JPH02287351A - Silver halide color photosensitive material - Google Patents

Abstract

PURPOSE:To provide high image quality and high sensitivity by incorporating one kind of specific compds. into one emulsion layer sensitive to light of the wavelength longer on the side further from a base viewed from the base. CONSTITUTION:At least one layer of the emulsion layers sensitive to the light of the wavelength longer on the side further from the base viewed from the base are provided and at least one kind of the compds. expressed by formulas I to IV are incorporated into the emulsion layers. In the formulas I to IV, A denotes a group which cleaves (L)n-DYP1 by reacting with the oxidant of a developing agent; L denotes a group to cleave DYP1 or DYP2 respectively after the cleavage from A or PWR; (n) denotes 0 or 1. The DYP1 denotes a dye precursor group which develops a color in the state of being combined with A-(L)n or B1-LVG respectively in the process of a development processing; B1 denotes a group to cleave LVG by reacting with the oxidant of the develop ing agent; LVG denotes an elimination group to combine with the coupling position of B1 is heteroatom. The high sensitivity and the high image quality are obtd. in this way.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a color photosensitive material for photographing with high sensitivity, and particularly to a color photosensitive material for photographing that is suitable for rapid processing and has good storage stability.

(Prior Art) In recent years, due to advances in the technology of light-emitting materials for photography, high-sensitivity photosensitive materials have been released one after another. Expanding the range of photography by increasing the sensitivity of photosensitive materials, such as shooting without a strobe in a dark room, shooting with a high-speed shutter using a telephoto lens for sports photography, and shooting that requires long exposures such as astronomical photography. is an eternal theme for this industry.

Many efforts have been made to increase the sensitivity of photosensitive materials. Numerous studies have been conducted on the shape and composition of silver halide grains, methods of forming them, chemical sensitization, spectral enhancement, additives, coupler structures, etc., and several useful inventions have been made. However, the demands for highly sensitive fluorescent materials are greater than the advances in technology, and unfortunately these methods alone have not been sufficient. Therefore, it has become common practice in the industry to increase the size of silver halide emulsion grains in combination with other techniques to produce high-sensitivity light-sensitive materials in order to increase sensitivity.

Increasing the size of silver halide emulsion grains increases sensitivity to a certain extent, but as long as the silver halide content is kept constant, the number of silver halide emulsion grains inevitably decreases, and therefore the development IQ starting point increases. The major disadvantages are that the number of particles decreases, the graininess becomes thicker, and the IR becomes thicker. In order to compensate for this drawback, British Patent No. 923,045,
A photographic material having two or more emulsion layers having the same color sensitivity and different sensitivities, that is, different silver halide grain sizes, as described in JP-A No. 9-15495, JP-A-55
- Method using fast-reacting couplers as described in Publication Ci2454 etc., U.S. Pat. No. 3,227.5
54, U.S. Pat. No. 3,632,435, etc., methods using so-called DIR couplers or DIR compounds, such as those described in British Patent No. 2,083,640, which yield mobile dyes. method using a coupler,
A method using silver halide having a high average silver iodide content is known, as described in JP-A-60128443. Although each of these methods is a clever invention with great effects, they are not sufficient technologies to meet the demands for high sensitivity and high image quality. Therefore, in order to increase the grain size of the silver halide emulsion grains and at the same time increase the number of development initiation points as much as possible, high-sensitivity color negative light-sensitive materials are manufactured within a range that allows for various performances such as desilvering properties during bleach-fixing processing. Designs have been made to increase the content of silver halide emulsion grains.

On the other hand, it has been known to change the arrangement of the layers of a color photosensitive material consisting of whites in order to increase the sensitivity of the color photosensitive material or to achieve both high sensitivity and high image quality. For example, as in U.S. Pat. Also, as in U.S. Patent No. 4.184.87G, the high-sensitivity layers of the green-sensitive layer and the red-sensitive layer are made into one unit, and the low-sensitivity layers of the green-sensitive layer and the red-sensitive layer are made into separate units. There is one that aims to increase the frequency range by placing the high frequency unit outside the low frequency unit. However, although these techniques have partially achieved their objectives, they still have some deficiencies, and many patents have been filed for the purpose of improving them. West German Patent No. 3,410,639 describes a technology that incorporates the high-sensitivity portion of the blue-sensing layer into a high-sensitivity unit.
．． No. 411,966, European Patent No. 155814, No. 1
24861, JP-A No. 59-177.552, JP-A No. 59180.556, etc. disclose a technique in which a high-sensitivity unit consisting of M, green, and red sensitive layers is combined with other techniques.

Furthermore, in U.S. Patent No. 4,129,446, the positional relationship between the high-sensitivity unit and the yellow filter is disclosed in U.S. Patent No. 4.186,
No. 016 describes the connection between the high-sensitivity unit and the low-sensitivity unit, and No. 4.267.264 describes the relationship between the green-sensing layer and the high-sensitivity red-sensing layer. British Patent No. 1,560,965 , U.S. Patent No. 4. , No. 186.011 defines the intermediate layer.

However, although all of the above-mentioned three techniques and their improvement techniques have partially achieved their objectives, satisfactory performance has not been achieved. In particular, when a part of the red-sensitive layer is placed outside the green-sensitive layer (as viewed from the support), colored couplers cannot be used in the red-sensitive layer placed outside, resulting in poor sensitivity and image quality. It is a trade-off relationship.

(Problems to be Solved by the Invention) The purpose of the present invention is, firstly, to provide a color photosensitive material with high sensitivity, and secondly, to provide a color photosensitive material with high image quality and high sensitivity. The third objective is to provide color photosensitive materials with high sensitivity and high image quality that can be processed quickly, and the fourth objective is to provide color photosensitive materials with high sensitivity that minimize performance deterioration such as increased fog that occurs during storage after production. The goal is to provide materials.

(Means for Solving the Problems) An object of the present invention is to provide a color photosensitive material having a plurality of silver halide emulsion layers having different color sensitivities on a support, on the side farther away from the support. 1. A silver halide color light-sensitive material, characterized in that there is at least one emulsion layer sensitive to longer wavelength light, and the emulsion layer contains at least one compound of the following types (1) to (IV).

-Format (I) A-(L), -DYPI-Format (n
) DY P IB + L V G-format (
I [I) BLK-Bz N=N R-format (I
V) PWR-(L) 1, -Dypz (wherein A reacts with the oxidized developing agent to form (L)).

-DYP represents a group that cleaves, L is A or PWR
represents a group that cleaves D Y P + or DYPZ after cleavage, n represents O or l, and DYP represents A-(L)7 or B+, respectively, during the development process.
B1 represents a dye precursor group that develops color when combined with LVG, and B1 reacts with the oxidized developing agent to form LVG.
LVG represents a group that cleaves B at the heteroatom.
+ represents a leaving group bonded to the campling position, BL
K represents a hydrolyzable group that is cleaved during development, and B2 has -N=N-R at its force/twisting position, and furthermore, it has a conjugated double group that is an even number counting from the carbon atom at the cuff blade position. Represents a group that holds 13LK, which is a group that holds an oxygen atom bonded to a carbon atom constituting a bond, and R is -N=N
- represents a 5- to 8-membered cyclic group having double viscosity that can be conjugated with
represents a group that cleaves fi-DYP2, and DYPZ is P
WR-(L) represents a dye precursor group that develops color in the development process after being cleaved. ) was achieved by

- The compound represented by format (1) will be described in detail below.

In the formula, a preferred example is when DYP flows out into the developer after cleavage and does not substantially remain in the photosensitive material. That is,
The compound represented by the general formula (1) that remains without reacting with the oxidized developing agent is DYP.

A dye for masking can be obtained by developing color in the group represented by . Therefore, the compound represented by the general formula N) is preferably diffusion resistant, and a preferred example is that the diffusion resistant group is included in A or L. During the ceremony,
As the dye precursor group represented by DYPI, those that develop color during the development process, for example, by a complex formation reaction (preferably divalent iron is used as the metal ion), oxidation reaction, or hydrolysis reaction are useful.

That is, DYPI, which develops color through a complex formation reaction, is DYP, which develops color when the ligand is oxidized.

Examples include leuco pigments, DYP, which develops color through hydrolysis,
Examples include dye precursors in which the chromophore or auxochrome is blocked by a hydrolyzable group. -Format (+
), for example, US Pat. No. 4+
555+ No. 477, No. 4, 557, 998, No. 4,749.641, JP-A-62-145243,
Compounds described in Japanese Patent Application No. 63-18636, No. 63-13G71.5, and No. 63-92058 are known.

- In form (1), DYP is preferably bonded to A-(L) at a heteroatom contained therein, preferably an oxygen atom, a sulfur atom or a nitrogen atom.

The compound represented by the -IC formula (TI) will be described in detail below.

The group represented by B reacts with the oxidized developing agent to form LVG.
A preferred example is when, after cleavage, DYP flows out from the photosensitive material into the developing solution in a bonded state with DYP. That is, the compound represented by the general formula (n) that remains without reacting with the oxidized developing agent is DYP.

A masking dye can be obtained by coloring the group shown in the formula during the development process.

