JPH0593992A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To enhance interimage effect and to improve sharpness, and fog during storage of raw photosensitive materials by incorporating a hydroquinone derivative substituted by an alkanamidogroup and capable of releasing a photographic useful group. CONSTITUTION:The photographic sensitive material contains at least one of the compound represented by formula I in which R1 is a >=2C alkyl, cycloalkyl, aryl, or heterocyclic group negative type substituted by a hetero atom on the carbon atom adjacent to the carbonyl group; each of R2 and R3 is H or a substituent having a Hamett' substituent coefficient of <=0.3; B is a group to be allowed to release a photographic useful group (development inhibitor) after being released from the oxidation product of a hydroquinone ring: l is an integer; and each of A and A' is H or a group to be removed by alkali. It is preferred that the compound of formula I is one of compounds represented by formula II in which R4 is a substituent and n is an integer of >=2.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material having an improved inter-image effect, an improved sharpness and an improved fog during raw storage.

[0002]

2. Description of the Related Art By color-developing a silver halide color photographic material, an oxidized aromatic primary amine color developing agent and a coupler react to react with indophenol, indoaniline, indamine, azomethine, phenoxazine, phenazine and It is known that similar dyes are formed and color images are formed. In this method, a subtractive color method is usually used for color reproduction, and a yellow, magenta, and cyan color image forming agents that have a complementary color relationship with a silver halide emulsion that selectively exposes to blue, green, and red, respectively. Is used. To form a yellow image,
For example, an acylacetanilide or dibenzoylmethane type coupler is used, and a pyrazolone, a pyrazolobenzimidazole, a pyrazolopyrazole, a pyrazolotriazole, a cyanoacetophenone or an indazolone type coupler is mainly used for forming a magenta color image. For forming a cyan image, a phenol type or a naphthol type is mainly used. By the way, the dyes produced from these couplers are not ideal spectral absorption spectra, and magenta and cyan dyes in particular have broad absorption spectra and have sub-absorption in the short wavelength region, which makes them suitable for color photography. Not desirable for color reproduction of material. In particular, the secondary absorption in the short wavelength region tends to cause a decrease in saturation. As one means for improving this, it can be improved to some extent by expressing an inter-image effect. As one of means for improving the inter-image effect, US Pat. No. 3,379,52 has been proposed.
No. 9, No. 3,620,746, No. 4,377,634
No. 4,332,878, JP-A-49-129,5.
36, etc., and DIR hydroquinone. These DIR hydroquinones are substances that release a development inhibitor by being oxidized during the development process. However, until now, DIR hydroquinone was oxidized during the development process so that the interimage effect was improved. However, if the speed is increased, the fog increases during the aging of the raw film and the fog increases during development, which is a very serious problem in photographic performance. On the other hand, if the reducing property of DIR hydroquinone is reduced to the extent that these fog increases do not occur, the reducing power during development processing is insufficient, the release of the development inhibitor is small, and the interimage effect can be improved almost. I couldn't do it. In addition, conventionally known U.S. Pat. Nos. 2131038 and 269471.
No. 6, No. 2,444,605, No. 2,232,707, the antifoggant used in combination with this DIR hydroquinone can suppress fog to some extent.
Since the development activity of hydroquinone decreases, the interimage effect also decreases. As described above, it has been extremely difficult to develop a large interimage effect without increasing the fog caused by DIR hydroquinone. A technique for exerting an inter-image effect while suppressing an increase in fog due to DIR hydroquinone has been strongly desired.

[0003]

SUMMARY OF THE INVENTION The first object of the present invention is to provide a multilayer color photographic light-sensitive material having a large inter-image effect without increasing fog during storage. A second object of the present invention is to provide a multilayer color photographic light-sensitive material having a high sharpness and a large inter-image effect without deteriorating graininess. The third object of the present invention is to provide a black-and-white silver halide light-sensitive material having high sharpness and good graininess without increasing fog.

[0004]

The object of the present invention is to provide a compound represented by the following formula (I) in a silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support. It has been achieved with a silver halide photographic light-sensitive material characterized by containing at least one kind. General formula [I]

[0005]

[Chemical 4]

(In the formula, R ₁ is an alkyl group, a cycloalkyl group, an aryl group having 2 or more carbon atoms in which a carbon atom adjacent to the carbonyl group is not substituted with a hetero atom, or
Represents a heterocyclic group, R ₂ and R ₃ represent a hydrogen atom or a substituent having a substituent constant σ _{p of} hamet of 0.3 or less, and B represents PUG after elimination from the hydroquinone mother nucleic acid product.
Represents a group releasing a group, PUG represents a development inhibitor,
l represents an integer, and A and A'represent a hydrogen atom or a group capable of being removed with an alkali. ) That is, the present inventors have conducted extensive studies in order to overcome the drawbacks of conventional DIR hydroquinone, and as a result, have decided to use DIR hydroquinone characterized by having an amide group represented by the formula [I]. Therefore, they have found that the inter-image effect is greatly improved without increasing the fog on the raw thermostat. As a result of a more detailed study, it was discovered that, among the group of compounds represented by the formula [I], the compounds represented by the formulas [III] and [III] exhibit excellent properties even when used in a small amount. Ivy. General formula [II]

[0007]

[Chemical 5]

In the formula [II], R ₄ represents a substituent, PUG, A, A ', B and l have the same meaning as in the formula [I] and n represents an integer of 2 or more. General formula [III]

[0009]

[Chemical 6]

In the formula [III], R ₅ represents a substituent, A, A ', B, PUG and l have the same meaning as in the formula [I], m represents an integer of 1 to 5, and m represents When two or more, R ₅ may be the same or different. Suppresses the increase in fog caused by DIR hydroquinone,
In addition, as a technique for improving the inter-image effect, the combined use with the compound disclosed in JP-A-63-17445 is known. In the present invention, by using the compound of the formula [I], it is possible to obtain a large interimage effect without using these fog-inhibiting agents and by using a smaller amount than that of the conventional DIR hydroquinone, without causing an increase in fog. Was achieved.

The present invention will be described in more detail. Formula [I]
In R ₁ is a substituted or unsubstituted alkyl group having 2 or more carbon atoms in which a carbon atom adjacent to the carbonyl group is not substituted with a hetero atom (preferably 2 to 30 carbon atoms, for example, ethyl, n-nonyl, n- Undecyl, n-pentadecyl, 1- (2,5-di-tert-amylphenoxy) -propyl, 1-hexylnonyl, etc., a substituted or unsubstituted aryl group (preferably having 6 to 3 carbon atoms)
0, for example, phenyl, naphthyl, m-dodecanamidophenyl, m-hexadecylsulfonamidophenyl, p
-Dodecyloxyphenyl etc.) or a heterocyclic group (eg 2-pyridyl, 4-pyridyl, 3-pyridyl, 2
-Furyl group), and the substituent on R ₁ is
Alkyl group, aryl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, carboxylic acid amide group, sulfonic acid amide group, alkoxycarbonylamino group, ureido group, carbamoyl group, alkoxycarbonyl group, sulfamoyl group, sulfonyl group, Examples thereof include a cyano group, a halogen atom, an acyl group, a carboxyl group, a sulfo group, a nitro group and a heterocyclic residue.

In the formula [I], R ₂ and R ₃ represent a hydrogen atom or a substituent having a substituent constant σ _{p of the} hamet of 0.3 or less, and examples thereof include a substituted or unsubstituted alkyl group ( Methyl, ethyl, n-nonyl, n-undecyl, etc.), or a substituted or unsubstituted aryl group (phenyl, naphthyl, m-dodecanamidophenyl, m-).
Hexadecylsulfonamidophenyl etc.), alkoxy groups (methoxy, ethoxy, n-hexyloxy, n-
Hexadecyloxy, etc.), aryloxy group (phenoxy, naphthoxy, etc.), alkylthio group (methylthio, n-butylthio, n-decylthio, etc.), arylthio group (phenylthio, 2-n-butyloxy-5-t)
ert-octylphenylthio, etc.), acylamino group (acetylaceamide, n-decanoic acid amide, benzoic acid amide, etc.), sulfonic acid amide group (methanesulfonic acid amide, n-butanesulfonic acid amide, n-dodecylsulfonic acid amide, etc.) ), Or a halogen atom (chlorine, bromine,
Fluorine) and the like.

R _{4 in the} formulas [II] and [III]
Preferred substituents for R ₅ and R ₅ are alkyl group (n-heptyl, n-nonyl, n-tridecyl, etc.), aryl group (phenyl, naphthyl, etc.), alkoxy group (n-hexyloxy, 2-ethylhexyloxy, n-decyloxy). , N-dodecyloxy, n-hexadecyloxy, etc.), aryloxy groups (phenoxy, 2,4-di-t
ert-amylphenoxy, 2-chloro-4-tert
-Amylphenoxy, 3-pentadecylphenoxy, etc.), alkylthio group (n-hexylthio, n-decylthio, n-hexadecylthio, etc.), arylthio group (phenylthio, 2-n-butyloxy-5-tert)
-Octylphenylthio, 4-dodecyloxyphenylthio, etc.), carboxylic acid amide group (n-decanoic acid amide, 2- (2 ', 4'-di-tert-amylphenoxy) -butanoic acid amide, n-hexadecane Acid amide, 2
-Ethylhexanoic acid amide, 3-decanoic acid amide benzoic acid, etc.), sulfonic acid amide group (n-dodecyl sulfonic acid amide, n-hexadecyl sulfonic acid amide, 4
-N-dodecyloxybenzenesulfonic acid amide, etc.), alkoxycarbonylamino group (n-dodecyloxycarbonylamino, n-hexyloxycarbonylamino, etc.), sulfamoyl group (n-decylsulfamoyl, n-hexadecylsulfamoyl) Etc.), sulfonyl group (n-octanesulfonyl, n-dodecanesulfonyl, benzenesulfonyl, etc.), ureido group (N-
n-dothesylcarbamoylamino, Nn-hexadecylcarbamoylamino, etc., carbamoyl group (Nn
—Dodecylcarbamoyl, Nn-hexadecylcarbamoyl and the like), alkoxycarbonyl group (2-ethylhexyloxycarbonyl, n-hexadecylcarbonyl and the like), cyano group, halogen atom, nitro group, hydroxyl group and the like. Further, these substituents may be further substituted with the above groups.

In the formula [II], preferred R ₄ is a substituent having 5 to 30 carbon atoms, and preferred n is 2 to 5. In the formula [III], the total number of carbon atoms contained in R ₅ is preferably 5 to 30. Formula [I]
In [II] and [III], when A and A'represent a group that can be removed by an alkali (hereinafter referred to as a precursor group), it is preferably an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, or imidoyl. Groups, hydrolyzable groups such as oxazolyl groups, sulfonyl groups, US Pat. No. 4,009,
No. 029 type precursor group utilizing the reverse Michael reaction, US Pat. No. 4,310,612 type precursor molecule utilizing the anion generated after the ring opening reaction as an intramolecular nucleophilic group, U.S. Pat. No. 3,674,4
78, 3,932,480 or 3,99
A precursor group in which the anion described in No. 3,661 causes electron transfer through a conjugated system to thereby cause a cleavage reaction,
Precursor groups described in U.S. Pat. No. 4,335,200, which cause a cleavage reaction by electron transfer of anions reacted after ring cleavage, or U.S. Pat. No. 4,363,865.
Precursor groups utilizing an imidomethyl group described in JP-A No. 4,410,618 are mentioned. Formula [I], [II]
And the group represented by B in [III] is a group in which after the hydroquinone mother nucleus is oxidized by the developing agent oxidation product during development to form a quinone form,

[Other 6 /] Represents a divalent group which can be released and may have a timing adjusting function, and also serves as a coupler which reacts with another molecule of an oxidized product of a developing agent to release PUG,
Alternatively, it may be a redox group. Here, when 1 is 0, it means that PUG is directly bonded to the hydroquinone mother nucleus, and when 1 is 2 or more, it represents the same or different combination of two or more B's.

