JP2678837B2 - Silver halide photographic material - Google Patents

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, and more particularly to a coupler capable of releasing a plurality of photographically useful groups from a released timing group.

[0002]

2. Description of the Related Art In recent years, in silver halide light-sensitive materials, especially in color light-sensitive materials for photographing, high sensitivity as represented by ISO 400 light-sensitive material (Super-HG-400) having high image quality as high as ISO sensitivity 100. Therefore, a sensitive material having excellent graininess and sharpness and excellent storability of the sensitive material has been demanded. As a material for improving image quality, a method is known in which a photographically useful group is bonded to the coupling position of a coupler through a timing group to release the photographically useful group imagewise and at an appropriate timing during photographic processing. , U.S. Pat.
No. 323 and JP-A-60-218645.

The methods disclosed therein release one molecule of photographically useful group from one molecule of coupler.
However, when a large amount of these couplers are added to the film, the film thickness becomes large, the sharpness becomes poor, and the cost becomes high. In addition, Japanese Patent Laid-Open No.
No. 57 and US Pat.
Couplers that release two molecules of a photographically useful group from one carbon atom have been proposed, but these couplers were inferior in stability such as releasing a photographically useful group even by hydrolysis.

[0004]

An object of the present invention is to propose a silver halide photographic light-sensitive material which is excellent in sharpness, graininess, color reproducibility and is inexpensive.

[0005]

The object of the present invention is to have at least one light-sensitive silver halide emulsion layer on a support,
In a silver halide photographic light-sensitive material containing a coupler that releases a photographically useful group or a precursor thereof through a timing group by a coupling reaction with an oxidized form of a developing agent, on different atoms constituting the timing group, It has been achieved by a silver halide photographic light-sensitive material characterized by having a plurality of photographically useful groups or precursors thereof.
However, when a plurality of photographically useful groups have different functions, the timing group does not utilize intramolecular nucleophilic substitution.

The function of the photographically useful group means the function exhibited by a development inhibitor, a dye, a fogging agent, a developer, a coupler, a bleaching accelerator or a fixing agent. The compound of the present invention is preferably one represented by the following general formula (I). General formula (I)

[0007]

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In the formula, A represents a coupler residue, and L ₁ is 2
Represents a valent timing group, L ₂ represents a timing group having a trivalent or higher valence bond, and PUG represents a photographically useful group. k and n each independently represent 0, 1 or 2, m represents 1 or 2, S represents the valence of L ₂ minus 1, and represents an integer of 2 or more. Also L
When a plurality of _1's are present in the molecule, they may all be the same or different. There are multiple PUGs
May all be the same or different.

The compound represented by formula (I) will be described in more detail below. In the general formula (I),
A represents a coupler residue.

For example, a yellow coupler residue (for example, an open-chain ketomethylene type coupler residue such as acylacetanilide or malondianilide), a magenta coupler residue (for example, a 5-pyrazolone type, a pyrazolotriazole type or an imidazopyrazole type coupler residue). ), A cyan coupler residue (for example, a phenol residue, a naphthol residue, an imidazole residue described in European Patent Publication 249,453 or a pyrazolopyrimidine residue described in 304,001) and a non-color coupler residue ( Examples thereof include indanone type or acetophenone type coupler residues. Also, U.S. Pat.Nos. 4,315,070 and 4,183,
752, 4,174,969, 3,961,959, 4,171,223
Or a heterocyclic coupler residue described in JP-A No. 52-82423.

A preferred example of A is the following general formula (Cp-
1), (Cp-2), (Cp-3), (Cp-4),
(Cp-5), (Cp-6), (Cp-7), (Cp-
8), (Cp-9), (Cp-10) or (Cp-
This is when it is a coupler residue represented by 11). These couplers are preferable because of their high coupling speed.

[0012]

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[0013]

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[0014]

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The asterisk * derived from the coupling position in the above formula represents the bonding position with X ₁ . In the above formula, R ₅₁ , R ₅₂ , R ₅₃ , R ₅₄ , R ₅₅ , R ₅₆ , R ₅₇ , R ₅₈ ,
When R ₅₉ , R ₆₀ , R ₆₁ , R ₆₂ , R ₆₃ , R ₆₄ or R ₆₅ contains a diffusion resistant group, it has a total carbon number of 8 to 40,
It is preferably selected to be 10 to 30, and in other cases, the total number of carbon atoms is preferably 15 or less.

R _{51 to} R ₆₅ , b, d, e and f will be described in detail below. Hereinafter, R ₄₁ represents an aliphatic group, an aromatic group or a heterocyclic group, R ₄₂ represents an aromatic group or a heterocyclic group, and R ₄₃ , R ₄₄ and R ₄₅ represent a hydrogen atom, an aliphatic group or an aromatic group. Represents a group or a heterocyclic group.