The compound represented by the -C formula (II) is preferably diffusion resistant, and the diffusion resistant group is preferably contained in LVG. In the formula, the dye precursor group represented by DYP has the same meaning as explained in the general formula (1). - Compounds of the designation (II) are known, for example, from US Pat. No. 4,764,454.

The group represented by LVG in general formula (b) is preferably bonded to DYP+ B+ at a hetero atom contained therein, such as an oxygen atom, a sulfur atom, or a nitrogen atom.

-a The compound represented by formula (III) will be described in detail below.

In the compound represented by the general formula (III), BLK is cleaved by hydrolysis during the development process, and is represented by 82N=N-R. group is generated. B generated here, -N=N
A preferred example is when -R functions as a normal colored coupler. In addition, in a state where BLK is bound, the maximum absorption wavelength shifts to the short wavelength side, and BLK is cleaved to restore the color to the dye having the original maximum absorption wavelength, which is a preferable example. Since the group represented by N=N-R is located at the cuff ring position of B2, it reacts with the oxidized developing agent, and N=N-11 is cleaved and the color is erased. For example, when B2 is a pyrazolone type coupler, the oxygen atom obtained by removing the hydrogen atom from the hydroxyl group when tautomerized to the enol type is B.
LK combines. Further, when B2 is, for example, a phenol or naphthol type cyan coupler, BLK is bonded to an oxygen atom obtained by removing a hydrogen atom from a hydroxyl group.

-i Compounds represented by formula (III) include, for example, US Pat. No. 4,427,763 or British Patent No. 853.
The compound described in No. 922 is known.

- The compound represented by Monka (IV) will be described in detail below.

In the formula, the group represented by DYP is a group that can develop a color only after being cleaved by PWR or silica. That is, PWR is a group that releases -Dypz when reduced (L), and since this reaction occurs in the undeveloped area, a dye for masking is obtained. Specifically, as DYP, a dye in which an auxochrome is bonded to PWR-(L) is useful. - Compounds represented by Monka (IV) are known, for example, as described in JP-A-62-293243.

-JiR> In formula (1), A specifically represents a coupler residue or a redox group.

The coupler residue represented by A is, for example, a yellow kuffler residue (for example, an IASM ketomethylene type capsicoupler residue such as acylacetanilide or malondianilide) or a zenta coupler residue (for example, a 5-pyrazolone type, pyrazolotriazole type or pyrazoloimidazole). type), cyan coupler residues (e.g. phenol type, naphthol type or European Published Patent Application No. 2)
49453) and colorless coupler residues (eg coupler residues of the indanone type or acetophenone type). Also, US Patent Nos. 4315070 and 41837
52, No. 4174969, No. 3961959, or No. 4171223.

When A represents a redox group, the redox group is a group that can be cross-oxidized by an oxidized developing agent, such as hydroquinones, catechols, pyrogallols, 1.
Examples include 4-naphthohydroquinones, 1,2-naphthohydroquinones, sulvonamidophenols, hydrazides, or sulfonamide naphthols. These groups are specifically described in, for example, JP-A No. 61-230135.
No. 62-2517, No. 16, No. 61-278852
No. 3,364,022, US Pat. No. 3,379,529, US Pat. No. 3,639,417, US Pat. No. 4,684,604 or J,
Org, Chem, 29, 588 (1964).

In general formulas (r) and (1), the linking group represented by is, for example, US Pat.
No. 2516 or No. 4,698,297, a group utilizing the hemisecure cleavage reaction, US Pat. No. 424
8962, a timing group that causes a cleavage reaction using an intramolecular nucleophilic reaction, US Pat. No. 44093
A timing group that causes a cleavage reaction using the electron transfer reaction described in No. 23 or No. 4421845,
A group that causes a cleavage reaction using the hydrolysis reaction of iminoketal described in U.S. Patent No. 4,546,073;
Alternatively, there may be mentioned a group that causes a cleavage reaction using an ester hydrolysis reaction described in West German Published Patent Application No. 2,626,317. (2) is bonded to A or P WR etc. at a petro atom, preferably an oxygen atom, a sulfur atom or a nitrogen atom contained therein.

In the formula, examples of the linking group include a methyleneoxy group, a 4-methylene-3-bilapryloxy group, a 2 (or 4)-methylenephenoxy group, and a 0-(methylene group having 1 to 4 carbon atoms +- A preferred example is a CO- group or a 2-carbonylaminomethylphenoxy group. At these oxygen atoms, it connects to the bond on the left side of the symbol (1) or (IV). Also, to these divalent groups may have a substituent at a substitutable position (for example, on the methylene group or benzene ring), and representative substituents include:
Alkyl groups (e.g. methyl, ethyl, isopropyl, dodecyl), acyl groups (e.g. benzo, acetyl)
, alkoxy) IE (e.g. methoxy, ethoxy), alkoxycarbonyl groups (e.g. methoxycarbonyl, butoxycarbonyl), carbamoyl groups (e.g. ethylcarbamoyl), nitro groups, carboxyl groups, sulfonyl groups (e.g. methanesulfonyl), aryl groups (e.g. 4
-nitrophenyl, 4-carboxyphenyl), a halogen atom (eg, chlorine atom, fluorine atom), or a sulfamoyl group (eg, octadecylsulfamoyl).

In -a formula (1) and -Momonana (n), D Y P
The group represented by l is preferably a ligand or a leuco dye.

As the ligand, those having two or more of the following partial structures are useful.

The heteroatoms of these groups (or their anions) form chelates with metal ions that involve the formation of a 4- or 7-membered ring, preferably a 5- or 6-membered ring. It has a three-dimensional positional relationship.

-N=N- Examples of useful Gants include terpyridines, bipyridines, hydrazones, tetrazolylpyridines, pyridyl; tonazolines, imines, bisisoquinolines,
Phenanthrolines, bidiazines, pyridyldiazines, pyridylbenzimidazoles, phenols, biimidazoles, diacyltriazine II, for O-nitrosoanilines, tetrazines, triazines, oximes, imidaprilpyridines, polypyrroles , and hydroxyanthraquinones. Useful ligands include those having at least two of the above partial structures in the combination of these basic bone cores and substituents on the bone cores.

The above-listed Gantts also include cases where they further have a substituent, and the general formula (N
In formula (II), it bonds with -(L) and %-, and in general formula (II), it bonds with B1.

When DYP represents a leuco dye, it is preferably represented by the symbol (D-1) below.

In the formula, at least one of R+, 8 R,, b R8 and R4 represents a group containing an oxygen atom, a sulfur atom or a nitrogen atom, and in one of the hetero atoms,
A-(L) Binds to fi- or -BlLVG. R+
, nz, R: When l and R4 represent a substituent,
R1 is Ro. 〇- group, R,, S- group, Rr o -N
-a, R+ o CON- group or R11
RI2 is preferably Rho 5, R2 and R3 are each R1
゜〇- group, R1゜S- group, R+zN- group, 1ff R1□C0N- group, halogen atom, Ro. - group, RI R, oSo, N- group, R, O3O□ - group, RIzc.

Group, R, □NG O- group, R+ z N S Oz
- group, cyanoR, 3R13 is a new example.

a and b are integers from O to 4, and when they are 2 or more, a plurality of R2 and R3 each represent the same or different. Also two R2 or two R3
When each represents an adjacent substituent, each represents a divalent group and may be connected to form a ring. At that time, it becomes a benzene condensed ring. Examples include naphthalene rings or quinoline rings. R4 is R1゜S Oz
- group or R1°CO- group.

In the above, R1° and R11 represent an aliphatic group, an aromatic group, or a heterocyclic group, and R32 and RI3 represent an aliphatic group, an aromatic group, a heterocyclic group, or a hydrogen atom. - When a plurality of any of the groups represented by Rho, Rz, R1□ and R1+ are present in the molecule, they represent the same or different groups.

The aliphatic group has 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms,
The aromatic group has 6 to 10 carbon atoms, preferably 6, and the heterocyclic group has 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms.

In general formula (D-1), R1, R2, F'! Either of the groups represented by 3 and R4 is l (L).

Or -B, -t, VC:a bond. That is, one group of Rr, Rz, R3 and R4 has 10-, -S- or -N- at a substitutable position, and A(L), - or - at this petero atom.
A good example is the combination with B, -LVG. Here, RI4 represents R,, CO-, R- or R1°SO-. However, in the case of Rr, Rz and R3, A-(L
) When bonding with n- or -B1-LVG, 10-
-S- or -N- itself may be used.

The group represented by the -IW formula (D-1) preferably has at least one of a carboxyl group, a sulfoxyl group, or a salt thereof (for example, a sodium salt, a potassium salt, or an ammonium salt).

- The group denoted by B in the hole (n) is preferably a coupler residue and has LVG at the coupling position.

DYP, binds to 81 at a position other than the B1 coupling position. B, to finish, first A of general formula (1)
The coupler residues described above are useful examples. LV
G is an aromatic oxy group, an aliphatic oxy group, an aromatic thio group, an aliphatic thio group, or a nitrogen-containing heterocyclic group (e.g., 1-pyrazolyl group, i
2,4-) leadazol-1-yl group, imidapridine-2,4-dione-3-yl group, oxazolidine-
2,4-dione-3-yl group or 1.2.4-1-lyasilydin-3,5-dione-4-yl group) are preferred examples. Particularly preferred examples of these groups include diffusion-resistant groups having 10 to 32 carbon atoms.