When B is a divalent linking group having a timing adjusting function, examples thereof include the following. (1) Group utilizing cleavage reaction of hemiacetal For example, US Pat. No. 4,146,396, JP-A-60-
249148 and 60-249149, which are groups represented by the following general formula. Here, the * mark represents the position bonded to the left side in the formulas [I], [II] and [III], and the ** mark represents the formulas [I], [II] and [I].
II] represents the position of binding to the right side. General formula (T-1)

[0016]

[Chemical 7]

In the formula, W is an oxygen atom, a sulfur atom or-
NR ₆₇ — group, R ₆₅ and R ₆₆ represent a hydrogen atom or a substituent, R ₆₇ represents a substituent, and t represents 1 or 2. When t is 2, two -W-C (R
₆₅ ) ( _R66 )-represents the same or different. When R ₆₅ and R ₆₆ represent a substituent and typical examples of R ₆₇ are R ₆₉ group, R ₆₉ CO— group,
R ₆₉ SO ₂ - _{group, R 69 N (R 70)} CO- group or _{R 69 N (R 70) SO} 2 - , etc. group. Here, R ₆₉ represents an aliphatic group, an aromatic group or a heterocyclic group, and R ₇₀ represents an aliphatic group aromatic group, a heterocyclic group or a hydrogen atom. Each of R ₆₅ , R ₆₆ and R ₆₇ represents a divalent group and is also included when they are linked to each other to form a cyclic structure. Specific examples of the group represented by the formula (T-1) include the following groups.

[0018]

[Chemical 8]

(2) Group that causes cleavage reaction utilizing intramolecular nucleophilic substitution reaction For example, a timing group described in US Pat. No. 4,248,962 can be mentioned. It can be represented by the following general formula. General formula (T-2)

[0020]

[Chemical 9]

In the formula, * marks represent the formulas [I], [II] and [I].
II] represents the position bonded to the left side, the ** symbol represents the position bonded to the right side in the formulas [I] [II] and [III], Nu represents a nucleophilic group, and an oxygen atom or a sulfur atom An example of a nuclide, E represents an electrophilic group, and is a group capable of cleaving the bond with the ** mark by a nucleophilic attack from Nu. The Link indicates that Nu and E can undergo an intramolecular nucleophilic substitution reaction. Represents a linking group that is sterically related. Specific examples of the group represented by formula (T-2) are as follows.

[0022]

[Chemical 10]

(3) A group which causes a cleavage reaction by utilizing an electron transfer reaction along a conjugated system. For example, U.S. Pat. No. 4,409,323 or 4,4
No. 21,845, which is a group represented by the following general formula. General formula (I-3)

[0024]

[Chemical 11]

In the formula, * mark, ** mark, W, R ₆₅ , R ₆₆
And t have the same meanings as described for (T-1). Specific examples include the following groups.

[0026]

[Chemical formula 12]

(4) A group which utilizes a cleavage reaction due to hydrolysis of an ester. For example, the following groups are the connecting groups described in West German Published Patent No. 2,626,315. In the formula, asterisks and asterisks have the same meanings as described for the general formula (T-1). General formula (T-4)

[0028]

[Chemical 13]

General formula (T-5)

[0030]

[Chemical 14]

(5) A group which utilizes a cleavage reaction of an imino ketal. For example, it is a linking group described in US Pat. No. 4,546,073, and is a group represented by the following general formula. -General formula (T-6)

[0032]

[Chemical 15]

In the formula, *, ** and W are general formulas (T
-1) has the same meaning as described above, and R
₆₈ has the same meaning as R ₆₇ . General formula (T-6)
Specific examples of the group represented by are the following groups.

[0034]

[Chemical 16]

The group represented by B is a group which becomes a coupler,
Alternatively, examples of the group that becomes the redox group include the following. In the case of a phenol type coupler, for example, a group serving as a coupler is a group bonded to a hydroquinone mother nucleus at an oxygen atom excluding a hydrogen atom of a hydroxyl group. Further, in the case of a 5-pyrazolone type coupler, it is bonded to a hydroquinone nucleus at an oxygen atom obtained by removing a hydrogen atom from a hydroxy group of a type tautomerized to 5-hydroxypyrazole. In each of these examples, a phenol type coupler or a 5-pyrazolone type coupler is not formed until they are released from the hydroquinone mother nucleus. Also, PUG binds to those coupling positions. When (()) B represents a group that is cleaved from an oxidized form of the hydroquinone nucleus to serve as a coupler, it is preferably the following formula (C-1), (C-2), (C-3), or (C- It is a group represented by 4). General formula (C-1)

[0036]

[Chemical 17]

General formula (C-2)

[0038]

[Chemical 18]

General formula (C-3)

[0040]

[Chemical 19]

General formula (C-4)

[0042]

[Chemical 20]

[Chemical 21]

In the formula, V ₁ and V ₂ represent a substituent,
V ₃ , V ₄ , V ₅ and V ₆ represent a nitrogen atom or a substituted or unsubstituted methine group, V ₇ represents a substituent, x represents an integer of 0 to 4, and when x is plural, V
_7's represent the same thing or different thing, and two V < ₇ > may connect and may form a cyclic structure. V ₈ is -CO-
A group, a —SO ₂ — group, an oxygen atom or a substituted imino group, and V ₉ is —V ₈ —N (− *) — C (V ₁₀ ) ═C (−
**)-represents a group of non-metal atoms for constituting a 5-membered to 8-membered ring, and V ₁₀ represents a hydrogen atom or a substituent. However, V ₁ and V ₂ each represent a divalent group, and may be connected to form a 5-membered to 8-membered ring together with -C (-O-*) = C (-**)-.

V ₁ preferably represents the group R ₇₁ , V ₂
Is R ₇₂ group, R ₇₂ CO- group, R ₇₃ N (-R ₇₄ ) C
O- _{group, R} 72 SO ₂ - _{group, R} 72 S- _{group, R} 72 O-
Group, or _{R 73 SO 3 N (-R 74} ) - group is a preferred example. When V ₁ and V ₂ are linked to each other to form a ring, examples thereof include indenes, indoles, pyrazoles, and benzothiophenes. V ₃ , V
Preferred substituents when ₄ , V ₅ or V ₆ represents a substituted methine group include R ₇₁ group, R ₇₃ O— group, and R ₇₁ S—.
Group, or R ₇₁ CONH-group.

A preferable example of V ₇ is a halogen atom,
R ₇₁ group, R ₇₁ CONH- group, R ₇₁ SO ₂ NH-
_{Group, R} 73 _{O-group, R} 71 S- _{group, R} 73 N (-
R ₇₄₎ CO- _{group, R 73 N (-R 74)} CON (-R
₇₅₎ - _group, R 71 CO- group or _R 73 OOC- group is a preferred example. Examples of the case where a plurality of V _7's are linked to each other to form a cyclic structure include naphthalene, quinoline, oxindole, benzodiazepine-2,4-dione, benzimidazol-2-one or benzothiophene. . Preferably when V ₈ represents a substituted imino group _R 73 N (-) - a group.

V ₉ is -V ₈ -N (-*)-C (-
Preferred ring structures constituting V ₁₀ ) = C (-**)-are indoles, imidazolinones, 1,2,5-thiadiazoline-1,1-dioxides, and 3-pyrazolin-5.
-Ones, 3-isoxazolin-5-ones, or those shown below.

[0047]

[Chemical formula 22]

Preferred examples of V ₁₀ are R ₇₃ group, R ₇₃ O
- _{group, R 73 N (-R 74)} - _group, R 71 CON (-R
₇₃ ) -group, or R ₇₁ S-group. In the above, R ₇₁ and R ₇₂ represent an aliphatic group, an aromatic group or a heterocyclic group, and R ₇₃ , R ₇₄ and R ₇₅ represent a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group. Here, the aliphatic group, aromatic group and heterocyclic group have the same meanings as described above, but the total number of carbon atoms contained in these groups is preferably 10 or less. The following groups may be mentioned as specific examples of the group represented by formula (C-1).

[0049]

[Chemical formula 22]

[0050]

[Chemical formula 23]

The following groups may be mentioned as specific examples of the group represented by formula (C-2).

[0052]

[Chemical formula 24]

The following groups may be mentioned as specific examples of the group represented by formula (C-3).

[0054]

[Chemical 25]

The following groups may be mentioned as specific examples of the group represented by formula (C-4).

[0056]

[Chemical formula 26]

When the group represented by B in the general formulas [I], [II] and [III] represents a group which is cleaved from the hydroquinone nucleus to become a redox group, the following general formula (R-1) is preferred. Represented. General formula (R-1)

[0058]

[Chemical 27]

In the formula, P and Q each independently represent an oxygen atom or a substituted or unsubstituted imino group, at least one of n X and Y represents a methine group having -PUG as a substituent, and X and Y each represent a substituted or unsubstituted methine group or a nitrogen atom, and n
Represents an integer of 1 to 3 (n X and n Y represent the same or different), A represents a hydrogen atom or a group removable by an alkali, and has the formula (I)
Has the same meaning as A in. Here, the case where any two substituents of P, X, Y, Q and A are connected as a divalent group to form a cyclic structure is also included. For example (X =
Y) When _n forms a benzene ring, a pyridine ring, or the like. When P and Q represent a substituted or unsubstituted imino group, it is preferably an imino group substituted with a sulfonyl group or an acyl group. Then P and Q
Is represented as follows.

General formula (N-1)

[Chemical 28]

General formula (N-2)

[0062]

[Chemical 29]

Here, the asterisk * indicates the position at which A is bonded,
The ** mark represents the position of bonding to one of the free bonds of-(X = Y) _n- . In the formula, the group represented by G has from 1 to 1 carbon atoms.
32, preferably 1 to 22 straight or branched, chain or cyclic, saturated or unsaturated, substituted or unsubstituted aliphatic group (eg, methyl, ethyl, benzyl, phenoxybutyl, isopropyl), 6 to 10 carbon atoms A substituted or unsubstituted aromatic group (for example, a phenyl group, a 4-methylphenyl group, a 1-naphthyl group, a 4-dodecyloxyphenyl group, etc.), or a 4-membered hetero atom selected from a nitrogen atom, a sulfur atom or an oxygen atom. To 7-membered heterocyclic groups (eg, 2-pyridyl group, 1-phenyl-4-imidazolyl group, 2-furyl group, benzothienyl group, etc.) are preferred examples.

In the general formula (R-1), P and Q are preferably each independently an oxygen atom or the general formula (N-
It is a group represented by 1). In the general formula (R-1), P is preferably an oxygen atom and A is a hydrogen atom. In the general formula (R-1), it is more preferable that X and Y be a substituted or unsubstituted methine group, except when X and Y are methine groups having PUG as a substituent. General formula (R-1)
Among the groups represented by, particularly preferred groups are those represented by the following general formula (R-2) or (R-3). General formula (R-2)

[0065]

[Chemical 30]

General formula (R-3)

[0067]

[Chemical 31]

In the formula, the * mark represents the position of bonding with the hydroquinone mother nucleus, and the ** mark represents the position of bonding with PUG. R ₆₄ represents a substituent, and q represents an integer of 0.1 to 3. When q is 2 or more, two or more R _64's may be the same or different, and when two R _64's are substituents on adjacent carbons, they are each linked to a divalent group to form a ring structure. Is also included. At that time, it becomes a benzene condensed ring, for example, a ring structure such as naphthalene, benzonorbornene, chroman, indole, benzothiophene, quinoline, benzofuran, 2,3-dihydrobenzofuran, indane, or indene, These may further have one or more substituents. Examples of preferred substituents when having substituents on these condensed rings and preferred examples of R ₆₄ when R ₆₄ does not form a condensed ring are those listed below.

