spectrally sensitized with blue sensitizing dye (ExS-5) (silver iodide 2.5 mol%, average grain size 1.2
μ, particle size distribution 21%, flat plate (aspect ratio = 14
)) ...0.25 gelatin
...1.00 Yellow coupler (ExY-1) -0,40 Stain inhibitor (Cpd-11) ...0.002 Anti-fading agent (Cpd-6) ...0.
10 coupler dispersion medium (Cpd-5)...
・0.15 coupler solvent (Solv-2)
-0,10 11th layer (ultraviolet absorbing layer) Gelatin...1.50 Ultraviolet absorber (Cpd-1,3,13) -1,
00 color mixing prevention agent (cpd-6, t4) ・
・・0.06 Dispersion medium (Cpd-5) Ultraviolet absorber solvent (Solv-1, 2) ・0
．． 15 anti-irradiation dye (Cpd-15,16)...
0.02 anti-irradiation dye (Cpd-t7.18)...
0.02 12th layer (protective layer) Fine grain silver chlorobromide (silver chloride 97 mol%, average size 0.2
μ) ...0.07 modified poval ...0.02 gelatin
...1.50 Gelatin hardening agent (H-1) ...0.17 Furthermore, in each layer,
Alkanol X C (Dupont
), and sodium alkylbenzenesulfonate,
Succinic acid ester and Magefac as coating aids
F-120 (manufactured by Dainippon Ink Co., Ltd.) was used. The layer containing silver halide or colloidal silver contains (C
pd-19,20,21 was used. The compounds used in the examples are shown below.

xS-5 o3H Cpd-2 O Cpd-3 xS-1 xS-2 xS-3 xS-4 Cpd-4 Cpd-5 Cpd-6 Cpd-7 Cpd-8 Polyethyl acrylate Cpd-10 Cpd-17 Cpd-18 Cpd-19 Cpd-20 5tJILK+ Cpd-14 Cpd-, 15 Cpd-16 Cpd-21 xC-1 xC-2 H H H C! (Included in U.S. Pat. No. 4.560.635) 5o
lv-1 di(2-ethylhexyl) phthalate xM-1 olv-2 trinonyl phosphate olv-3 di(3-methylhexyl) phthalate olv-4 tricresyl phosphate 01v-5 dibutyl phthalate 0IV-6 trioctyl phosphate-1 1゜2Bis(vinylsulfonylacetamido)ethane (emulsion A) Preparation of a monodisperse emulsion with (Zoo) crystal habit Silver nitrate aqueous solution and KBr were added to a gelatin aqueous solution kept at 70°C while keeping pB and r at 4.5. An aqueous solution containing % KI was added using a double jet to prepare a monodispersed emulsion (100) having a crystal habit (principal diameter: 0.68 μm). Next, this core emulsion was used to form a shell under the following conditions, and the final grain size was adjusted to 0.7.
μm, and the AgI content was 3 mol%.

Chemical sensitization was performed by adding sodium thiosulfate and potassium chloroaurate to the above core. Thereafter, the shell was precipitated under the same conditions as for core formation.

The following process was used for color reproduction evaluation.

Anal plate craftsmanship plate -Development Water washing Reverse exposure color development Water washing bleach fixing Water washing drying Kakiyama [First developer] Nitrilo-N,N,N-)-li Methylenephosphonic acid thorium salt diethylenetriaminepentaacetic acid pentasodium salt potassium sulfite potassium thiocyanate potassium carbonate hydroquinone monosulfo 38℃ 38℃ 500lux or more 38℃ 38℃ 38℃ 38℃ (black and white development) 45 seconds 45 seconds 15 seconds or more 60 seconds 15 seconds 60 seconds 60 seconds 0.6g 4゜ 30° 1゜ 35° 0g 0g 0g g nate potassium salt diethylene glycol 1-phenyl-4-hydroxy dimethyl-4-methyl-3 One pyrazolidone potassium bromide add water [Color developer] triethanolamine N,N-diethylhydroxy Ruamine 3.6-Sythia 1.8-O Cutanediol Ethylenediaminetetraacetic acid di Sodium trihydrate sodium sulfite potassium carbonate N-ethyl-N-(β-meta sulfonamide ethyl)− 25.0g 15.0m1 2.0g 5.0mg 1000Tng (pH9,7) 8.0g 4.0g 0.2g 2.0g 0.2g 25.0g 3-methyl-4-aminoa Niline sulfate potassium bromide potassium iodide add water [Bleach-fix solution 1 2-mercapto-1,3,4 monotriazole Ethylenediaminetetraacetic acid di Sodium trihydrate Ethylenediaminetetraacetic acid/ Fe (III) / Ammonium - water salt sodium sulfite sodium thiosulfate (700g #2 liquid) glacial acetic acid add water 8.0g 0.5g 1, otng 1000m [1 (pH 10,4) 0.5g 5.0g 80.0g 15.0g 160.0 yen 6.0- 1000 yen (pH6.0)

[Brief explanation of drawings]

Figure 1 is a visual isochromatic relative spectral sensitivity distribution diagram, Figure 2 is a chromaticity diagram that reproduces the dominant wavelength of a positive image, and Figure 3 is the relationship between the wavelength of exposed spectral light and the dominant wavelength of color reproduction. This is a graph showing. Diagram 50 50 Spectrum wavelength (nm) 50

Claims (3)

[Claims] (1) Containing at least one layer of yellow couplers on each support, the specific spectral sensitivity range of which is from 400 nm to 5 nm.
A silver halide emulsion layer (BL) spectrally sensitized to have a specific sensitivity between 20 nm and BL, a silver halide emulsion layer containing a magenta coupler and spectrally sensitized so that its specific sensitivity range is between 470 nm and 600 nm. (GL) and cyan coupler, and its specific sensitivity range is from 540 nm to 7.
In a reversal color photographic light-sensitive material each having a silver halide emulsion layer (RL) spectrally sensitized so that the wavelength is between 00 nm and 00 nm;
λ@_G) is between approximately 520 nm and 580 nm,
The centroid sensitivity wavelength (@λ@_R) of the spectral sensitivity distribution of RL is between about 590 nm and 650 nm, and the centroid sensitivity wavelength (@λ@_R) of the spectral sensitivity distribution of BL is between about 430 nm and 480 nm, A reversal color photographic light-sensitive material characterized in that it has a silver halide grain-containing layer adjacent to at least GL or RL and covering the surface and/or inside thereof. (2) The reversal color photographic light-sensitive material according to claim (1), which has at least one silver halide emulsion layer (ICL) that exhibits a multilayer effect during black-and-white negative development and does not substantially form an image dye. (3) The reversal color photographic material according to claim (1) or (2), wherein the ICL contains a compound that exhibits a multilayer effect during color development and does not substantially form an image dye.