The protecting group represented by BLK in the general formula (DI) represents, for example, a hydrolyzable group, and typical examples include an acyl group (such as acetyl, hendiyl, or propanoyl).
, alkoxycarbonyl (e.g. ethoxycarbonyl,
butoxycarbonyl), a sulfonyl group (eg evamethanesulfonyl, butanesulfonyl or benzenesulfonyl) or a carbamoyl group (eg N,N-diethylcarbamoyl).

In the general formula (III), the group represented by 32 is preferably a phenol- or naphthol-type cyan coupler residue whose hydroxyl group is protected by BLK, or a 5-pyrazolone tautomer whose hydroxyl group is protected by BLK.
Represents a pyranduron type coupler residue. Each has -N=N-R at the coupling position. R preferably represents an aromatic group.

The compound represented by the -S formula (IV) is preferably one represented by the following formula (P-1).

-Momona (1"-1) In the above -Momona (P-1), EAG corresponds to the PWR of -Momona (TV). (L), DYP
2 binds to at least one of R21 or EAG.

- The part corresponding to the PWR of the pattern hole (P-1) will be explained. Y is a divalent linking group, preferably -(C=O)
-or -SO□-. X represents an oxygen atom, a sulfur atom or a -N- group. R2 here! represents a substituent, and preferred examples thereof include an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, and a sulfonyl group. EAG represents an electron acceptor group, preferably an aromatic group substituted with an electron withdrawing group. E
A particularly preferred example of AG is an aromatic group having at least one of a nitro group, a sulfonyl group, a sulfamoyl group, an acyl group, a carbamoyl group, or a cyano group as a substituent. R21 represents an atomic group that combines with X and Y to form a 5- to 8-membered monocyclic or condensed heterocycle including a nitrogen atom.

In general formula (P-1), preferably X is oxygen\ represents an atom, and Y represents a C=O group.

Preferably, the heterocycle consisting of EAG express meaning.

In the -a formula (rV), the group represented by DYPt is particularly preferably one represented by the following -Momona (D-2).

(D-2) W-Z, -N=N-Z.

In the formula, the free bond represents a bond bonding to PWR~(L), , W represents an oxygen atom, a sulfur atom, or an imino group, and zl and Z2 each represent an aromatic group or an unsaturated heterocyclic group. represent. Preferred examples of the aromatic group include a substituted or unsubstituted phenyl group or naphthyl group. Further, as the unsaturated heterocyclic group, a 5- to 8-membered, preferably 5- to 6-membered heterocyclic group (eg, pyrazole, pyridine, or benzoxazole) is used.

Specific examples of the compounds represented by the general formula (1), (Il), (III) or (IV) are shown in Table A below.

The silver halide color bright light material of the present invention has a plurality of silver halide emulsion layers having different color sensitivities on a support. There is at least one emulsion layer that is sensitive.

Here, "being confused by light with a longer wavelength" means that the maximum spectral sensitivity is at a longer wavelength.

In the present invention, at least one blue-sensitive silver halide emulsion layer (also referred to as "blue-sensitive emulsion layer") is provided, preferably two or three blue-sensitive silver halide layers having substantially the same color sensitivity. An emulsion layer is preferred. Here, substantially the same color sensitivity means that the sensitivity maximum is 400-500 nm.
This means that the spectral sensitivity distribution is the same or similar. When a plurality of blue-sensitive emulsion layers are provided, it is preferable that the blue-sensitive emulsion layer with relatively high sensitivity is provided on the side far from the support.

Regarding the red-sensitive silver halide emulsion N (hereinafter also referred to as "red-sensitive emulsion layer") and the green-sensitive silver halide emulsion layer (hereinafter also referred to as "green-sensitive emulsion layer J"), "high sensitivity" or "low anger" ” are all relative. The relatively high-sensitivity and relatively blue, green, and red-sensitive layers may be layers that are sensitive to partially different wavelength regions, or may be layers that are sensitive to infrared light or ultraviolet light. The coupler can be selected depending on the purpose.

The present invention is preferably a negative color photosensitive material. For this reason, a transparent flexible support is used as the support.
It is preferable to use a photographic window light material having a specific photographic sensitivity of 320 to 6400, which will be described later.

Specific examples of the arrangement order of each layer in the color photosensitive material of the present invention are listed below, but the present invention is not limited thereto.

(1) Support, low-speed red-sensitive emulsion layer (GL), high-speed blue-sensitive emulsion layer (GL), intermediate layer (IL), low-speed red-sensitive emulsion layer (RL), high-speed blue-sensitive emulsion layer ( RH), yellow filter layer (YF), low-speed blue-sensitive emulsion [(BL)
, high-speed blue-sensitive emulsion layer (BH), protected N (PL) (2) support, GL, IL, RL, R11
, IL.

GH, YF, BL, B Summer I, PL.

(3) Support, OL, IL, RL, IL,
Oh.

These low-sensitivity emulsion layers have a sensitivity difference of 0.1-1.0, preferably 0.2-0, according to the common logarithm of exposure.
．． 7 It is preferable that they are different. Also, as explained later,
The red-sensitive or green-sensitive emulsion layer with high sensitivity or low sensitivity may be further formed into two layers with different sensitivities, and the relative difference in sensitivity in this case is the same as when the emulsion layer is divided into two layers.

Here, the red-sensitive or green-sensitive emulsion layers having different sensitivities, for example high and low two, or high, medium and low, have substantially the same color sensitivity. Substantially the same color sensitivity means that the maximum sensitivity of each emulsion layer is 600 for each of the red-sensitive emulsion layer and the green-sensitive emulsion layer.
-700nm and 500-600nm,
This means that the spectral sensitivity distributions are the same or similar.

In the present invention, it is preferred that the blue-sensitive, green-sensitive and red-sensitive emulsion layers each contain at least one yellow, magenta and cyan coupler.

Furthermore, in the present invention, an emulsion layer having a fourth color sensitivity may be present, and the fourth color sensitivity refers to the above-mentioned IL, R1
(, YF, I3L, BH, PL.

(4) Support, RL, IL, OL, TL, BL.

TL, R1(, IL, GH, IL, BH,
P.L.

(5) Support, GL, IL, RL, IL, BL.

IL, GH, rL, RH, fL, BH, P
L.

(6) Support, RL, IL, OL, IL, RH.

IL, Gll, YF, BL, BH
, P.L.

Although the antihalation layer is omitted in +1) to (61 above), it is usually used at a position between the support and the emulsion layer.An intermediate layer may also be provided between the antihalation layer and the emulsion layer. In addition, in the above structure, only the low-sensitivity layer and the high-sensitivity layer are shown as the emulsion layers, but the low-sensitivity emulsion layer (L), the medium-sensitivity emulsion! (M), and the high-sensitivity emulsion layer (L) It may be composed of two layers having different sensitivities. (1) to (6)
), it is preferable to divide the low-speed emulsion layer into a low-speed emulsion layer and a medium-speed emulsion layer.

There may be only one blue-sensitive layer. Japanese Unexamined Patent Publication No. 59-16
As in No. 01.35, between two emulsion layers having substantially the same color sensitivity but different sensitivities, adjacent to the emulsion layer, a substantial grain size of 0.05 to 0.6 μm is provided. A light-reflecting layer (Ref) is provided under the high-sensitivity layer, such as a non-photosensitive silver halide grain-containing layer, for example, BL, B
A configuration such as M, Ref, and BH may be used. Tabular grains are preferably used in the reflective layer. A non-light-sensitive fine grain emulsion layer may be provided in a non-light-sensitive intermediate layer adjacent to the high-speed layer in order to accelerate the development of the high-speed layer. As a fine grain emulsion for promoting this phenomenon, it is recommended that the silver iodide content is not high (
For example, silver iodobromide (for example, 2 mol % or less), silver chlorobromide, etc. can be preferably used. The medium-sensitivity layer may be adjacent to the low-sensitivity layer or may be adjacent to the high-sensitivity layer.

An intermediate layer separating emulsion layers of the same color sensitivity (e.g. GL, GM
, IL, and GH) may contain a compound (so-called scavenger) that captures the oxidized form of the developing agent.

Further, an emulsion may be added to this layer to form a four-layer structure; the protective layer PL may be one layer, or may have a thickness of 21W or more. Among these, the outermost layer preferably contains a matting agent. When oil droplets are included to adjust film physical properties, a structure of two or more layers is preferred, and the outermost layer preferably has a smaller oil droplet/binder (weight ratio) than the inner adjacent layer. For the protective layer and the various intermediate layers mentioned above, JP-A No. 61-437
No. 48, No. 59-113438, No. 59-11344
It may contain couplers and DIR compounds as described in No. 0, No. 61-20037, and No. 61-20038.

Compounds (I) to (rV) of the present invention can be added to various emulsion layers and intermediate layers depending on the purpose.