That is, an alkoxy group (eg, methoxy group, ethoxy group, etc.), an acylamino group (eg, acetamide group, benzamide group, etc.), a sulfonamide group (eg, methanesulfonamide group, benzenesulfonamide group, etc.), an alkylthio group (eg, A methylthio group,
Ethylthio group, etc., carbamoyl group (for example, N-propylcarbamoyl group, Nt-butylcarbamoyl group,
Ni-propylcarbamoyl group etc.), alkoxycarbonyl group (eg methoxycarbonyl group, propoxycarbonyl group etc.), aliphatic group (eg methyl group, t
-Butyl group), a halogen atom (for example, a fluoro group,
Chloro group etc.), sulfamoyl group (eg N-propylsulfamoyl group, sulfamoyl group etc.), acyl group (eg acetyl group, benzoyl group etc.), hydroxyl group, carboxyl group, or heterocyclic thio group (eg 1-phenyl group). Examples thereof include groups represented by PUG described later such as an enyltetrazolyl-5-thio group and a 1-ethyltetrazolyl-5-thio group. In addition, typical examples of the case where two R ₆₄ are linked to each other to form a cyclic structure are as follows.

[0070]

[Chemical 32]

(The symbols * and ** have the same meanings as described in formula (R-3)). The group represented by PUG in the general formulas [I], [II] and [III] represents a development inhibitor. Specifically, tetrazolylthio group, benzimidazolylthio group, benzothiadiazolylthio group, benzoxazolylthio group, benzotriazolyl group, benzoindazolyl group, triazolylthio group, oxadiazolylthio group, imidazolylthio group, thiadiazolylthio group. Group, a thioether-substituted triazolyl group (for example, a development inhibitor described in U.S. Pat. No. 4,579,816), an oxazolylthio group, or the like, which may have a substituent, and preferable substituents are as follows. The ones are listed. That is, R ₇₇ group, R
₇₈ O- group, R ₇₇ S- group, R ₇₇ OCO- group, R ₇₇
OSO ₂ − group, halogen atom, cyano group, nitro group, R
₇₇ SO ₂ - _group, R 78 CO- _groups, R 77 COO- groups,
R ₇₇ SO ₂ N (-R ₇₈ )-group, R ₇₈ N (-
R ₇₉₎ SO ₂ - _{group, R 78 N (-R 79)} CO- group,
_R77 ( _R78- ) C = N- group, _R78 ( _R79- ) N
- _{group, R 78 CON (-R 79)} - _group, R 77 OCON
_{(-R 78)} - _group, R 77 _SO 2 O- _{group, R} 78 (R
_{79 -) NCON (-R 80)} - group, or include a group represented by the following.

[0072]

[Chemical 33]

Here, R ₇₇ represents an aliphatic group, an aromatic group or a heterocyclic group, and R ₇₈ , R ₇₉ and R ₈₀ represent an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom.
When two or more R ₇₇ , R ₇₈ , R ₇₉ and R ₈₀ are present in one molecule, they are linked to form a ring (eg benzene ring).
May be formed. Here, the aliphatic group has 1 to 2 carbon atoms.
0, preferably 1-10 saturated or unsaturated, branched or straight-chain, chain-like or cyclic, substituted or unsubstituted aliphatic hydrocarbon groups. An aromatic group has 6 to 2 carbon atoms
0, preferably 6 to 10 substituted or unsubstituted phenyl group or substituted or unsubstituted naphthyl group. The heterocyclic group has 1 to 18 carbon atoms, preferably 1 to 7 carbon atoms, and is selected as a hetero atom from a nitrogen atom, a sulfur atom or an oxygen atom. It is a saturated or unsaturated, substituted or unsubstituted heterocyclic group, preferably a 4- to 8-membered heterocyclic group. When these aliphatic group, aromatic group and heterocyclic group have a substituent, examples of the substituent include a substituent which the heterocyclic thio group or the heterocyclic group mentioned as the example of the development inhibitor may have. The substituents listed as the group can be mentioned. Particularly preferred development inhibitors in the general formulas [I], [II] and [III] are compounds having a development inhibitory property when cleaved, but they are substantially photographed after they flow out into a color developing solution. It is a development inhibitor having the property of being decomposed (or changed) into a compound that does not affect the property.

For example, US Pat. No. 4,477,563,
JP-A-60-218644 and 60-221750.
No. 60-233650 or 61-1174.
The development inhibitors described in No. 3 are mentioned. Formula [I],
In [II] and [III], preferable l is 0.1
Or 2. Specific examples of the compound used in the present invention are listed below, but the present invention is not limited thereto.

[0075]

[Chemical 34]

[0076]

[Chemical 35]

[0077]

[Chemical 36]

[0078]

[Chemical 37]

[0079]

[Chemical 38]

[0080]

[Chemical Formula 39]

[0081]

[Chemical 40]

[0082]

[Chemical 41]

Some synthetic sequences of specific compounds are shown below, but the compounds used in the present invention can be synthesized very easily by utilizing these methods.

Synthesis Example 1. Synthesis of compound (1) 1-1) Synthesis of 2,5-dimethoxy-n-hexadecanoylanilide (1-1) 153 g of 2,5-dimedoxyaniline and 97 m of pyridine
1 was mixed with 1 l of acetonitrile, and 275 g of n-hexadecanoyl chloride was put under water cooling. After stirring at room temperature for 1 hour, the precipitated crystals were filtered, washed with acetonitrile and dried to obtain 313 g of (1-1). 1-2) n-hexadecanoylaminohydroquinone (1
-2) 114 g of (1-1) obtained above was melt | dissolved in 500 ml of toluene, and 117 g of aluminum chloride was added loosely while stirring on an oil bath of 50 degreeC. After stirring at 50 ° C. for 2 hours, the oil bath temperature was raised to 80 ° C. and stirring was continued for another hour.
After completion of the reaction, the mixture was returned to room temperature and slowly poured into ice water to precipitate crystals. After filtering the crystals and washing with water,
After further washing with acetonitrile and drying, 103.7
g (1-2) was obtained.

1-3) Synthesis of n-hexadecanoylaminobenzoquinone (1-3) 30 g of (1-2) obtained above was dissolved in 600 ml of ethyl acetate, and 60 g of manganese dioxide was added. At room temperature, 4
After stirring for an hour, the mixture was heated and the filtrate was concentrated. Recrystallized from the concentrate with acetonitrile, 27
g of (1-3) was obtained. 1-4) Synthesis of Compound (1) 2-mercapto-5-methylthio-1,3,4-thiadiazole 11.5 g and p-toluenesulfonic acid 2 g
It was dissolved in 00 ml of chloroform, and 25 g of (1-3) obtained in 3) above was added with stirring at room temperature. The mixture was stirred at room temperature for 30 minutes, the precipitated crystals were separated by filtration, and the obtained crude crystals were recrystallized from acetonitrile to obtain 31 g of the objective compound (1) as colorless crystals. (Melting point 165-1
66 ° C)

Synthesis Example 2 Synthesis of compound (17) 2-1) Synthesis of m-nitrobenzoic acid-2,5-dimethoxyanilide (2-1) m-nitrobenzoic acid 56.1 g, acetonitrile 300
26 ml of thionyl chloride was added dropwise to ml under ice cooling. After the dropping, the mixture was stirred for 30 minutes, and 52.1 g of 2,5-dimethoxyaniline was added to the reaction mixture. 30 at room temperature
After stirring for minutes, the precipitated crystal was separated by filtration and the crude crystal was recrystallized from acetonitrile to obtain 61 g of (2-1). 2-2) Synthesis of m-aminobenzoic acid 2,5-dimethoxyanilide (2-2) Reduced iron 45 g, ammonium chloride 4.5 g, water 60 ml
And a solution of 400 ml of isopropanol was heated and stirred on a steam bath, and 60 g of (2-1) obtained above was added little by little. After heating under reflux for 1 hour, the reaction mixture was returned to room temperature, the iron powder was filtered off, and the filtrate was concentrated. The residue was dissolved in ethyl acetate, washed with water and dried, and the solvent was evaporated to give 53 g (2-2) as an oil.
2-3) Synthesis of m-hexadecanesulfonic acid amide benzoic acid 2,5-dimethoxyanilide (2-3) 20 g of (2-2) obtained above was added to 100 m of acetonitrile.
1 and pyridine (7.1 ml), and hexadecanesulfonyl chloride (26.3 g) was added. The reaction mixture at 60 ° C.
After heating and stirring for 3 hours, 100 ml of water was added.
The precipitated crystals were separated by filtration and the crude crystals were recrystallized from acetonitrile to obtain 35 g of (2-3) as crystals.

2-4) Synthesis of m-hexadecanesulfonic acid amide benzoic acid amide hydroquinone (2-4) 15 g of (2-3) obtained above was dissolved in 200 ml of toluene, and 12.5 g of aluminum chloride was dissolved at room temperature. Was added. The reaction mixture was stirred on an oil bath at 40 ° C. for 30 minutes, then the oil bath temperature was further raised to 90 ° C. and stirred for 2 hours. After the reaction was completed, the mixture was poured into ice water, and the precipitated crystals were filtered off,
After washing with water and heating with acetonitrile, 11g
(2-4) was obtained. 2-5) Synthesis of m-hexadecane sulfonic acid amide benzoic acid amide benzoquinone (2-5) 11 g of (2-4) obtained above was added to 300 ml of chloroform.
It was dissolved in 50 ml of dimethylacetamide, 20 g of manganese dioxide was added, and the mixture was stirred at room temperature for 1 hour. The reaction mixture was filtered, the filtrate was concentrated, water was added, and the precipitated crystals were separated by filtration and washed with acetonitrile to obtain 8.7 g of (2-5). 2-6) Synthesis of compound (17) 8.7 g of (2-5) obtained above was added to 60 ml of chloroform.
Dispersed in 2-mercapto-5-methylthio-1,3,
2.7 g of 4-thiadiazole and 0.5 g of p-toluenesulfonic acid were added, and the mixture was stirred at room temperature for 1 hour. When the precipitated crystals were separated by filtration and recrystallized from acetonitrile, 7.2
g (17) was obtained as colorless crystals. (Melting point 189-1
90 ° C)

The light-sensitive material of the present invention may have at least one layer of a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer of a silver halide emulsion layer provided on a support. There is no particular limitation on the number and order of layers of the silver halide emulsion layer and the non-photosensitive layer. As a typical example, a silver halide photographic light-sensitive material having at least one light-sensitive layer composed of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities on a support. And the photosensitive layer is blue light, green light,
And a unit light-sensitive layer having color sensitivity to red light, and in a multilayer silver halide color photographic light-sensitive material, the unit light-sensitive layers are generally arranged in order from the support side to the red-color-sensitive layer and green. The color sensitive layer and the blue color sensitive layer are installed in this order. However, the order of installation may be reversed depending on the purpose, or the order of installation may be such that different photosensitive layers are sandwiched between the same color-sensitive layers. A non-photosensitive layer such as various intermediate layers may be provided between the above-described silver halide photosensitive layers and as the uppermost layer and the lowermost layer. For the intermediate layer, JP-A-61-43748,
No. 59-113438, No. 59-113440, No. 61-20037, No. 61-20038 may contain a coupler, a DIR compound, etc., and a mixed color as usually used. It may contain an inhibitor. A plurality of silver halide emulsion layers constituting each unit photosensitive layer are composed of a high-sensitivity emulsion layer and a low-sensitivity emulsion layer as described in West German Patent No. 1,121,470 or British Patent No. 923,045. A two-layer structure can be preferably used. Usually, it is preferable that the layers are arranged so that the sensitivities are gradually lowered toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer. Further, JP-A-57-112751, JP-A-62-200350,
As described in JP-A Nos. 62-206541 and 62-206543, a low-sensitivity emulsion layer may be provided on the side farther from the support, and a high-sensitivity emulsion layer may be provided on the side closer to the support.
As a specific example, from the farthest side from the support, a low-sensitivity blue photosensitive layer (BL) / high-sensitivity blue photosensitive layer (BH) / high-sensitivity green photosensitive layer (GH) / low-sensitivity green photosensitive layer (GL) / High-sensitivity red photosensitive layer (RH) / Low-sensitivity red photosensitive layer (RL), or BH / BL / GL / GH / RH / RL, or BH / BL / GH / GL / RL / RH Can be installed in order. Further, as described in JP-B-55-34932, the layers can be arranged in the order of blue-sensitive layer / GH / RH / GL / RL from the side farthest from the support. Further, JP-A-56-25738 and 62-639.
As described in the specification No. 36, it is also possible to arrange the order of blue-sensitive layer / GL / RL / GH / RH from the side farthest from the support.