For example, when the purpose is to correct yellow sub-absorption in a magenta color image, it is preferable to add the yellow coloring compound of the present invention to a layer forming a magenta color image (usually a green-sensitive layer). At this time, it may be added not only to the emulsion layer but also to the adjacent intermediate layer. In order to correct magenta sub-absorption and yellow sub-absorption in a cyan image, it is preferable to add the compound of the present invention that develops magenta or yellow color to the layer forming the cyan image.

Further, when emphasizing the interlayer effect, the additive layer can be selected depending on the purpose. Which of the low-speed to high-speed emulsion layers to use depends on the degree of sub-absorption of the chromophoric dye by the coupler used in that layer and the rate of reaction. The amount of the main coupler may be distributed to the two or three layers in proportion to the amount of the main coupler, or may be distributed in accordance with the rate of the cleavage reaction. If the rate of reaction is slower than that of the main coupler, it can be used more in the high-speed layer, and vice versa, it can be used more in the low-speed layer and omitted from the high-speed layer.

Compounds (1) to (IV) of the present invention may be used after being emulsified and dispersed together with a highly oil-soluble organic compound such as another coupler in the additive layer, or may be used alone. The amount used is 30% of the total coupler in the color-sensitive emulsion layer used.
It is preferably mol % or less, preferably 2 to 25%.

The photosensitive material of the present invention has a specific photographic sensitivity of 320 or more,
And all contained in the photosensitive material! j! The amount is 3.
It is preferable to set it as 0-13.0g/m.

When the specific photographic sensitivity is 320 or less, it is not necessary to adopt the layer structure as in the present invention. Furthermore, if the silver amount is 13 g/m or more, bleaching takes time and it is difficult to shorten the desilvering process.

Specific photographic sensitivity is the JIS standard that measures RSO sensitivity.
Photographic sensitivity obtained by a method according to K 7614-1981, which is obtained 1 hour after exposing a photosensitive material for sensitometry without leaving it for 5 days, using Fuji Photo Film's negative processing prescription CN. -16 photographic sensitivity obtained through development processing. The reason for shortening the number of days specified in the JIS test method is to obtain results quickly, and the development process is specified as specified by each company.

The details of the test method for measuring this specific photographic sensitivity can be found in Japanese Patent Application Laid-Open No. 1983-226650 (Japanese Patent Application No. 1983-226650).
Patent application 1986- claiming priority based on No. 201756
159115), page (4) [page 440] From the upper left column (
Page 6) [page 442] It is written in the upper right column.

Several methods are known for analyzing the silver content of photosensitive materials, and any method may be used. For example, elemental analysis using fluorescent X-rays is convenient.

When the specific photographic sensitivity of the color photosensitive material of the present invention is lower than 320, the effect of the combination of the arrangement order of the layers of the multilayer color negative photosensitive material of the present invention and the amount of silver contained is not very effective. It is. Preferably it is 400 or more, more preferably 800 or more.

Any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride may be used as silver halide in the photographic emulsion layer of the silver halide photographic light-sensitive material of the present invention. A preferred silver halide is silver iodobromide containing up to 30 mole percent silver iodide. Particularly preferred is silver iodobromide containing from 2 mol % to 20 mol % silver iodide. In addition, in order to achieve both high sensitivity and high image quality, the average silver iodide content of silver halide in all emulsion layers must be 8 mol% or more, as described in JP-A-60-128,443. It is preferable to

It is known that graininess is significantly improved by increasing the average silver iodide content of silver halide, but if the silver iodide content exceeds a certain level, development speed may be delayed, desilvering, and fixing speed may be reduced. There are drawbacks such as delays.

However, in the present invention, even if the silver iodide content is increased, these drawbacks hardly become a problem, which is very preferable.

The silver halide grains used in the photographic emulsion layer of the silver halide photographic light-sensitive material of the present invention include a core consisting essentially of iodobromide containing 5 mol% or more of silver iodide, and a core that is coated with iodobromide and contains 5 mol% or more of silver iodide. It is preferred to have a double structure constituted by a shell consisting essentially of iodobromide or silver bromide, the silver iodide content of which is lower than the silver iodide content of the core. The silver iodide content of the core is more preferably 10 mol% or more, and most preferably 20 mol% or more and 44 mol% or less.

The silver iodide content of the shell is preferably 5 mol% or less.

The core may contain silver iodide uniformly, or may have a multilayer structure consisting of phases having different silver iodide contents. In the latter case, the silver iodide content of the phase with the highest silver iodide content is 5 mol% or more, more preferably 10
% by mole or more, and the silver iodide content of the shell is lower than that of the highest silver iodide content phase of the core. or,
"Substantially composed of silver iodobromide" means that it is mainly composed of silver iodobromide, but may also contain up to about 1 mol% of other components (for example, silver chloride). do.

In a further preferred embodiment of the silver halide grains used in the photographic emulsion layer of the silver halide photographic light-sensitive material of the present invention, the silver halide grains have a diffraction angle (2θ) in the range of 38 to 42'', and the silver halide grains are When we obtain a curve of diffraction intensity versus diffraction angle for the (220) plane of The particles have a structure such that the diffraction intensity corresponding to the core portion is 1/10 to 3/1 of that of the shell portion. Particularly preferably, the diffraction intensity ratio is 115 to 3/1, and more preferably 1/3. This is the case of ~3/1.

Such a double structure makes it possible to use a high-iodine silver iodobromide emulsion without causing a delay in development speed, and it is possible to achieve a photosensitive material with excellent graininess even with a small amount of coated silver. I can do it.

The average grain size of the silver halide grains in a photographic emulsion (grain diameter for spherical or near-spherical grains).

In the case of cubic particles, the stack is taken as the particle size, and the projected area is also expressed as an average. ) is not particularly important, but 0.05
The thickness is preferably 10 μm or more. The average size of silver halide grains in the emulsion layer with each highest degree of anger is 0.5
The range is preferably 0.6 μm or more, 2.
More preferably, the thickness is 5 μm or less.

The particle size distribution may be narrow or wide.

The silver halide grains in the photographic emulsion may have a regular crystalline structure such as a cube or a hexagonal, or may have a spherical or hexagonal shape.
It may have an irregular crystalline shape such as a plate shape, or it may have a composite shape of these crystalline shapes. It may also consist of a mixture of particles of various crystalline forms.

Further, it is preferable to use tabular grains having a high efficiency of color enhancement by sensitizing dyes and having an aspect ratio of 5 or more.

Tabular grains are described by Gutoff, Phetographic Science and Engineering (Gutoff).

Photographic 5science and
Engineering)% Volume 14, 248-25
7 pages (1970); U.S. Patent Nos. 4,434,226, 4,414,310, 4,433,048,
4,439.520 and British Patent No. 2,112.
It can be easily prepared by the method described in No. 157 and the like.

The photographic emulsion used in the present invention is P, Glarkide.
Written by Chimie et Physique Photo
ographique (Published by Pau1Monte1,
(1967), Photo by G.F. Duffin
graphig E+++ulsion Chemis
try (The Focal Press, 1966
Making and Coating Photo by V. L. Zelikman et al.
rapic Emulsion (The Focal
Press, 1964). That is, acidic method, neutral method,
Any method such as ammonia method may be used, and methods for reacting soluble root salts with soluble halogen salts include one-sided mixing method,
Either a simultaneous mixing method or a combination thereof may be used.

It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method).

As one type of simultaneous mixing method, a method in which pl'1g in the liquid phase in which silver halide is produced can be kept constant, that is, a so-called Chondrald double jet method can also be used. According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained.

Two or more silver halide emulsions formed separately may be mixed and used in one emulsion layer.

The silver halide emulsion used in the present invention has a crystal plane defined by the Miller index (nnl) (n≧2, n is a natural number) on the outer surface as described in Publication No. 9186-9598. Silver halide grains are preferably used.

Also preferably used is a silver halide emulsion having a hollow conductive portion from the surface toward the inside, as described in JP-A-61-75337. Such a silver halide emulsion having a large specific surface area is more effective when combined with the present invention because it is easier to achieve sensitivity than an emulsion having the same volume, especially when color sensitized.

Also, JP-A-57-133540, JP-A No. 5B-1085
Composite grains in which silver salts having different compositions are epitaxially grown on host grains as described in No. 26 or No. 59-162540 can be preferably used in the present invention. Since such particles exhibit photographic properties with high sensitivity and high contrast, they are preferably used in combination with the present invention.

Also, JP-A-61-14630 and JP-A-60-122
The silver halide emulsion grown in the presence of tetrazaindene as described in No. 935 has a high silver iodide content and excellent monodispersity, so it exhibits high sensitivity and excellent graininess. It is preferably used as a silver halide emulsion.

Also, as shown in Japanese Patent Application Laid-Open No. 58-126526,
A silver halide emulsion subjected to gold sulfur sensitization or gold selenium sensitization in the presence of a nitrogen-containing heterocyclic compound exhibits low fog and high sensitivity, and is therefore preferably used as the silver halide emulsion used in the present invention.

Also, JP-A-59-149345 or JP-A No. 59-1
The slightly rounded cubic or tetradecahedral crystals described in No. 49344 are preferred as silver halide emulsions for use in the present invention because of their high sensitivity performance.

In the process of silver halide grain formation or physical ripening, cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or complex salts thereof, rhodium salts or complex salts thereof, iron salts or complex salts thereof, etc. may be allowed to coexist.

Among these, silver halide emulsions whose grains are formed in the coexistence of iridium are highly sensitive (Japanese Patent Publication No. 43-49
No. 35, Japanese Patent Publication No. 45-32738) is particularly preferred as the silver halide emulsion used in the present invention.

After the emulsion is precipitated or physically ripened, soluble salts are usually removed. For this purpose, the long-known Tardel water washing method, which involves gelling gelatin, may be used. Inorganic salts such as sodium sulfate, anionic surfactants, anionic polymers (e.g. polystyrene sulfonic acid), or gelatin derivatives (e.g. aliphatic acylated gelatin, aromatic acylated gelatin, aromatic carbamoylated gelatin, etc.) A flocculation method may also be used.

Silver halide emulsions are usually chemically sensitized.

For chemical sensitization, for example H, Fr1eser 11
5 “DieGrundlagender Photo5
raphischen r”rozesse mitS
ilber-halogeniden” (Akad
emischeVerlagsgesellchaft
, 1968), pages 675-734, can be used.

Namely, sulfur sensitization using active gelatin and sulfur-containing compounds that can react with silver (e.g., thiosulfates, thioureas, mercapto compounds, rhodanines); reducing substances (e.g., stannous salts); , amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds); noble metal compounds (e.g., complex salts of metals of group II of the periodic table, such as gold complex salts and Pt, rr+ Pd, etc.); The exacerbation method and the like can be used alone or in combination.

Further, it is preferable to use a selenium enhancement method using a selenium-containing compound capable of reacting with active gelatin or silver in combination with other sensitization methods because a highly sensitive emulsion can be obtained. This technique is described in U.S. Pat. No. 1.574.944, 1,602.
No. 592, No. L623,499, Special Publication No. 523840
No. 8, Special Publication No. 57-22090, Japanese Patent Publication No. 59-180
No. 536, U.S. Patent No. 4,565.778, JP-A No. 5
It is described in No. 9-185329, Japanese Patent Application Laid-Open No. 150046/1980, etc.

The photographic emulsion used in the present invention is spectrally sensitized with methine dyes and other dyes, if necessary. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. That is, pyrroline nucleus, oxapurine nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and these A nucleus in which an aromatic hydrocarbon ring is fused to the nucleus of Thiazole nuclei, quinoline nuclei, etc. can be applied. These nuclei may be substituted on carbon atoms.

Merocyanine dyes or complex merocyanine dyes include a pyrazolin-5-one nucleus, a thiohydantoin nucleus, and a 2-thioxazolindine-
2,4-dione nucleus, thiazolidine-2,4-dione nucleus,
5-6R heterocyclic nuclei such as rhodanine nuclei and thiobarbic acid nuclei can be applied.

Useful sensitizing dyes include, for example, German Patent No. 929.0
No. 80, U.S. Patent No. 2,231.658, U.S. Patent No. 2,493
, No. 748, No. 2,503.776, No. 2,519.
No. 001, No. 2,912.329, No. 3,656.9
No. 59, No. 3,672.897, No. 3,694.21
No. 7, No. 4,025,349, No. 4.046.572
No., British Patent No. L242,588, Special Publication No. 1977-140
Examples include those described in No. 30 and No. 52-24844.

These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization.

Typical examples are U.S. Pat. Nos. 2,688,545 and 2,9
No. 77.229, No. 3,397.060, No. 3.52
No. 2.052, No. 3,527.641, No. 3,617
, No. 293, No. 3,628,964, No. 3,666.
No. 480, No. 3,672,898, No. 3,679,4
No. 28, No. 3,703,377, No. 3,769,30
No. 1, No. 3,814,609, No. 3,837.862
No. 4,026,707, British Patent No. 1,344.2
No. 81, No. 1.507, 803, Special Publication No. 43-493
No. 6, No. 53-12375, JP-A No. 52-11061
No. 8, No. 52-109925.

Along with the sensitizing dye, it is a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light,
A substance exhibiting supersensitization may also be included in the emulsion. for example,
Aminostyl compounds substituted with nitrogen-containing heterocyclic groups (for example, U.S. Pat. No. 2,933,390, U.S. Pat. No. 3,635,7)
21), aromatic organic acid formaldehyde condensates (such as those described in US Pat. No. 3,743.510), cadmium salts, azaindene compounds, and the like.

U.S. Patent No. 3,615,613, U.S. Patent No. 3,615,641
The combinations described in No. 3,617,295 and No. 3,635,721 are particularly useful.

Photographic additives that can be used in the present invention include Research Disclosure N [No. 117643 and No. 111a 18
No. 716, and the relevant parts are summarized in the table below.

Additive type 1 Chemical sensitizer 2 Sensitivity enhancer 4 Brightener 9 Hardener 10 Binder 11 Plasticizer, lubricant prevention agent RD17643 Page 23 RD18716 Page 648 Right column Same as above Page 24 Page 26 Page 26 Page 27 Page 651 Left Column Same as above, page 650, right column In addition, in order to prevent deterioration of photographic performance due to formaldehyde gas, it is fixed by reacting with formaldehyde as described in U.S. Patent Nos. 4,411,987 and 4,435,503. It is preferable to add a compound that can be converted into a photosensitive material.

Various color couplers can be used in the present invention, specific examples of which can be found in the above-mentioned Research Disclosure (
RD) No. 17643, ■-〇-G.

As a yellow coupler, for example, U.S. Patent No. 3,93
3.501, same No. 4,022,620, same No. 4,3
No. 26,024, No. 4,401.752, No. 4,2
48.961, Japanese Patent Publication No. 58-10739, British Patent No. 1,425,020, British Patent No. 1.476.760,
U.S. Patent No. 3,973,968, U.S. Patent No. 4.314,0
No. 23, No. 4,511.649, European Patent No. 249
, No. 473 A, etc. are preferred.

As magenta couplers, 5-pyrazolone and pyrazoloazole compounds are preferred, and US Pat.
No. 0,619, European Patent No. 4,351.897, European Patent No. 73.636, US Patent No. 3.061.432, European Patent No. 3.725,067, Research Disclosure No. 24220 (June 1984) month), JP-A-60-3
No. 3552, Research Disclosure N1124
230 (June 1984), JP-A-60-43659, JP-A No. 61-72238, JP-A No. 60-35730, JP-A No. 5
Particularly preferred are those described in US Pat. No. 5-118034, US Patent No. 60-185951, US Pat.

Cyan couplers include phenolic and naphthol couplers, and are disclosed in U.S. Patent No. 4.052.212.
No. 4.146.396, No. 4.228.23
No. 3, No. 4,296,200, No. 2,369,9
No. 29, No. 2.801.171, No. 2.772.
No. 162, No. 2,895,826, No. 3.772
, No. 002, No. 3,758.308, No. 4.33
No. 4,011, No. 4.327.173, West German Patent Publication No. 3,329.729, European Patent No. 121,365
No. A, No. 249.453A, U.S. Patent No. 3,446
．． No. 622, No. 4.333.999, No. 4,45
No. 1,559, No. 4.427.767, No. 4.6
No. 90.889, No. 4.254.212, No. 4.
296.199, JP-A No. 61-42658, etc. are preferred.

Colored couplers for correcting unnecessary absorption of coloring dyes are available at Research Disclosure Floor 17643.
- Section G, U.S. Patent No. 4,163,670, Special Publication No. 1983
-39413, U.S. Patent No. 4,004,929, U.S. Patent No. 4.138.258, British Patent No. 1.146.36
No. 8, and may be used in combination with the compounds of the present invention.

Couplers whose colored dyes have appropriate diffusivity include U.S. Patent No. 4,366.237 and British Patent No. 2,125.
．． 570, European Patent No. 96,570, and German Patent Publication No. 3.234,533 are preferred.

Typical examples of polymerized dye-forming couplers are U.S. Pat.
No. 4,576.910, British Patent No. 2.102
．． It is described in No. 173, etc.

Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. DIR couplers that release development inhibitors include the aforementioned RD17643.
, Patent described in Section ■-F, JP-A-57-15194
No. 4, No. 57-154234, No. 60-184.24
No. 8, No. 63-37346, U.S. Patent No. 4,248,
The one described in No. 962 is preferred.

As a coupler that releases a nucleating agent or a development accelerator imagewise during development, British Patent No. 2.097.140;
No. 2.131.188, JP 59-157638
No. 59-170840 is preferred.

Other couplers that can be used in the light-sensitive material of the present invention include competitive couplers described in U.S. Pat. No. 4,130.427, U.S. Pat. , DTP redox compound releasing couplers or DIR coupler releasing couplers described in JP-A-60-185950, JP-A-6224252, JP-A-62-291645, etc. or DIR coupler-releasing redox compounds or DIR redox compound-releasing redox compounds, couplers that release dyes that recolor after separation as described in EP 173.302 A, R, D, NC
L11449, 24241, JP-A-61-20124
Bleach accelerator releasing coupler described in US Pat. No. 7, etc., U.S. Pat.
．． Examples include ligand-releasing couplers described in No. 553,477 and the like.