As described in JP-B-49-15495, the upper layer is the silver halide emulsion layer having the highest photosensitivity, the middle layer is the silver halide emulsion layer having a lower photosensitivity, and the lower layer is the middle layer. Another example is an arrangement in which a silver halide emulsion layer having a lower photosensitivity is arranged and three layers having different sensitivities are sequentially lowered toward the support. Even when it is composed of three layers having different sensitivities, as described in JP-A-59-202464, a medium-sensitivity emulsion from the side remote from the support in the same color-sensitive layer. It may be arranged in the order of layer / high-speed emulsion layer / low-speed emulsion layer. In addition, they may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer, or low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer.
Also, in the case of four layers or more, the arrangement may be changed as described above. In order to improve color reproduction, US Pat. No. 4,66
No. 3,271, No. 4,705,744, No. 4,7
07,436, JP-A-62-16048, 63-
It is preferable to dispose a donor layer (CL) having a multi-layer effect, which has a spectral sensitivity distribution different from that of a main photosensitive layer such as BL, GL, or RL, described in the specification of No. 89850, adjacent to or in proximity to the main photosensitive layer. As described above, various layer configurations and arrangements can be selected according to the purpose of each light-sensitive material. The preferred silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention is silver iodobromide, silver iodochloride, or silver iodochlorobromide containing about 30 mol% or less of silver iodide. .. Particularly preferred is from about 2 mol% to about 2
Silver iodobromide or silver iodochlorobromide containing up to 5 mol% silver iodide. Silver halide grains in photographic emulsions have regular crystals such as cubes, octahedra and tetradecahedrons, grains having irregular crystal forms such as spheres and plates, twin planes, etc. It may have a crystal defect of, or a composite form thereof. The grain size of silver halide is about 0.2
It may be fine particles of micron or less or large size particles having a projected area diameter of up to about 10 microns, and may be a polydisperse emulsion or a monodisperse emulsion. The silver halide photographic emulsion which can be used in the present invention is, for example, Research Disclosure (R
D) No. 17643 (December 1978), 22-2
P. 3, "I. Emulsion preparation
relation and types) ”, ibid. 18
716 (November 1979), page 648, ibid. Thirty
7105 (November 1989), pages 863-865, and Graphide, "Physics and Chemistry of Photography," published by Paul Montel, P. Glafkides, Chemie et.
Phisique Photographique, Pa
ul Montel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (G.F. Duffi).
n, Photographic Emulsion C
chemistry (Focal Press, 196)
6)), "Production and Coating of Photographic Emulsions" by Zelikmann et al., Published by Focal Press (VL Zelikmaneta).
l. , Making and Coating Pho
graphical Emul-sion, Focal
Press, 1964) and the like. US Pat. No. 3,574,628
No. 3,655,394 and British Patent No. 1,41
Monodisperse emulsions described in 3,748 and the like are also preferable.

Further, tabular grains having an aspect ratio of about 5 or more can be used in the present invention. Tabular grains are described in Gutoff, Photographic Science and Engineering (Gutoff, Photograph).
ic Science and Engineering
g), 14: 248-257 (1970); U.S. Pat. Nos. 4,434,226 and 4,414,310.
No. 4,433,048, No. 4,439,520 and British Patent No. 2,112,157, and the like. The crystal structure may be uniform, may have different halogen compositions inside and outside, and may have a layered structure.
Silver halides having different compositions may be joined by epitaxial joining, or may be joined with compounds other than silver halide such as silver rhodanide and lead oxide. Also, a mixture of particles having various crystal forms may be used.
As the silver halide emulsion, those which have been physically ripened, chemically ripened and spectrally sensitized are usually used. Additives used in such a process are Research Disclosure No.
17643, the same No. 18716, and the same No. Thirty
No. 7105, the relevant parts are summarized in the table below. In the present invention, it is preferable to use a non-photosensitive fine grain silver halide. The non-photosensitive fine grain silver halide is a fine grain of silver halide which is not exposed to light during imagewise exposure for obtaining a dye image and is not substantially developed in the developing treatment, and it is preferable that the fog is not fogged in advance. .. The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and may optionally contain silver chloride and / or silver iodide. Preferred is one containing 0.5 to 10 mol% of silver iodide. The fine grain silver halide preferably has an average grain diameter (average value of circle-equivalent diameters of projected areas) of 0.01 to 0.5 μm, and 0.02 to
0.2 μm is more preferable. The fine grain silver halide can be prepared in the same manner as in the case of ordinary photosensitive silver halide. In this case, the surface of the silver halide grain does not need to be optically sensitized nor spectral sensitization. However, prior to adding this to the coating liquid, it is preferable to add a known stabilizer such as a triazole-based, azaindene-based, benzothiazolium-based, mercapto-based compound or zinc compound in advance. Known photographic additives that can be used in the present invention are also described in the above three Research Disclosures, and the relevant portions are shown in the following table.

[0091]

[Table 1]

In order to prevent deterioration of photographic performance due to formaldehyde gas, US Pat. No. 4,411,98
It is preferable to add a compound capable of being immobilized by reacting with formaldehyde described in No. 7 and No. 4,435,503 to the light-sensitive material. Various color couplers can be used in the present invention, and specific examples thereof include Research Disclosure No. 17643, VII-C
~ G, and No. 307105, VII-C to G. Examples of yellow couplers include U.S. Pat. Nos. 3,933,501, 4,022,620, 4,326,024, 4,401,752, and 4,248,961. issue,
Japanese Patent Publication No. 58-10739, British Patent No. 1,425,0
20, No. 1,476,760, and U.S. Pat. No. 3,9.
73,968, 4,314,023, 4,
Those described in 511,649, European Patent 249,473A, etc. are preferable. 5 as a magenta coupler
-Pyrazolone-based and pyrazoloazole-based compounds are preferable, and US Pat. Nos. 4,310,619 and 4,35.
No. 1,897, European Patent No. 73,636, U.S. Patent Nos. 3,061,432, 3,725,067, Research Disclosure No. 24220 (198
June 4), JP-A-60-33552, Research Disclosure No. 24230 (June 1984)
Mon), JP-A-60-43659, JP-A 61-72238.
No. 60-35730, No. 55-118034,
No. 60-185951, U.S. Pat. No. 4,500,63.
No. 0, No. 4,540, 654, No. 4,556, 6
Those described in No. 30, International Publication No. W088 / 04795 and the like are particularly preferable. Examples of cyan couplers include phenol-type and naphthol-type couplers, and US Pat. Nos. 4,052,212, 4,146,396, 4,228,233, and 4,296,200. issue,
No. 2,369,929, No. 2,801,171
No. 2,772,162, No. 2,895,82
No. 6, No. 3,772,002, No. 3,758,3
No. 08, No. 4,334, 011, No. 4,327,
173, West German Patent Publication 3,329,729, European Patents 121,365A, 249,453A,
U.S. Pat. Nos. 3,446,622 and 4,333,9
No. 99, No. 4,775, 616, No. 4,451,
No. 559, No. 4,427,767, No. 4,69
No. 0,889, No. 4,254,212, No. 4,2
Those described in, for example, 96,199 and JP-A-61-42658 are preferable. Typical examples of polymerized dye-forming couplers are U.S. Pat.
080,211, 4,367,282, 4,409,320, 4,576,910, British Patent 2,102,137, European Patent 341,18.
8A and the like. Examples of the coupler in which the color forming dye has an appropriate diffusibility include US Pat. No. 4,366,23.
7, British Patent 2,125,570, European Patent 9
No. 6,570, West German Patent (Publication) No. 3,234,533
Those described in No. 10 are preferable. A colored coupler for correcting unnecessary absorption of a coloring dye is Research Disclosure No. 17643, Item VII-G, ibid.
307105, Section VII-G, U.S. Pat.
670, Japanese Patent Publication No. 57-39413, U.S. Pat. No. 4,
Those described in 004,929, 4,138,258 and British Patent 1,146,368 are preferable. Also, a coupler described in US Pat. No. 4,774,181 for correcting unnecessary absorption of a coloring dye by a fluorescent dye released at the time of coupling, and US Pat. No. 4,777,120.
It is also preferable to use a coupler having as a leaving group a dye precursor group capable of reacting with a developing agent to form a dye as described in JP-A No.

A coupler which releases a photographically useful residue upon coupling is also preferably used in the present invention. The DIR coupler releasing a development inhibitor is the above-mentioned R
D17643, Item VII-F and No. 30710
5, patents described in section VII-F, JP-A-57-15
1944, 57-154234, 60-184.
No. 248, No. 63-37346, No. 63-37350.
U.S. Pat. Nos. 4,248,962 and 4,782,0
Those described in No. 12 are preferable. Examples of couplers that release a nucleating agent or a development accelerator imagewise during development include British Patents 2,097,140 and 2,13.
1,188, JP-A-59-157638, 59-59
The one described in 170840 is preferable. Other compounds that can be used in the light-sensitive material of the present invention include competitive couplers described in US Pat. No. 4,130,427, US Pat. Nos. 4,283,472 and 4,33.
Multi-equivalent couplers described in JP-A-8-393, JP-A-4310-618, JP-A-60-185950 and JP-A-6-195950.
2-24252 and the like DIR redox compound releasing coupler, DIR coupler releasing coupler, DIR coupler releasing redox compound or DIR redox releasing redox compound, EP 173,302A,
No. 313,308A, a coupler that releases a dye that recovers color after withdrawal, R.I. D. No. 11449 and 24
241, a bleaching accelerator releasing coupler described in JP-A-61-2201247, a ligand-releasing coupler described in U.S. Pat. No. 4,555,477, and JP-A-63-7574.
Examples thereof include a coupler releasing a leuco dye described in No. 7, a coupler releasing a fluorescent dye described in U.S. Pat. No. 4,774,181, and the like. The coupler used in the present invention is
It can be incorporated into the photographic material by various known dispersion methods. Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027. Specific examples of the high-boiling point organic solvent having a boiling point of 175 ° C. or higher at atmospheric pressure used in the oil-in-water dispersion method include phthalic acid esters (dibutyl phthalate, 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, etc. ), Phosphoric acid or phosphonic acid esters (triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tryptoxyethyl phosphate, trichloropropyl phosphate, The-
2-ethylhexyl phenylphosphonate, etc.), benzoic acid esters (2-ethylhexyl benzoate, dodecyl benzoate, 2-ethylhexyl-p-hydroxybenzoate etc.), amides (N, N-diethyldodecane amide, N, N-diethyllaurylamide) , N
-Tetradecylpyrrolidone etc.), alcohols or phenols (isostearyl alcohol, 2,4-di-tert-amylphenol etc.), aliphatic carboxylic acid esters (bis (2-ethylhexyl) sebacate, dioctyl azelate, glycerol) Tributyrate, isostearyl lactate, trioctyl citrate, etc.), aniline derivative (N, N-dibutyl-2-butoxy-5-tert-octylaniline, etc.), hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.) And so on. As the auxiliary solvent, an organic solvent having a boiling point of about 30 ° C. or higher, preferably 50 ° C. or higher and about 160 ° C. or lower can be used. Typical examples are ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2- Examples include ethoxyethyl acetate and dimethylformamide. The steps of latex dispersion method, effects and specific examples of latex for impregnation are described in US Pat. No. 4,199,363.
It is described in West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230.