Table A lists specific examples of color couplers that can be used in the present invention, but is not limited thereto.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods.

Examples of high boiling point solvents used in the oil-in-water dispersion method are described in U.S. Pat. No. 2,322.027 and the like.

Specific examples of high-boiling organic solvents with a boiling point of 175°C or higher at normal pressure used in the oil-in-water dispersion method include phthalic acid esters (e.g., dibutyl tucrate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate). , decyl phthalate, bis(2゜4-di-t-amylphenyl)
Phthalate, bis(2,4-di-t-amylphenyl)
isophthalate, bis(1,1-diethylpropyl) phthalate), esters of phosphoric or phosphonic acids (e.g. triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl) phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di2-ethylhexylphenyl phosphonate)
, benzoic acid esters (e.g. 2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate), amides (e.g. N
, N-diethyldodecanamide, N,N-diethyllaurylamide, N-tetradecylpyrrolidone), alcohols or phenols (e.g. isostearyl alcohol, 2,4-di-t-amylphenol), aliphatic carboxylic acid esters l (e.g. bis(2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate), aniline derivatives (e.g. N,N-dibutyl-2-butoxy-5-octylaniline) ), hydrocarbons (eg, paraffin, dodecylbenzene, chlorine, soprovilnaphthalene), and the like. Further, as an auxiliary solvent, the melting point is about 30°C or higher, preferably 50°C.
Any organic solvent having a temperature above about 160° C. or below can be used, and typical examples thereof include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide, and the like.

Specific examples of latex dispersion processes, effects, and latex for impregnation are described in U.S. Pat. No. 4,199,363, OLS No. 2,54L274 and
, No. 541, 230, etc.

The present invention can be applied to various color photosensitive materials. Typical examples include color negative film for general use or movies, and color reversal film for slides or television.

Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D, page 28 of 11kL17643, and Arashi 1871
6, from the right column on page 647 to the left column on page 648.

The color photographic material according to the present invention includes the above-mentioned RD, N
28-29 summer of 1117643 and the same day 18716
However, it can be developed by the usual methods described in the left column to right column of 651.

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-
Examples include β-methoxyethylaniline and their sulfates, hydrochlorides, and p-)luenesulfonates. Two or more of these compounds can be used in combination depending on the purpose.

The color developer may contain pH buffering agents such as alkali metal carbonates, borates or phosphates, bromide salts, iodide salts,
It is common to include developer 1 printing agents or antifoggants such as benzimidazoles, benzothiazoles or mercapto compounds. In addition, as necessary, various types of compounds such as hydroxylamine, diethyl hydroxyl amine, sulfite hydrazines, phenyl semicarbazides, triethanolamine, catechol sulfonic acids, and triethylenediamine (1,4-diazabicyclo[22,2]octane) may be added. Preservatives, organic solvents such as ethylene glycol and diethylene glycol, development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts, amines, fogging agents such as dye-forming couplers, competitive couplers sodium boron hydride, Auxiliary developing agents such as 1-phenyl-3-birapritone, viscosity-imparting agents, various chelating agents such as aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, and phosphonocarboxylic acids, such as ethylenediaminetetra Acetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,
1-didiphosphonic acid, nitrilo-N,N,N-trimethylenephosphonic acid, ethylenediamine-N,N.

Representative examples include N',N'-tetramethylenephosphonic acid, ethylene glycol (0-hydroxyphenylacetic acid), and salts thereof.

Further, when performing reversal processing, black and white development is usually performed and then color development is performed. In this black and white developer, known black and white developing agents such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as -phenyl-3-pyrazolidone, or aminophenols such as N-methyl-p-aminophenol are used alone or It can be used in combination with AM.

The pH of these color developing solutions and black and white developing solutions is generally 9 to I2. The amount of replenishment of these developing solutions depends on the color photographic light-sensitive material being processed, but it is generally less than 3β per square meter of light-sensitive material, and by reducing the bromide ion concentration in the replenisher, it can be increased to 50 Qm.
It can also be less than ff. When reducing the amount of replenishment, it is preferable to reduce the area of contact with the air in the processing tank to prevent shading of the liquid and air oxidation. Furthermore, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developer.

Example 1 On a subbed cellulose triacetate film support,
Sample 101, which is a multilayer color light-sensitive material consisting of each layer having the composition shown below, was prepared.

(Composition of photosensitive layer) The unit of coating amount is "g/m".However, silver halide,
The colloid content is expressed in units of g/d of silver, and the sensitizing dye is expressed in moles per mole of silver halide in the same layer.

1st N = antihalation layer black colloidal silver silver coating amount 0.2 gelatin 2.2 u v -t
o, iUV-2 Cpd-I olv-1 olv-2 olv-3 2nd layer: Intermediate layer 0.2 0.05 0.01 0.0I O2O3 Fine particle silver bromide (equivalent sphere diameter 0.07μ) Silver coating i 0.15 Gelatin 1. OCp d -2
0,2 3rd layer: Low-sensitivity red-sensitive emulsion layer Silver iodobromide emulsion (Agl IQ, 0 mol%, internal high Ag
L-type, equivalent sphere diameter 0.8μ, coefficient of variation of equivalent sphere diameter 14%, 14% dodecahedral grain) Silver coated l O,52 Silver iodobromide emulsion (Agl 4.0 mol%, internal height Agl
type, equivalent sphere diameter 0.5 μ, coefficient of variation of equivalent sphere diameter 22%, tetradecahedral grain) xS-3 xS-4 xC-3 xC-4 xC-6 olv-2 5th layer: High-sensitivity red-sensitive emulsion layer Silver iodobromide emulsion (Agr 10.0 mol%, internal high Ag
L-type, equivalent sphere diameter 1.5μ, coefficient of variation of equivalent sphere diameter 28%, plate-shaped particles, diameter/thickness ratio 6.0) Silver coating amount 0.3xlQ-'0.3X10-' 0.05 0.10 0.08 0.12 0.9 0.6 2X10-'0.6xlO-'0.2X10-' 0.07 0.06 0.12 0.12 Gelatin xS-I xS-2 xS-3 xC-4 xC-5 olv-I 0IV-2 Silver coating amount 0.4 1.5 4.5XIO-'mol 1.5X10-'mol 0.4X10-'mol 0.3X10-'mol 0.33 0.01 0. 023 0.14 0.2 Gelatin xS-1 xS-2 xS-3 xS-4 xC-1 xC-2 xC-3 xC-6 olv-1 4th layer: Medium-sensitivity red-sensitive emulsion layer Silver iodobromide emulsion (Ag1 16 mol%, internal high Agl type, equivalent sphere diameter 1.0μ, coefficient of variation of equivalent sphere diameter 25%, plate-shaped particles, diameter/thickness ratio 4.0) Silver coating amount 0.8 1.2 3X10- ' I X 1 0-' Gelatin xS-1 xS-2 6th N: Intermediate layer gelatin 1. OCp d -4
0,1 7th layer: Low-sensitivity green-sensitive emulsion layer Silver iodobromide emulsion (Agl 10.0 mol% internal high Agl
type, equivalent sphere diameter 0.7μ, coefficient of variation of equivalent sphere diameter 14%, 14%, tetradecahedral grains) Silver coating amount 0.2 Silver iodobromide emulsion (Agl 4.0 mol% internal high Agr type, equivalent sphere diameter 0. 4 μ, coefficient of variation of equivalent sphere diameter 22%, tetradecahedral particles) Gelatin F, x S -5 x S-6 x S-7 x M-I x M-5 Silver coating amount 0.1 1.2 5X10-'2X10-' I X 1 0-' 0.21 0.17 ExM-20,10 ExM-30,02 Solv-10,2 Solv-50,03 8th layer: Medium-sensitivity green-sensitive emulsion layer Silver iodobromide emulsion (Agl 10 mol %, internal high iodine type, equivalent sphere diameter 0.85μ, coefficient of variation of equivalent sphere diameter 25%, plate-shaped particles, diameter/thickness ratio 3.0) Coating amount per 1.7 0.7 3.5X10-'1.4X10-' 0,7 5 9th layer: Intermediate layer gelatin 0.5 10th layer: High-sensitivity green-sensitive emulsion layer Silver iodobromide emulsion (Ag1 10.0 mol%, internal high Agl
Mold, equivalent sphere diameter 1.2μ, coefficient of variation of equivalent sphere diameter 28%, plate-shaped particles, diameter/thickness ratio 6.0) Silver coating amount 1.0 0.8 2× 10 0.8x10 0.8xlF' 0 .01 0.04 0.005 0.2 Gelatin xS-5 xS-6 xS-7 ExM-3 ExM-4 xC-4 olv-f 11th layer: Yellow filter layer pd-3 Gelatin olv-1 0,05 0,5 0,1 121st: Intermediate layer latin 0.5Cp d -2
0,1 Thirteenth stone: Low-frequency blue-sensitive emulsion layer Silver iodobromide emulsion (Ag1 10 mol%, internal high iodine type, equivalent sphere diameter 0.7μ, coefficient of variation of equivalent sphere diameter 14%, tetradecahedral grains) i-coating 10.1 Silver iodobromide emulsion (Ag1 4.0 mol%, internal high iodine type, equivalent sphere diameter 0.4 μ, coefficient of variation of equivalent sphere diameter 22%, 14-hedral grains) Gelatin X5-8 xY- I xY-2 o1v-1 Coating amount 0.05 1,0 3X10-' 0.53 0.02 0.15 14th layer: Medium-sensitivity blue-sensitive emulsion layer Silver iodobromide emulsion (Ag1 19.0 mol %, internal high Agl
Mold, equivalent sphere diameter 1.0 μ, coefficient of variation of equivalent sphere diameter 16%, tetradecahedral particles) Silver coating amount 0.19 0, 3 2X10-' 0.22 0.07 Gelatin xS-8 xY-1 o1v-1 15th layer: Intermediate layer fine grain silver iodobromide (Agr 2 mol%, uniform type, equivalent sphere diameter 0.13μ) vA coating amount 0.2 Gelatin 0.36 16th layer: High-strength blue emulsion layer Iodobromide layer Silver oxide emulsion (Agl 14.0 mol%, internal high Agl
Mold, equivalent sphere diameter 1.5 μ, coefficient of variation of equivalent sphere diameter 28%, plate-like particles, diameter/thickness ratio 5.0) Silver coating ■ Gelatin xS-8 xY-1 Solv-1 17th layer: 1st protection Layer gelatin V-1 V-2 Solv-1 Solv-'1 18N=Second protective layer fine grain silver iodobromide (equivalent sphere diameter o).