In the color light-sensitive material of the present invention, phenethyl alcohol, JP-A-63-257747 and JP-A-62-257747 are used.
No. 272248, and 1,2-benzisothiazolin-3-one, n-butyl p-hydroxybenzoate, phenol, 4-chloro-3,5-dimethylphenol, 2-phenoxyethanol described in JP-A No. 1-80941. It is preferable to add various preservatives or antifungal agents such as-(4-thiazolyl) benzimidazole. The present invention can be applied to various color light-sensitive materials. Color negative film for general use or movies,
Representative examples include color reversal films for slides or televisions, color papers, color positive films, and color reversal papers. Suitable supports that can be used in the present invention are described, for example, in RD. N
o. 17643, page 28, ibid. 18716, 647
Page right column to page 648 left column, and the same No. 307105
Pp. 879. In the light-sensitive material of the present invention, the total thickness of all hydrophilic colloid layers on the emulsion layer side is 2
It is preferably 8 μm or less, more preferably 23 μm or less, further preferably 18 μm or less, and particularly preferably 16 μm or less. The film swelling speed T _1/2 is preferably 30 seconds or less, more preferably 20 seconds or less. The film thickness is 25
The film swelling rate T _1/2 can be measured according to a method known in the art, which means a film thickness measured under the condition of a temperature of 55 ° C. and a relative humidity of 55% (2 days). For example,
Photographic Science and Engineering (Photo) by A. Green et al.
ogr. Sci. Eng. ), Volume 19, Issue 2, 124-
It can be measured by using a swellometer (swelling meter) of the type described on page 129, and T _1/2 is 3 for a color developing solution.
The saturated film thickness is defined as 90% of the maximum swollen film thickness reached at 0 ° C. for 3 minutes and 15 seconds, and is defined as the time required to reach 1/2 of the saturated film thickness. The film swelling speed T _1/2 can be adjusted by adding a film hardening agent to gelatin as a binder or changing the aging condition after coating. The swelling rate is preferably 150 to 400%. Swelling rate, from the maximum swollen film thickness under the conditions described above,
It can be calculated according to the formula: (maximum swollen film thickness-film thickness) / film thickness. The color photographic light-sensitive material according to the present invention has the above-mentioned R
D. No. 17643, pages 28-29, ibid. 187
No. 16 651 left column to right column, and No. 16 of the same. 307105
It can be developed by a usual method described on pages 880-881.

The color developing solution used in the development processing of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine type color developing agent as a main component. Although aminophenol compounds are also useful as the color developing agent, p-phenylenediamine compounds are preferably used, and a typical example thereof is 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-β-methoxyethylaniline and their sulfates, hydrochlorides or p-toluenesulfonates, etc. may be mentioned. Of these, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline sulfate is particularly preferable. Two or more kinds of these compounds can be used in combination depending on the purpose. The color developer is a pH buffer such as an alkali metal carbonate, borate or phosphate, a chloride salt, a bromide salt, an iodide salt, a benzimidazole, a benzothiazole or a mercapto compound. It is common to include an inhibitor or an antifoggant. If necessary, hydroxylamine,
Diethylhydroxylamine, sulfite, hydrazines such as N, N-biscarboxymethylhydrazine, various preservatives such as phenylsemicarbazides, triethanolamine and catechol sulfonic acids, organic solvents such as ethylene glycol and diethylene glycol, benzyl alcohol , Polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competing couplers, auxiliary developing agents such as 1-phenyl-3-pyrazoline, tackifiers, amino polycarboxylic acids, amino poly Various chelating agents represented by phosphonic acid, alkylphosphonic acid and phosphonocarboxylic acid, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyl Minoji acetate, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo -N, N,
N-trimethylenephosphonic acid, ethylenediamine-N,
Representative examples are N, N, N-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and salts thereof. When the reversal process is performed, black and white development is usually performed before color development. In this black-and-white developing solution, known black-and-white developing agents such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone or aminophenols such as N-methyl-p-aminophenol are used alone. Alternatively, they can be used in combination. The pH of the color developing solution and the black and white developing solution is 9 to 1
Generally, it is 2. The replenishing amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 3 l or less per square meter of the light-sensitive material, and it is possible to reduce the bromide ion concentration in the replenishing solution to 5
It can be less than 00 ml. When the replenishment amount is reduced, it is preferable to prevent the liquid evaporation and air oxidation by reducing the contact area with the air in the processing tank. The contact area between the photographic processing liquid and air in the processing tank can be represented by the aperture ratio defined below. That is,

[0096]

[Equation 1]

The aperture ratio is preferably 0.1 or less, more preferably 0.001 to 0.05. As a method of reducing the aperture ratio in this way, in addition to providing a cover such as a floating lid on the photographic processing liquid surface of the processing tank,
The method using a movable lid described in JP-A-1-82033 and the slit development processing method described in JP-A-63-216050 can be mentioned. Reducing the aperture ratio is not limited to both color development and black and white development,
Subsequent steps, such as bleaching, bleach-fixing, fixing, washing,
It is preferably applied in all steps such as stabilization. Further, the amount of replenishment can be reduced by using a means for suppressing the accumulation of bromide ions in the developing solution. The color development processing time is usually set to 2 to 5 minutes, but the processing time can be further shortened by setting the temperature and high pH and using the color developing agent at a high concentration. The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed at the same time as the fixing process (bleach-fixing process) or separately. Further, in order to speed up the processing, a processing method of bleach-fixing processing after bleaching processing may be used. Further, treatment with two continuous bleach-fixing baths, fixing treatment before the bleach-fixing treatment, or bleaching treatment after the bleach-fixing treatment can be optionally carried out. As the bleaching agent, compounds of polyvalent metals such as iron (III), peracids, quinones, nitro compounds and the like are used. As a typical bleaching agent, an organic complex salt of iron (III), for example, an amino acid such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, and glycol etherdiaminetetraacetic acid. Polycarboxylic acids or complex salts of citric acid, tartaric acid, malic acid and the like can be used. Of these, aminopolycarboxylic acid iron (III) complex salts including ethylenediaminetetraacetic acid iron (III) complex salts and 1,3-diaminopropanetetraacetic acid iron (III) complex salts are preferable from the viewpoint of rapid treatment and prevention of environmental pollution. .. Further, the aminopolycarboxylic acid iron (III) complex salt is particularly useful in both the bleaching solution and the bleach-fixing solution. The pH of a bleaching solution or a bleach-fixing solution using these iron (III) aminopolycarboxylic acid complex salts is usually 4.0 to 8, but lower pH can be used for speeding up the processing.

If necessary, a bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their pre-bath.
Specific examples of useful bleaching accelerators are described in the following specifications: US Pat. No. 3,893,858, West German Patents 1,290,812, 2,059,988, JP No. 53-32736, No. 53-57831, No. 53
-37418, 53-72623, 53-95.
No. 630, No. 53-95631, No. 53-10423.
No. 2, No. 53-124424, No. 53-141623.
No. 53-28426, Research Disclosure No. 17129 (July 1978) and the like, which have a mercapto group or a disulfide group.
Thiazolidine derivatives described in JP-A-50-140129; JP-B-45-8506, JP-A-52-20832
No. 53-32735, U.S. Pat. No. 3,706,5
Thiourea derivatives described in No. 61; West German Patent No. 1,12
7,715, iodide salts described in JP-A-58-16,235; West German Patent Nos. 966,410 and 2,748,
No. 430, polyoxyethylene compounds; Japanese Patent Publication No. 45-8836, polyamine compounds; Others, JP-A-49-40,943, 49-59,644, 53-94,927 54-35, 727, 5
Compounds described in Nos. 5-26,506 and 58-163,940; bromide ion and the like can be used. Among them, compounds having a mercapto group or a disulfide group are preferable from the viewpoint of having a large accelerating effect, and in particular, US Pat. No. 3,893,
858, West German Patent 1,290,812, JP-A-5
The compounds described in 3-95,630 are preferred. Furthermore,
The compounds described in US Pat. No. 4,552,834 are also preferred. These bleaching accelerators may be added to the light-sensitive material.
These bleaching accelerators are particularly effective when bleach-fixing a color light-sensitive material for photographing. In addition to the above compounds, the bleaching solution and the bleach-fixing solution preferably contain an organic acid for the purpose of preventing bleach stain. Particularly preferable organic acid is a compound having an acid dissociation constant (pKa) of 2 to 5, and specifically, acetic acid, propionic acid and the like are preferable. Examples of the fixing agent used in the fixing solution and the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas, and a large amount of iodide salts, but thiosulfates are generally used. In particular, ammonium thiosulfate can be used most widely. Further, the combined use of thiosulfate and thiocyanate, thioether compounds, thiourea and the like is also preferable. As a preservative for the fixing solution and the bleach-fixing solution, sulfites, bisulfites, carbonyl bisulfite adducts or sulfinic acid compounds described in European Patent 294769A are preferable. Further, various aminopolycarboxylic acids and organic phosphonic acids are preferably added to the fixing solution and the bleach-fixing solution for the purpose of stabilizing the solution. In the present invention, the fixer or the bleach-fixer has a pKa of 6.0 to adjust the pH.
It is preferable to add a compound of 9.0, preferably imidazoles such as imidazole, 1-methylimidazole, 1-ethylimidazole and 2-methylimidazole in an amount of 0.1 to 10 mol / l. The total time of the desilvering process is preferably as short as possible in the range where desilvering failure does not occur. The preferred time is 1 to 3 minutes, more preferably 1 to 2 minutes. The treatment temperature is 25 ° C to 50 ° C, preferably 35 ° C.
C to 45C. In the preferable temperature range, the desilvering rate is improved and the stain generation after the processing is effectively prevented.

In the desilvering process, it is preferable that the stirring is strengthened as much as possible. As a concrete method for strengthening the stirring, a method of causing a jet of a processing solution to collide with an emulsion surface of a light-sensitive material described in JP-A-62-183460, and stirring using a rotating means of JP-A-62-183461. A method to improve the effect, further a method to improve the stirring effect by moving the light-sensitive material while bringing the emulsion surface into contact with the wiper blade provided in the solution and making the emulsion surface turbulent, circulation of the entire processing solution There is a method of increasing the flow rate. Such stirring improving means includes a bleaching solution, a bleach-fixing solution,
It is effective with any of the fixing solutions. It is considered that the improvement of the stirring speeds up the supply of the bleaching agent and the fixing agent into the emulsion film and, as a result, increases the desilvering rate. Further, the above-mentioned stirring improving means is more effective when a bleaching accelerator is used, and it is possible to remarkably increase the accelerating effect and eliminate the fixing inhibiting effect of the bleaching accelerator. The automatic processor used for the light-sensitive material of the present invention is disclosed in JP-A-60-19125.
No. 7, No. 60-191258, No. 60-191259
It is preferable to have the photosensitive material conveying means described in No. As described in JP-A-60-191257, such a conveying means can significantly reduce the carry-in of the treatment liquid from the front bath to the rear bath and has a high effect of preventing the performance deterioration of the treatment liquid. Such effects are particularly effective in shortening the processing time in each step and reducing the amount of processing liquid replenishment. The silver halide color photographic light-sensitive material of the present invention is generally subjected to a washing and / or stabilizing step after desilvering. The amount of rinsing water in the rinsing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), application, and further, the rinsing water temperature, the number of rinsing tanks (number of stages), replenishment system such as countercurrent, forward flow, and other various conditions. It can be set in a wide range. Of these, the relationship between the number of washing tanks and the amount of water in the multi-stage countercurrent system is described in Journal.
-Al of the Society of Mot
Ion Picture and Tele-visio
n Engineers, Vol. 64, P.N. 248-253
(May, 1955 issue). According to the multi-stage counter-current method described in the above literature, the amount of washing water can be significantly reduced, but due to the increase in the residence time of water in the tank, bacteria propagate, and the suspended matter produced adheres to the photosensitive material, etc. Problems arise. In the processing of the color light-sensitive material of the present invention, the method of reducing calcium ion and magnesium ion described in JP-A-62-288838 can be used very effectively as a solution to such a problem. In addition, JP-A-57-8,
No. 542, isothiazolone compounds, siabendazoles, chlorinated fungicides such as chlorinated sodium isocyanurate, and other benzotriazoles, etc. Hiroshi Horiguchi, "Chemistry of Antibacterial and Antifungal Agents" (1986) Sankyo Publishing, "Sterilization, sterilization and antifungal technology of microorganisms" edited by Sanitary Technology Association (1982) Industrial Technology Association, "Antibacterial and Antifungal Agent Encyclopedia" edited by Japan Society for Antibacterial and Antifungal Agents (1
It is also possible to use the fungicide described in 986). The pH of washing water in the processing of the light-sensitive material of the present invention is 4 to 9, preferably 5 to 8. The washing water temperature and washing time can be set variously depending on the characteristics of the light-sensitive material, the use, etc., but generally 15 to 45 ° C. and 20 seconds to 10 minutes, preferably 25.
A range of 30 seconds to 5 minutes at -40 ° C is selected. Further, the light-sensitive material of the present invention can be directly processed with a stabilizing solution instead of the above washing with water. In such stabilizing treatment, JP-A-57-8543 and JP-A-58-14834 are used.
All of the known methods described in No. 60-220345 can be used.

In some cases, the washing treatment may be followed by a further stabilizing treatment. As an example of the stabilizing treatment, a stabilizer containing a dye stabilizer and a surfactant, which is used as a final bath of a color light-sensitive material for photographing, is used. You can mention the bath. Examples of dye stabilizers include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine, and aldehyde sulfite adducts. Various chelating agents and antifungal agents can also be added to this stabilizing bath. The overflow solution accompanying the above washing with water and / or supplementation of the stabilizing solution can be reused in other steps such as the desilvering step. In the processing using an automatic processor or the like, when each of the above processing solutions is concentrated by evaporation, it is preferable to add water to correct the concentration. The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and accelerating the processing. For incorporation, it is preferable to use various precursors of color developing agents. For example, U.S. Pat. No. 3,342,597
Indoaniline compounds described in No. 3,342,5
No. 99, Research Disclosure No. 14,8
50 and No. 50. Schiff base type compounds described in JP-A Nos. 15,159,159, aldol compounds described in JP-A No. 13,924, metal salt complexes described in US Pat. No. 3,719,492, and urethane compounds described in JP-A-53-135628. be able to. The silver halide color light-sensitive material of the present invention may contain various 1-phenyl-3-pyrazolidones in order to accelerate color development, if necessary.
Typical compounds are JP-A Nos. 56-64339 and 57-57.
Nos. 144547 and 58-115438. Various treatment liquids in the present invention are 10 ° C to 5 ° C.
Used at 0 ° C. Usually, a temperature of 33 ° C. to 38 ° C. is standard, but a higher temperature is used to accelerate the processing to shorten the processing time, and a lower temperature is used to improve the image quality and the stability of the processing liquid. be able to. The silver halide light-sensitive material of the present invention is disclosed in US Pat. No. 4,500,6.
26, JP-A-60-133449 and 59-218.
No. 443, No. 61-238056, European Patent 210,
It can also be applied to the photothermographic material described in 660A2.

[0101]

Use of the compound of the present invention has a great effect of preventing color mixture and can improve storage stability. This effect is particularly great when the pH of the color developer is high.

[0102]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited thereto.

Example 1 Preparation of Sample 101 Sample 101 was prepared by preparing a multilayer color light-sensitive material having the following compositions on a cellulose triacetate film support having a thickness of 127 μm and having an undercoat. The numbers represent the amount added per m ² . The effect of the added compound is not limited to the described use. First layer: anti-halation layer Black colloidal silver 0.25 g Gelatin 1.9 g UV absorber U-1 0.04 g UV absorber U-2 0.1 g UV absorber U-3 0.1 g UV absorber U-6 0.1 g High boiling organic solvent Oil-1 0.1 g Second layer: intermediate layer Gelatin 0.40 g High boiling organic solvent Oil-3 40 mg Third layer: intermediate layer Fogging fine grain silver iodobromide emulsion (average grain size 0.06 μm, AgI content 1 mol%)
Silver amount 0.05 g Gelatin 0.4 g Fourth layer: low-sensitivity red-sensitive emulsion layer Silver iodobromide emulsion spectrally sensitized with sensitizing dyes S-1 and S-2 (average grain size 0.4 μm, AgI content 4 1: 1 mixture of 0.5 mol% monodisperse cubes and monodisperse cubes having an average particle size of 0.3 μm and an AgI content of 4.5 mol%) Silver amount 0.4
g Gelatin 0.8 g Coupler C-1 0.20 g Coupler C-9 0.05 g Compound Cpd-D 0.015 g High boiling point organic solvent Oil-2 0.10 g Fifth layer: middle-sensitive red-sensitive emulsion layer Sensitizing dye S -1 and S-2 spectrally sensitized silver iodobromide emulsion (monodisperse cube with an average grain size of 0.5 μm and an AgI content of 4 mol%) silver amount 0.4 g gelatin 0.8 g coupler C-1. 2 g Coupler C-2 0.05 g Coupler C-3 0.2 g High boiling point organic solvent Oil-2 0.1 g Sixth layer: high sensitivity red sensitive emulsion layer Spectral sensitized with sensitizing dyes S-1 and S-2. Silver iodobromide emulsion (monodisperse twin grains having an average grain size of 0.7 μm and AgI content of 2 mol%) Silver amount 0.4 g Gelatin 1.1 g Coupler C-3 0.7 g Coupler C-1 0.3 g 7 layers: Intermediate layer Gelatin 0.6 g Dye D-1 0.0 g

Eighth layer: intermediate layer Fogging silver iodobromide emulsion (average grain size 0.06 μm, Ag
I content 0.3 mol%) 0.02 g Gelatin 1.0 g Anti-color mixing agent Cpd-A 0.2 g Ninth layer: low-sensitivity green sensitive emulsion layer Spectral sensitized with sensitizing dyes S-3 and S-4. Silver iodobromide emulsion (1: 1 mixture of monodisperse cubes having an average particle size of 0.4 μm and AgI content of 4.5 mol% and monodisperse cubes having an average particle size of 0.2 μm and AgI content of 4.5 mol%)
Silver amount 0.5 g Gelatin 0.5 g Coupler C-4 0.20 g Coupler C-7 0.10 g Coupler C-8 0.10 g Compound Cpd-B 0.03 g Compound Cpd-E 0.02 g Compound Cpd-F 0. 02g Compound Cpd-G 0.02g Compound Cpd-H 0.02g Compound Cpd-D 10mg High-boiling point organic solvent Oil-1 0.1g High-boiling point organic solvent Oil-2 0.1g 10th layer: Medium-sensitive green sensitive emulsion layer Silver iodobromide emulsion spectrally sensitized with sensitizing dyes S-3 and S-4 (monodisperse cube having an average grain size of 0.5 μm and an AgI content of 3 mol%) Silver amount 0.4 g Gelatin 0.6 g Coupler C- 4 0.1 g Coupler C-7 0.1 g Coupler C-8 0.1 g Compound Cpd-B 0.03 g Compound Cpd-E 0.02 g Compound Cpd-F 0.02 g Compound Cpd- G 0.05 g Compound Cpd-H 0.05 g High boiling point organic solvent Oil-2 0.01 g 11th layer: High sensitivity green sensitive emulsion layer Silver iodobromide spectrally sensitized with sensitizing dyes S-3 and S-4 Emulsion (average particle size in terms of spheres 0.6 μm, AgI scene 1.3 mol%, monodisperse plate having average diameter / thickness of 7) Silver amount 0.5
g Gelatin 1.0 g Coupler C-4 0.4 g Coupler C-7 0.2 g Coupler C-8 0.2 g Compound Cpd-B 0.08 g Compound Cpd-E 0.02 g Compound Cpd-F 0.02 g Compound Cpd- G 0.02 g Compound Cpd-H 0.02 g High boiling point organic solvent Oil-1 0.02 g High boiling point organic solvent Oil-2 0.02 g 12th layer: Intermediate layer Gelatin 0.6 g Dye D-2 0.05 g Thirteenth Layer: Yellow filter layer Yellow colloidal silver Amount of silver 0.1 g Gelatin 1.1 g Color mixing inhibitor Cpd-A 0.01 g High boiling point organic solvent Oil-1 0.01 g

Layer 14: Intermediate layer Gelatin 0.6 g Layer 15: Low sensitivity blue sensitive emulsion layer Sensitizing dyes S-5 and S-
6 silver sensitized silver iodobromide emulsion (average grain size 0.4 μm, A
Monodisperse cube with gI content of 3 mol% and average particle size 0.2μ
m, 1: 1 mixture of monodisperse cubes with AgI content of 3 mol%) Silver amount 0.6 g Gelatin 0.8 g Coupler C-5 0.6 g High boiling point organic solvent Oil-2 0.02 g 16th layer: Medium sensitivity Blue-sensitive emulsion layer Silver iodobromide emulsion sensitized with sensitizing dyes S-5 and S-6 (monodisperse cube having an average grain size of 0.5 μm and AgI content of 2 mol%) Silver amount 0.4 g Gelatin 0. 9 g Coupler C-5 0.3 g Coupler C-6 0.3 g High boiling point organic solvent Oil-2 0.02 g 17th layer: High-sensitivity blue-sensitive emulsion layer Sensitized with sensitizing dyes S-5 and S-6. Silver iodobromide emulsion (tabular grains having an average grain size in terms of spheres of 0.7 μm, an AgI content of 1.5 mol%, and an average diameter / thickness value of 7) of silver 0.4
g Gelatin 1.2g Coupler C-6 0.7g 18th layer: 1st protective layer Gelatin 0.7g UV absorber U-1 0.04g UV absorber U-3 0.03g UV absorber U-4 0. 03g UV absorber U-5 0.05g UV absorber U-6 0.05g High boiling point organic solvent Oil-1 0.02g Formalin scavenger Cpd-C 0.8g Dye D-3 0.05g 19th layer: 2nd Protective layer Fogging fine grain silver iodobromide emulsion (average grain size 0.06μ
m, AgI content 1 mol%) Silver amount 0.1 g Gelatin 0.4 g 20th layer: Third protective layer Gelatin 0.4 g Polymethylmethacrylate (average particle size 1.5 μm)
1 g Methyl methacrylate / acrylic acid 4: 6 copolymer (average particle size 1.5 μm) 0.1 g Silicone oil 0.03 g Surfactant W-1 3.0 mg Each layer contains gelatin in addition to the above composition. Hardener H-1 and surfactants for coating and emulsification were added. Furthermore, antiseptic
1,2-Benzisothiazolin-3-one, 2-phenoxyethanol, and phenethyl alcohol were added as antifungal agents. In the emulsion used here, the monodisperse means that the coefficient of variation is 20% or less.

[0106]

[Chemical 42]

[0107]

[Chemical 43]

[0108]

[Chemical 44]

[0109]

[Chemical 45]

[0110]

[Chemical 46]

[0111]

[Chemical 47]

[0112]

[Chemical 48]

[0113]

[Chemical 49]

[0114]

[Chemical 50]

[0115]

[Chemical 51]

[0116]

[Chemical 52]

[0117]

[Chemical 53]

[0118]

[Chemical 54]

Preparation of Samples 101 to 114 In Sample 101, the DIR compound Cpd-D of the fourth layer was prepared.
Instead of Comparative Compound A, Comparative Compound B, Comparative Compound C, compounds (1), (2), (3), (4) of the present invention,
(6), (13), (15), (16), (17),
A sample was prepared in the same manner as Sample 101 except that equimolar amounts of (18), (27) and (30) were added. The obtained samples 101 to 116 were cut into strips, exposed to a wedge through a red filter, and then uniformly exposed to a green filter. Next, exposure to 20 μm and 1 mm width with soft X-ray was performed to evaluate the edge effect. The treatment was performed according to the following prescription. The inter-image effect is that the cyan color density is 2.0 and the cyan color density is Dm.
Evaluation was made based on the difference in magenta density in the in part. Edge effect is 1mm through R filter with micro densitometer
The densities in the width and 20 μm width were measured, and the ratio of these densities was taken for evaluation. Next, each sample was stored under conditions of 40 ° C. and 80% RH for 14 days, and processed at the same time as that stored at room temperature to compare the maximum densities of the cyan color-developing layers. The obtained results are shown in Table 2. As is clear from Table 2, when the DIR compound of the present invention is used, the interimage effect and the edge effect are large, and the decrease in the maximum density during storage (corresponding to the increase in fog) is small. Similar results were obtained when the DIR / compound was added to the second layer, the third layer, the eighth layer, the ninth layer, the fourteenth layer, and / or the fifteenth layer instead of the fourth layer.