Silver coating amount gelatin polymethyl methacrylate particles (1.5μm in diameter) 1.0 0.5 1.5X10-' 0.2 0.07 1.8 0.1 0, 2 0.01 o,oi 7μ) 0.18 0.7 0.2 0.02 0, 4 1, 0 -I F(-I pd-5 The structural formulas of the compounds used are shown in Table 8.

Sample 102 with the following composition was prepared by replacing the red-sensitive layer and green-sensitive layer of sample 101 and changing the emulsion. Sample 10
Sample No. 3 was made in the same manner as Sample No. 102 except that ExC-3 of Sample No. 102 was removed.

Samples 101 to 103 have a constant amount of coated silver.

1st layer: antihalation layer black colloidal silver Silver coating amount 0.2 gelatin
2.2UV-10,1 UV-20,2 Cp d-10,05 Solv-10,01 Solv-20,01 Solv-30,08 2nd N: Intermediate layer fine grain silver bromide (equivalent sphere diameter 0.07 μm ) Silver coating! It
0.15 Gelatin 1. OCp d -2
0,2 3rd layer: Low-sensitivity green-sensitive emulsion layer (CL) Silver iodobromide emulsion (Ag1 10.0 mol%) Internal high Agl
Type, equivalent sphere diameter 0.8 μm, coefficient of variation of equivalent sphere diameter 28%,
Plate grains, diameter/thickness ratio 3.0) Silver coating amount 0.2 Silver iodobromide emulsion (Ag1 6.0 mol%, internal high Agl
Type, equivalent sphere diameter 0.5 μm, coefficient of variation of equivalent sphere diameter 26%,
Plate-shaped particles, diameter/thickness ratio 3.0) Silver coating amount 0.1 1.2 5XlO-'mol 2XIO-'mol lXl0-'mol 0.21 0.10 0.17 0.02 0.2 Gelatin xS -5 xS-6 xS-7 xM-I xM-2 xM-5 xM-3 Solv-1 Solv-50,03 4th layer: medium-sensitivity green-sensitive emulsion layer (GM) Silver iodobromide emulsion <Ag1 10. 0 mol%, internal high iodine type, equivalent sphere diameter 1.0 μm, coefficient of variation of equivalent sphere diameter 28%,
Plate-shaped particles, diameter/thickness ratio 3.0) Silver coating amount 0.7 0.7 3.5X10-'mol 1.4XIO-'mol 0.7X10-'mol 0.09 0.09 0.03 0, Engineering 5 0.03 Gelatin xS-5 xS-6 xS-7 xM-1 xM-5 xM-3 Solv-1 o1v-5 5th N = Intermediate layer Gelatin 6th layer: High-sensitivity green-sensitive emulsion layer Silver iodobromide Emulsion (Agl 1 0.5 (Grl) 0.0 mol%, internal high Agl type, equivalent sphere diameter 1.5 μm, coefficient of variation of equivalent sphere diameter 32%, plate-like grains, diameter/thickness ratio 6.0) Silver Coating amount 1.0 Gelatin 0.8ExS-52X
10-'mol ExS-6'0.8xlO-'mol ExS-70,
8X10””mol ExM-40,04 ExM-30,01 ExC-40,005 Solv-10,2 7th layer: Intermediate layer gelatin 1.0Cp d -4
0,1 8th N: Low-sensitivity red-sensitive emulsion layer (RL) Silver iodobromide emulsion (Ag1 10.0 mol%, internal high Agl
Type, equivalent sphere diameter 0.7 μm, coefficient of variation of equivalent sphere diameter 28%,
Plate-shaped particles, diameter/thickness ratio 3.0) Silver coating amount 0.5
Silver iodobromide emulsion (AgI 6.0 mol%, internal high Ag
L type, equivalent sphere diameter 0.4 μm, coefficient of variation of equivalent sphere diameter 26%
, plate-shaped particles, diameter/thickness ratio 3.0) Silver coating amount 0.
4 Gelatin 1.5ExS-1
4,5xto-'molExS-21,5xlO-'molExS-30,4x 10-'molExS-4o,3xio-'molExC-10,33 ExC-20,01 ExC-30,023 ExC-60, 14 Solv-10,2 9th N: Medium-sensitivity red-sensitive emulsion Jif (RM) Silver iodobromide emulsion (Ag1 10.0 mol%, internal high Agr type, equivalent sphere diameter 0.85 μm, coefficient of variation of equivalent sphere diameter 30 %, platelet particles,
Diameter/thickness ratio 4.0) Silver coating amount 0.8 Gelatin 1.2ExS-13x
lO-'mol ExS-2txto-'mol ExS-30,3X10-'mol ExS-40,3X10-'mol ExC-60,08 EXC-30,05 EXC-40,10 Solv-20,12 10th layer: High red-sensitive emulsion layer (RH) Silver iodobromide emulsion (AgI 10.0 mol%, internal high Agl
Type, equivalent sphere diameter 1.2 μm, coefficient of variation of equivalent sphere diameter 32%,
Plate-shaped particles, diameter/thickness ratio 6.0) Silver coating amount 0.9 Gelatin 0.6ExS-12x
lO-'mol ExS-20,6xlO-'molExS-30,2x L (1-'-T:/I/EXC
-40,07 ExC-50,06 Solv-10,12 Solv-20,12 The 11th layer to the 18th layer are exactly the same as sample 101.

After the samples 101 to 103 were subjected to imagewise exposure, they were subjected to the next process.

Color development processing was carried out at 38° C. according to the following processing steps.

Color development 3 minutes 15 seconds Bleach White 6 minutes 30 seconds Water Wash 2 minutes 10 seconds Fixed arrival time: 4 minutes 20 seconds Water Wash 3 minutes 15 seconds Safe Fixed 1 minute 05 seconds The composition of the treatment liquid used in each step was as follows.

Color developer diethylenetriaminepentaacetic acid 1.0g 1-Hydoxyethylidene-1.1-diphosphonic acid Sodium sulfite Potassium carbonate Potassium bromide Potassium iodide Hydroxylamine sulfur 62 salt 4-(N-ethyl-N-β-hydroxyethylamino)- Add 2-methylaniline sulfate solution and add H 2.0 g 4.0 g 30.0 g 1.4 g 1.3 mg 2.4 g 4.5 g 1.0 N 10.0 100.0 g Bleach solution Ethylenediaminetetraacetic acid secondary Iron ammonium salt Ethylenediaminetetraacetic acid disodium salt Ammonium bromide Ammonium nitrate Add water and add 10.0 g 1 50,0 g 10,0 g 1.01 pi-16,0 Fixer Ethylenediaminetetraacetic acid disodium salt 1.0 g Sodium sulfite Add 4.0g ammonium 1000sulfate aqueous solution (70%) 175.0m/sodium bisulfite 4.6g water
1.0g pH6.6 Stabilized liquid formalin (40%) 2.0ml l'
Add 0.3g of polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 1. O1 The density of the obtained image was measured and the relative sensitivity was determined. The results are shown in Table 2. Is the sensitivity like Cub'J? The exposure amount at a density of 14 degrees + 0.1 was used, and the sensitivities of B, G, and R of sample 101 were determined as relative values with lOO.

Further, similar color development was performed by exposure through a stepped wedge for RMS grain measurement, and RMS values were measured using a 48 μm diameter aperture.