[0120]

[Table 2]

[0121]

[Chemical 55]

[0122]

[Table 3]

[0123]

[Table 4]

[0124]

[Table 5]

[0125]

[Table 6]

[0126]

[Table 7]

[0127]

[Table 8]

[0128]

[Table 9]

[0129]

[Table 10]

Example 2 On a subbed cellulose triacetate film support,
A sample 201, which is a multi-layer color light-sensitive material having the following composition, was prepared. The amount coated amount (Composition of photosensitive layer) is represented in units of g / m ² of silver for silver halide and colloidal silver, also couplers, the amount for the additives and gelatin, expressed in units of g / m ^2, The sensitizing dye is shown by the number of moles per mole of silver halide in the same layer. The symbols indicating additives have the following meanings. However, when there are multiple utilities, one of them is listed as a representative. UV: UV absorber, Solv: High boiling organic solvent, ExF: Dye, ExS: Sensitizing dye, ExC: Cyan coupler, Ex
M: Magenta coupler, ExY: Yellow coupler,
Cpd; Additive First layer (antihalation layer) Black colloidal silver 0.15 Gelatin 2.0 ExM-6 0.2 UV-1 0.03 UV-2 0.06 UV-3 0.07 Solv-10 .3 Solv-2 0.08 ExF-1 0.01 ExF-2 0.01 ExF-3 0.005 Cpd-6 0.001 Second layer (low-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, uniform AgI type, sphere equivalent diameter 0.4 μm, variation coefficient of sphere equivalent diameter 30%, plate-like particles, diameter / thickness ratio 3.0) Silver iodobromide emulsion (AgI 6 mol%, core-shell ratio 2: 1)
Internal high AgI type, sphere equivalent diameter 0.45 μm variation coefficient of sphere equivalent diameter 23%, plate-like particles, diameter / thickness ratio 2.0)

Third Layer (Medium Sensitivity Red Sensitive Emulsion Layer) Silver iodobromide emulsion (AgI 6 mol%, core-shell ratio 2: 1)
Internal high AgI type, sphere equivalent diameter 0.65 μm, variation coefficient of sphere equivalent diameter 23%, plate-like particles, diameter / thickness ratio 2.0) 4th layer (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (9.3 mol% of AgI, multi-structured grains having a core-shell ratio of 3: 4: 2, AgI content of 2 from the inside)
4,0,6 mol%, equivalent sphere diameter 0.75 μm, coefficient of variation of equivalent sphere diameter 23%, plate-like particles, diameter / thickness ratio 2.5) Sixth layer (low-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, uniform AgI type, sphere equivalent diameter 0.33 μm, variation coefficient of sphere equivalent diameter 37%, plate-like grain, diameter / thickness ratio 2.0) Seventh layer (medium-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, uniform AgI type, equivalent sphere diameter 0.55 μm, variation coefficient of equivalent sphere diameter 15%, plate-like grain, diameter / thickness ratio 4.0)

Eighth layer (high-sensitivity green emulsion layer) Silver iodobromide emulsion (AgI 8.8 mol%, silver amount ratio 3:
4: 2 multilayer structure particles, AgI content from the inside 24 mol, 0 mol, 3 mol%, sphere equivalent diameter 0.75 μm, variation coefficient of sphere equivalent diameter 23%, plate-like particles, diameter / thickness ratio 1.6. ) The 10th layer (donor layer having a multilayer effect for the red-sensitive layer) Silver iodobromide emulsion (AgI 8 mol%, internal high AgI type having a core-shell ratio of 2: 1, spherical equivalent diameter 0.65 μm, variation coefficient of spherical equivalent diameter 25 %, Plate-like particles, diameter / thickness ratio of 2.0) Silver iodobromide emulsion (AgI 4 mol%, uniform AgI type, sphere equivalent diameter 0.4 μm, variation coefficient of sphere equivalent diameter 30%, plate-like grain, diameter / thickness ratio 3.0)

Twelfth Layer (Low Sensitivity Blue Sensitive Emulsion Layer) Silver iodobromide emulsion (AgI 4.5 mol%, uniform AgI type,
Equivalent sphere diameter 0.7 μm, variation coefficient of sphere equivalent diameter 15%, plate-like particles, diameter / thickness ratio 7.0) Silver iodobromide emulsion (AgI 3 mol%, uniform AgI type, sphere-equivalent diameter 0.3 μm, variation coefficient of sphere-equivalent diameter 30%, plate-like grain, diameter / thickness ratio 7.0) 14th layer (high-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion (AgI 10 mol%, internal high AgI type,
Equivalent sphere diameter 1.0 μm, variation coefficient of sphere equivalent diameter 25%, multiple twinned plate-like particles, diameter / thickness ratio 2.0) In addition to the above components, each layer contains an emulsion stabilizer Cpd-3.
(0.07 g / m ² ), surfactant W-1 (0.006
g / m ² ), W-2 (0.33 g / m ² ), W-3
(0.10 g / m ² ) was added as a coating aid or an emulsifying dispersant. In addition, 1,2-benzisothiazolin-3-one, 2-phenoxyethanol, and phenethyl alcohol were added mainly for the purpose of improving antifungal and antibacterial properties.

[0134]

[Chemical 56]

[0135]

[Chemical 57]

[0136]

[Chemical 58]

[0137]

[Chemical 59]

[0138]

[Chemical 60]

[0139]

[Chemical formula 61]

[0140]

[Chemical formula 62]

[0141]

[Chemical 63]

[0142]

[Chemical 64]

[0143]

[Chemical 65]

[0144]

[Chemical 66]

[0145]

[Chemical 67]

[0146]

[Chemical 68]

Preparation of Samples 202 to 214 Comparative compounds as shown in Table 1 in place of the DIR coupler ExY-9 added to the tenth layer in Sample 201,
The compound of the present invention was treated with 3 × 10 exp (−4) mole / m
A sample was prepared in the same manner as Sample 201 except that xm was added.
The obtained samples 201 to 214 were evaluated for the interimage effect, the edge effect, the fog during long-term storage, and the like in the same procedure as in Example 1. The treatment was performed in the following steps. As a result, the same results as in Example 1 were obtained. Replenishment amount is per 35 mm width and 1 m length. Next, the composition of the treatment liquid will be described.

Tap water was used as an H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas).
And OH type anion exchange resin (the same Amberlite IR-
400) and passed through a mixed bed type column to treat calcium and magnesium ions at a concentration of 3 mg / L or less, and then 20 mg of sodium isocyanurate dichloride.
/ L and 0.15 g / l sodium sulfate were added. The pH of this solution was in the range of 6.5-7.5.

Example 3 Preparation of Irregular (Twin Crystal Plate) Silver Halide Emulsion 25 g of potassium bromide, 24 g of potassium iodide, 1.9 g of potassium thiocyanate and 24 g of gelatin were added to 1 liter of water. While maintaining the temperature at 60 ° C. and stirring vigorously, an aqueous solution of silver nitrate and an aqueous solution of potassium bromide were added by a double jet method by an ordinary ammonia method, and finally an iodine content of 8 mol% and an average particle diameter of 1. A thick plate-like silver iodobromide emulsion having a thickness of 0 μm and having a relatively irregular shape was prepared. After this,
A photosensitive silver iodobromide emulsion was prepared by adding 230 mg / Ag mol of dye (a) and 50,000 ppm of phenoxyethanol (against gelatin), followed by chemical sensitization (post-ripening) with sodium thiosulfate and chloroauric acid. (B) was obtained. Same as Emulsion (B), except that the amount of potassium iodide in the first solution was 18 g, the temperature was 40 ° C., the iodide content was 6 mol%, and the average grain size was 0.6 μm. An emulsion (C) was obtained. Further, a photosensitive silver iodobromide emulsion (D) which was not chemically sensitized was obtained in the same manner as the emulsion (C).

[0150]

[Chemical 69]

Preparation of Coating Samples The following formulation was coated using a polyethylene terephthalate support having both sides undercoated. (Back side) Bottom layer gelatin 0.45 g / m ² anionic polymer ^* 0.37 g / m ² W-1 2 mg / m ² second layer gelatin 5 g / m ² anionic polymer ^* 2.9 g / m ² top layer gelatin 1 g / m ² W-2 21 mg / m ² C ₈ F ₁₇ SO ₃ K 6 mg / m ² polypotassium p-vinylbenzene sulfonate
51 mg / m ² polymethylmethacrylate fine particles (average particle size 3 μm)
^{35mg / m 2 D-4 113mg} / m 2 D-5 53mg / m 2 D-6 72mg / m 2 bis - (vinylsulfonyl acetamide) ethane
470 mg / m ² (emulsion layer) Bottom layer Ag amount 0.8 g / m ² gelatin using emulsion (D) 1.1 g / m ² polyethylene oxide 4 mg / m ² 4-hydroxy-6-methyl-1,3,3 3a, 7- tetrazaindene ^{8.5mg / m 2 Cpd-8 0.8mg} / m 2 Poripotashiumu p- vinyl sulfonate
17 mg / m ² Cpd-9 0.5 mg / m ²

Second layer Ag amount 1.4 g / m ² gelatin using emulsion (C) ² g / m ² polyethylene oxide 7 mg / m ² 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaine Den 15 mg / m ² Cpd-8 1.5 mg / m ² Polypotassium p-vinylbenzene sulfonate
50 mg / m ² Cpd-9 0.4 mg / m ² 3rd layer Ag amount 4.5 g / m ² gelatin using the emulsion (B) 8.3 g / m ² polyethylene oxide 55 mg / m ² 4-hydroxy-6- Methyl-1,3,3a, 7-tetrazaindene 45 mg / m ² CH ₃ CH ₂ C (CH ₂ OH) ₃ 210 mg /
m ² polypotassium p-vinylbenzene sulfonate
63 mg / m ² phenoxyethanol 205 mg / m ² top layer gelatin 0.9 g / m ² Cpd-10 13 mg / m ² Cpd-11 50 mg / m ² Cpd-12 88 mg / m ² 4-hydroxy-6-methyl- 1,3,3a, 7-Tetrazaindene 15 mg / m ² Polymethylmethacrylate fine particles (average particle size 3 μ)
24 mg / m ² polypotassium p-vinylbenzene sulfonate
6 mg / m ² fluorine-containing surfactant Cpd-13

[0153]

[Chemical 70]

[0154]

[Chemical 71]

[0155]

[Chemical 72]

[0156]

[Chemical 73]

[0157]

[Chemical 74]

[0158]

[Chemical 75]

Preparation of Samples 302 to 315 In the sample 301, the DIR compound Cpd-D used in the samples 101 to 114 of Example 1 to the compound (18) of the present invention were applied to the second and third layers as coated silver in each layer. Amount 1 mole
5 × 10 ⁻⁴ mole was added. These were dissolved in the same amount of tricresylphosphate and 10 times the amount of ethyl acetate added as a cosolvent, and then dispersed by a homogenizer. Example 1 for the obtained samples 301 to 315
The edge effect was evaluated in the same manner as in. These samples are D
Treatment was carried out in a small tank at −20 ° C. for 7 minutes using the −76 treatment recipe. As a result, the samples to which the DIR compound was added had a higher edge effect, but the samples using the compound of the present invention had a particularly high edge effect.