In Sample 102, the graininess of the red-sensitive layer was significantly improved compared to Sample 101, but the sensitivity of the green-sensitive layer was significantly lower. This could not be recovered by increasing the grain size of the emulsion. In sample 103, the sensitivity of the green-sensitive layer was almost recovered, and the graininess of the red-sensitive layer was significantly improved in slightly higher frequencies, but there was an increase in magenta density when exposed to red light.
Unfavorable image quality.

As described above, the method of changing the arrangement of the photosensitive material in order to improve the image quality of the red photosensitive layer has disadvantages and has not been a satisfactory technique.

Example 2 In Sample 103 of Example 1, the sample was Samples 201 and 20 in the same manner as 103
I made 2.

Samples 102, 103, 201, and 202 were exposed to uniform green light, imagewise exposed to red light, and then subjected to the processing described below. A color image density of 2 was obtained. Here, ΔD indicates the degree of suppression that a uniformly fogged green-sensitive emulsion layer receives when the red-sensitive emulsion layer is developed from an unexposed area (point A) to an exposed area (point B). That is, in FIG. 1, curve 1 represents the characteristic curve for a cyan image of a red-sensitive emulsion, and curve 2 represents the magenta image density of a green-sensitive layer upon uniform green exposure. Point A represents the capri portion of the cyan image, and point B represents the exposure amount portion that provides a cyan density of 2.0.

Magenta 4 degrees (a) at point A in the unexposed area and point B in the exposed area
The difference between and (bl) ΔD=ab is expressed as a measure of color turbidity.

The fixing tank of the automatic developing machine used was equipped with a jet stirring device described on page 3 of Japanese Patent Application Laid-Open No. 183460/1983, and the jet of fixer was collided with the emulsion surface of the photosensitive material during processing. I did this.

(Color development) Mother solution (g) Replenisher (g) Diethylenetriaminepentaacetic acid 5.0 6.0 Sodium sulfite 4.0 5.0 Potassium carbonate lb 30.0 37.0 Potassium bromide 1.3 0.5 Potassium iodide 1.2 mg Hydroxylamine sulfate 2.8 3.64-(N-ethyl-N-β monohydroxyethylamine)-2-methylaniline sulfate 4.7 6.2 Add water 1.0ffi 1.0Qp
H10,0010,15 (Bleach solution) Mother liquor (g) Replenisher solution (g) 1.3-diaminopropane 130 190 Tetraacetic acid ferric complex salt (0,36 mol/j2) (0,53
Mol/I 1.3-diaminopropanetetraacetic acid 3.0 4.0 Ammonium bromide 85 120 Acetic acid
5070 Ammonium nitrate 3040 Add water
1. Of f, (H! PN adjustment with acetic acid and ammonia pH 4,3 pH 3,5 (fixer) Mother liquor (g) Replenisher (g) 1-hydroxyethylidene 1,1-diphosphonic acid ethylenediaminetetraacetic acid disodium salt sodium sulfite bisulfite Sodium ammonium 1000 sulfate 5.0?, 0 0.5 0.7 1O10 8,0 12,0 10,0 Aqueous solution (700g/l) 170.0+ej'
200.0mj! Rodan ammonium 100,
0 150.0 Thiourea 3.0
5.03.6-Sythia 1.8-Octanediol 3,0 5.0Add water 1.0! 1.01 acetic acid,
Add ammonia to pH 6,56,7 (Stable solution) Mother liquor, replenisher Common formalin (37%) 1.2ml 15-chloro-2-methyl-4-isothiazolin-3-one
5.0mg 2-methyl-4-isothiazoen-3-one 3. On+g surfactant 0.4 [C1°Ht, -0-+
CHz CHzAdd ethylene glycol water and pH O+711-H] 1.0 1.0! 5.0-7.0 The magenta and cyan concentrations of each sample after treatment were measured and the results are shown in the table below. The sensitivity was expressed as a relative value with the sensitivity of sample 102 set as 100.

From the above results, it can be seen that the structure and compound of the present invention have a remarkable effect of improving image quality. Furthermore, sample 201.20
The graininess of the red-sensitive layer of Sample 2 and the sensitivity of the green-sensitive layer were the same as Sample 103.

Also, when comparing the processing of Example 1 and Example 2 (the processing of Example 1 takes a longer time after the bleach bath, and the processing of Example 2 is faster),
Samples 102 and 103 show an increase in the minimum RL concentration due to speeding up, whereas samples 201 and 20
2 has a small processing difference.

Further, the sample treated in Example 2 was heated at 60℃70% after concentration measurement.
After storage for 3 days under RH, the concentration was measured again, and it was found that RL
A large increase in the minimum concentration of was observed in samples 102 and 103, and a small increase in samples 201 and 201.

Example 3 Compound (I-7), (1-10) of the present invention was used in place of ExC-3 used in sample 102 of Example 1.

Samples 301 to 303 were prepared in the same manner as Sample 102 except that (1-13) and ExC-3 were used in equal moles.

This sample 102.1'03, 301-303 was subjected to the same treatments and operations as in Example 2. However, after stabilization (1) in the processing steps shown in Table 1, the samples were immersed in the bath described below, and then rinsed with water for 2 minutes.

As a result, samples 301 to 303 of the present invention are 201.
It showed almost the same results as No. 202.

Additional bath Red blood salt 60g KBr 25g Naz HPO417,8g Na Hz P04 6-5g Add water
1i pH6,8 Treatment time 1 minute Example 4 Compound 1 instead of compound 1-2 of the present invention in sample 201
Sample 4o1. Sample 301, compound 1-7 of the present invention, was added with 1.3 times the mole of I[I-5,
Samples 402 and 403 were prepared using equimolar amounts of IV-1.

Samples 201, 301, 401-403 were passed through the process of Example 3 with results substantially similar to Samples 201 and 301.

Table A Examples of compounds represented by monomer formula (1) ([ (r-10) (I (I Examples of compounds represented by general formula (II) -Example CI of the compound represented by Monka (III)! Examples of compounds represented by general formula (IV) (rV-1) (fV-2) (III-3) (rV-4) <IV-5) l (TV-6) NOI C-(61 No. table molecular weight about 40.000 C-(7) C 0υ 0no l @H+7 (1) 0■ (Sushi, H C-Q3) α H Q61 CI(.

顛51,;112+;+12 0□II (20+ lu αe a odor H c - (22) ) Ribo Na H L C H C- (30) C c - (36) N□δ C- (38 ) C-(40) R C N H C-(47) C-(49) CI! H C (t)C1H C4119 \ CsH+t(t) CIIll+t(t) CI! C-(5B) C1 CI+3 l C-(64) I C Cρ H CO! II ShiIIkoH OzCHi C xM-3 xC 0■ (t)CJqOCOCNtl Table V-1 V-2 F, x C C1]2 xC H ExC-6 ExC H ExC-5 ttLs xM-4 2 F, x M -5 xM-1 lh しEx xM-2 xY-1 F, x Y -2 ExS -1 1F, x S -2 ExS ExS-8 ExS-7 ol ExS-4 ExS olv-3 olv pd- 1 Js C18゜pd pd C! 13 ■ pd -t ■ CsF+? 5OtNIIClhC1hCHzOC)Iz
CIhN (CH2)3pd-4 Cilltz(n) Hz = CHSOz H2 CON HCHz Ht = CH3O.

Hz CONH-CΣ(2 U■ CJts (n) 4,

[Brief explanation of drawings]

FIG. 1 is a diagram for explaining how to determine color turbidity. l... Characteristic curve regarding cyan image of red-sensitive emulsion, 2... Magenta image density of green-sensitive layer due to uniform green exposure.

Claims (1)

[Claims] (1) In a color photosensitive material having a plurality of silver halide emulsion layers having different color sensitivities on a support, at least one emulsion layer that is more sensitive to longer wavelength light on the side farther away from the support exists, and the emulsion layer has the following general formula (
A silver halide color light-sensitive material containing at least one of the compounds listed in (I) to (IV). General formula (I) A-(L)_n-DYP_1 General formula (II) DYP_1-B_1-LVG General formula (III) BLK-B_2-N=N-R General formula (IV) PWR-(L)_n-DYP_2 In the formula, A
represents a group that reacts with the oxidized developing agent to cleave (L)_n-DYP_1, and L represents D after cleavage from A or PWR.
represents a group that cleaves YP_1 or DYP_2, respectively,
n represents 0 or 1, DYP_1 represents a dye precursor group that develops color when combined with A-(L)_n or B_1-LVG during the development process, and B
_1 represents a group that reacts with the oxidized developing agent to cleave LVG, LVG represents a leaving group that bonds to the coupling position of B_1 at the heteroatom, BLK represents a protecting group that is cleaved during development, and B_2 represents its At the coupling position
A group having N=N-R and further having BLK, which is a group that protects the oxygen atom bonded to the even-numbered carbon atom that constitutes a conjugated double bond counting from the carbon atom at this coupling position. where R represents a 5- to 8-membered cyclic group having a double bond that can be conjugated with -N=N-, PWR represents a group that cleaves (L)_n-DYP_2 upon reduction, and DYP_2 represents PWR -(L) Represents a dye precursor group that develops color in the development process after being cleaved from n.