Example 4 A color photographic light-sensitive material was prepared by applying the following first to twelfth layers to a paper support laminated on both sides with polyethylene in multiple layers. 15% by weight on the coated side of the first layer of polyethylene
Of anatase type titanium oxide as a white pigment and a trace amount of ultramarine as a bluish dye. (Photosensitive layer composition) The components and the coating amounts shown in g / m ² are shown below. For silver halide, the coating amount in terms of silver is shown. First layer (gelatin layer) Gelatin ・ ・ ・ 1.30 Second layer (antihalation layer) Black colloidal silver ・ ・ ・ 0.10 Gelatin ・ ・ ・ 0.70 Third layer (low sensitivity red sensitive layer) Red increase Silver chloroiodobromide spectrally sensitized with a dye (ExS-1, 2, 3) (1 mol% silver chloride / 4 mol% silver iodide, average grain size 0.3 μ, grain size distribution 10%, cubic) , Core iodide type core shell ... 0.06 Silver iodobromide spectrally sensitized with a red sensitizing dye (ExS-1, 2, 3) (4 mol% silver iodide, average grain size 0. 5μ,
Particle size distribution 15%, cube) ... 0.10 Gelatin ... 1.00 Cyan coupler (ExC-1) ... 0.14 Cyan coupler (ExC-2) ... 0.07 Anti-fading agent (Cpd-2, 3, 4 equivalents) ...
12 Coupler dispersion medium (Cpd-6) ... 0.03 Coupler solvent (Solv-1, 2, 3 equivalents)
0.06 Development accelerator (Cpd-13) ... 0.05 Fourth layer (high-sensitivity red-sensitive layer) Iodobromide spectrally sensitized with a red sensitizing dye (ExS-1, 2, 3) Silver (silver iodide 6 mol%, average grain size 0.8 μ,
Grain size distribution 20%, flat plate (aspect ratio = 8, core iodine) ・ ・ ・ 0.15 gelatin ・ ・ ・ 1.00 cyan coupler (ExC-1) ・ ・ ・ 0.20 cyan coupler (ExC-2) ) ... 0.10 Anti-fading agent (Cpd-2, 3, 4 equivalents) ...
15 Coupler dispersion medium (Cpd-6) ... 0.03 Coupler solvent (Solv-1, 2, 3 equivalents)
・ 0.10

Fifth layer (intermediate layer) Magenta colloidal silver: 0.02 Gelatin: 1.00 Color mixing inhibitor (Cpd-7, 16): 0.08 Color mixing inhibitor solvent (Solv-4) 5) ... 0.16 Polymer latex (Cpd-8) ... 0.10 DIR-HQ (Cpd-24) ... 0.015 6th layer (low sensitivity green sensitive layer) Green sensitizing dye Silver chloroiodobromide spectrally sensitized with (ExS-3, 4) (1 mol% silver chloride / 2.5 mol% silver iodide, average grain size 0.28 μ, grain size distribution 8%, cubic, core Iodine core shell)) ... 0.04 Silver iodobromide spectrally sensitized with a green sensitizing dye (ExS-3, 4) (silver iodide 2.5 mol%, average grain size 0.48 μm, Grain size distribution 12%, cubic) 0.06 Gelatin 0.80 Magenta coupler ( ExM-1, 2 equivalents)
0.10 Anti-fading agent (Cpd-9) ... 0.10 Anti-staining agent (Cpd-10, 11 equivalents) ...
0.01 Anti-staining agent (Cpd-5) ... 0.001 Anti-staining agent (Cpd-12) ... 0.01 Coupler dispersion medium (Cpd-6) ... 0.05 Coupler solvent (Solv- 4, 6) ... 0.15 DIR-HQ (Cpd-24) ... 0.015 7th layer (high sensitivity green sensitive layer) Spectral sensitized with a green sensitizing dye (ExS-3, 4). Silver iodobromide (3.5 mol% silver iodide, average grain size 1.0 μ,
Grain size distribution 21%, flat plate (aspect ratio = 9, uniform iodine type) ... 0.10 Gelatin ... 0.80 Magenta coupler (ExM-1, 2 equivalents) ...
0.10 Anti-fading agent (Cpd-9) ... 0.10 Anti-staining agent (Cpd-10, 11, 22 equivalents)
... 0.01 Anti-staining agent (Cpd-5) ... 0.001 Anti-staining agent (Cpd-12) ... 0.01 Coupler dispersion medium (Cpd-6) ... 0.05 Coupler solvent (Solv-4, 6) ... 0.15 Eighth layer (yellow filter layer) Yellow colloidal silver ... 0.20 Gelatin ... 1.00 Color mixing inhibitor (Cpd-7) ... 06 Color-mixing inhibitor solvent (Solv-4, 5) ... 0.15 Polymer latex (Cpd-8) ... 0.10 9th layer (low-sensitivity blue-sensitive layer) Blue sensitizing dye (ExS-5, 6) Spectral-sensitized silver chloroiodobromide (2 mol% silver chloride / 2.5 mol% silver iodide, average grain size 0.38μ, grain size distribution 8%, cubic, core-iodine core shell) ) ... 0.07 Spectral sensitization with blue sensitizing dye (ExS-5, 6) Silver iodobromide (2.5 mol% silver iodide, average grain size 0.55)
μ, particle size distribution 11%, cube) ... 0.10 gelatin ... 0.50 yellow coupler (ExY-1, 2 equivalents) ...
0.20 Anti-staining agent (Cpd-5) ... 0.001 Anti-fading agent (Cpd-14) ... 0.10 Coupler dispersion medium (Cpd-6) ... 0.05 Coupler solvent (Solv- 2) ... 0.05

Layer 10 (high-sensitivity blue-sensitive layer) Silver iodobromide spectrally sensitized with a blue sensitizing dye (ExS-5, 6) (2.5 mol% silver iodide, average grain size 1.4 μm) ,
Particle size distribution 21%, flat plate (aspect ratio = 14))
・ ・ ・ 0.25 Gelatin ・ ・ ・ 1.00 Yellow coupler (ExY-1, 2 equivalents) ・ ・ ・
0.40 Anti-staining agent (Cpd-5) ... 0.002 Anti-fading agent (Cpd-14) ... 0.10 Coupler dispersion medium (Cpd-6) ... 0.15 Coupler solvent (Solv- 2) ... 0.10 11th layer (ultraviolet absorbing layer) Gelatin ... 1.50 ultraviolet absorber (Cpd-1, 2, 4, 15 equivalents)
..1.00 Color mixing inhibitor (Cpd-7, 16) ... 0.06 Dispersion medium (Cpd-6) UV absorber solvent (Solv
-1, 2) ... 0.15 Anti-irradiation dye (Cpd-17, 18)
... 0.02 Irradiation prevention dye (Cpd-19, 20)
... 0.02 12th layer (protective layer) Fine silver chlorobromide (97 mol% silver chloride, average size 0.2)
μ) ・ ・ ・ 0.07 Modified Poval ・ ・ ・ 0.02 Gelatin ・ ・ ・ 1.50 Gelatin hardening agent (H-1, 2 equivalents) ・ ・ ・ 0.17 Further, in each layer, an emulsification dispersion aid As alkanol XC
(Dupont) and sodium alkylbenzene sulfonate as succinic acid ester as a coating aid, and
Magefac F-120 (manufactured by Dainippon Ink and Chemicals, Inc.) was used. For the silver halide or colloidal silver-containing layer, (Cpd-21, 22, 23) was used as a stabilizer.
The compounds used in the examples are shown below.

[0163]

[Chemical 76]

[0164]

[Chemical 77]

[0165]

[Chemical 78]

[0166]

[Chemical 79]

[0167]

[Chemical 80]

[0168]

[Chemical 81]

[0169]

[Chemical formula 82]

[0170]

[Chemical 83]

[0171]

[Chemical 84]

[0172]

[Chemical 85]

[0173]

[Chemical formula 86]

Treatment process Composition of treatment liquid (first developer) Nitrilo-N, N, N-trimethylene phosphonic acid pentasodium salt 0.6 g Diethylenetriamine pentaacetic acid pentasodium salt
4.0 g Potassium sulfite 30.0 g Potassium thiocyanate 1.2 g Potassium carbonate 35.0 g Hydroquinone monosulfonate / potassium salt
25.0 g Diethylene glycol 15.0 ml 1-phenyl-4-hydroxymethyl-4-methyl-3
-Pyrazolidone 2.0 g Potassium bromide 0.5 g Potassium iodide 5.0 mg Water was added to 1 l (pH 9.70) (color developer) benzyl alcohol 15.0 ml Diethylene glycol 12.0 ml 3,6-dithia-1, 8-octanediol
0.2 g Nitrilo-N, N, N-trimethylenephosphonic acid pentasodium salt 0.5 g Diethylenetriamine pentaacetic acid pentasodium salt
2.0 g sodium sulfite 2.0 g potassium carbonate 25.0 g hydroxylamine sulfate 3.0 g N-ethyl-N- (β-methanesulfonamidoethyl)
-3-Methyl-4-aminoaniline sulfate 5.0 g Potassium bromide 0.5 g Potassium iodide 1.0 mg Water was added to 1 l (pH 10.40) (bleach-fixing solution) 2-mercapto-1,3. 4-triazole
1.0 g ethylenediaminetetraacetic acid / disodium / dihydrate
5.0g Ethylenediaminetetraacetic acid / Fe (III) / ammonium-hydrate 80.0g Sodium sulfite 15.0g Sodium thiosulfate (700g / l liquid)
160.0 ml Glacial acetic acid 5.0 ml Add water 1 liter (pH 6.50)

The above sample was designated as Sample 401. Sample 401
In place of Cpd-24 in the fifth and sixth layers of Comparative Compound A, Comparative Compound B, Comparative Compound C (described in Example 1) and Compounds (1), (2), (3) and (4) of the present invention. ), (27),
Samples 402 to 410 were prepared as shown in Table 2 by adding equimolar amounts of (30). The obtained sample is 320
The pattern for sharpness measurement was printed with a light source of 0 ° K.
In addition, a reversal film (RTP manufactured by Fuji Film) on which a Macbeth color chart was taken was printed on each sample. Each exposed sample was processed in the following processing steps. The sharpness was judged by the MTF value. On the other hand, Table 2 shows the results of the measurement of the saturation of green color on the Macbeth color chart by the Munsell method with a color computer. As is apparent from Table 11, when the compound of the present invention is used, sharpness and chroma are improved.

[0176]

[Table 11]

[0177]

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Megumi Sakagami 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Fuji Photo Film Co., Ltd.

Claims (3)

[Claims] 1. A silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, containing at least one compound represented by formula (I). Silver photographic light-sensitive material. General formula [I] (In the formula, R ₁ is an alkyl group having 2 or more carbon atoms in which a carbon atom adjacent to the carbonyl group is not substituted with a hetero atom,
Represents a cycloalkyl group, an aryl group or a heterocyclic group, R ₂ and R ₃ represent a hydrogen atom or a substituent having a Hammett's substituent constant σ _p of 0.3 or less, and B represents a hydroquinone mother nucleic acid compound. After elimination, it represents a group which releases PUG, PUG represents a development inhibitor, l represents an integer, and A and A ′ represent a hydrogen atom or a group which can be removed with an alkali. ) 2. A compound represented by formula (I) is represented by formula (II)
The silver halide photographic light-sensitive material according to claim 1, which is a compound represented by: General formula [II] (In the formula, R ₄ represents a substituent, and PUG, A, A ′, B
And l have the same meaning as in formula (I), and n represents an integer of 2 or more. ) 3. A compound of formula (I) is represented by formula (II
The light-sensitive material according to claim 1, which is a compound represented by I). General formula [III] (In the formula, R ₅ represents a substituent, and A, A ′, B, PUG
And l have the same meaning as in formula [I], and m is 1 to 5
When m is 2 or more, R _{5 s} may be the same or different. )