R ₅₁ has the same meaning as R ₄₁ . R ₅₂ and R ₅₃ each have the same meaning as R ₄₂ . b is 0 or 1
Represents R ₅₄ represents a group having the same meaning as R _41, R ₄₁ CON (R
₄₃ ) -group, R ₄₁ R ₄₃ N-group, R ₄₁ SO ₂ N (R ₄₃ )-
Group, R ₄₁ S- group, R ₄₃ O- group, R ₄₅ N (R ₄₃ ) CON
It represents a (R ₄₄ )-group or an N≡C- group. R ₅₅ is R ₄₁
Represents a group having the same meaning as. R ₅₆ and R ₅₇ are each a group having the same meaning as R ₄₃ , R ₄₁ S-group, R ₄₃ O-group, R ₄₁ CON
It represents a (R ₄₃ ) -group or an R ₄₁ SO ₂ N (R ₄₃ ) -group. R ₅₈ represents a group having the same meaning as R ₄₁ . And R ₅₉ groups of the same meaning as _{R 41, R 41 CON (R} 43) - group, R ₄₁ OCON
(R ₄₃ ) -group, R ₄₁ SO ₂ N (R ₄₃ ) -group, R ₄₃ R ₄₄ N
CON (R ₄₅₎ - represents group R ₄₁ O-group, R ₄₁ S- group, a halogen atom or R ₄₁ R ₄₃ N- group. d represents 0 to 3. When d is plural, plural R _59s represent the same substituent or different substituents. Also, each R ₅₉ is 2
They may be linked to each other to form a cyclic structure. Examples of forming a cyclic structure include a pyridine ring and a pyrrole ring. R ₆₀ represents a group having the same meaning as R ₄₁ . R ₆₁ represents a group having the same meaning as R ₄₁ . R ₆₂ is R
₄₁ the same meanings of the group, R ₄₁ OCONH- group, R ₄₁ SO ₂ N
H-group, R ₄₃ R ₄₄ NCON (R ₄₅ ) -group, R ₄₃ R ₄₄ NS
O ₂ N (R ₄₅₎ represents group, R ₄₃ O-group, R ₄₁ S- group, a halogen atom or R ₄₁ R ₄₃ N- group. R ₆₃ is a group having the same meaning as R ₄₁ , R ₄₃ CON (R ₄₅ ) -group, R ₄₃ R ₄₄ NCO-
Group, R ₄₁ SO ₂ N (R ₄₄ ) − group, R ₄₃ R ₄₄ NSO ₂ −
R ₄₁ SO ₂ —, R ₄₃ OCO—, R ₄₃ O—SO ₂
Group, halogen atom, nitro group, cyano group or R ₄₃ C
Represents an O-group. e represents an integer of 0 to 4. Each represent the same or different when there are a plurality of R ₆₂ or R _63. R ₆₄ and R ₆₅ are each R ₄₃ R ₄₄ NC
O-group, R ₄₁ CO-group, R ₄₃ R ₄₄ NSO ₂ -group, R ₄₁ O
It represents group, a nitro group or a cyano group - CO- group, R ₄₁ SO _2. Z ₁ is a nitrogen atom or a ═C (R ₆₆ ) — group (R ₆₆
Represents a hydrogen atom or a group having the same meaning as R ₆₃ ). Z ₂ represents a sulfur atom or an oxygen atom. f is 0
Or represents 1.

In the above, the aliphatic group has 1 to 3 carbon atoms.
2, preferably 1 to 22 saturated or unsaturated, linear or cyclic, linear or branched, substituted or unsubstituted aliphatic hydrocarbon groups. Representative examples include methyl, ethyl, propyl, isopropyl, butyl, (t) -butyl, (i) -butyl, (t) -amino, hexyl, cyclohexyl, 2-ethylhexyl, octyl, 1,1,
3,3-tetramethylbutyl, decyl, dodecyl, hexadecyl, or octadecyl.

The aromatic group is a phenyl group having 6 to 20 carbon atoms, preferably a substituted or unsubstituted phenyl group, or a substituted or unsubstituted naphthyl group.

The heterocyclic group is a hetero atom having 1 to 20 carbon atoms, preferably 1 to 7 carbon atoms, and is selected from nitrogen atom, oxygen atom or sulfur atom. It is preferably a substituted or unsubstituted heterocyclic group having a 3- to 8-membered ring. Representative examples of the heterocyclic group include 2-pyridyl, 2-furyl, 2-imidazolyl, 1-indolyl, 2,4-dioxo-1,3-
Imidazolidine-5-yl, 2-benzoxazolyl,
Examples include 1,2,4-triazol-3-yl or 4-pyrazolyl.

When the aliphatic hydrocarbon group, aromatic group and heterocyclic group have a substituent, typical substituents are:
Halogen atom, R ₄₇ O-group, R ₄₆ S-group, R ₄₇ CON
(R ₄₈₎ - _{group, R 47 N (R 48)} CO- group, R ₄₆ OCON
(R ₄₇₎ - _{group, R 46 SO 2 N (R} 47) - group, R ₄₇ R ₄₈ N
SO ₂ - group, R ₄₆ SO ₂ - group, R ₄₇ OCO- group, R ₄₇ R
₄₈ NCON (R ₄₉₎ - group, a group having the same meaning as R _46, R ₄₆ C
Examples thereof include an OO- group, an R ₄₇ OSO ₂ -group, a cyano group or a nitro group. Here, R ₄₆ represents an aliphatic group, an aromatic group, or a heterocyclic group, and R ₄₇ , R _48, and R ₄₉ each represent an aliphatic group, an aromatic group, a heterocyclic group, or a hydrogen atom. The meaning of the aliphatic group, the aromatic group or the heterocyclic group is the same as defined above.

Next, preferable ranges of R _{51 to} R ₆₅ , b, d, e and f will be described. R ₅₁ is preferably an aliphatic group or an aromatic group. R ₅₂ and R ₅₅ are preferably an aromatic group. R ₅₃ is preferably an aromatic group or a heterocyclic group.

In the general formula (Cp-3), R ₅₄ is R ₄₁
A CONH-group or an R ₄₁ R ₄₃ N-group is preferred. R ₅₆
And R ₅₇ is an aliphatic group, an aromatic group, R ₄₁ O-group, or R ₄₁ S- groups are preferred. R ₅₈ is preferably an aliphatic group or an aromatic group. In the general formula (Cp-6), R ₅₉ is preferably a chlor atom, an aliphatic group or an R ₄₁ CONH- group.
d is preferably 1 or 2. R ₆₀ is preferably an aromatic group. In the general formula (Cp-7), R ₅₉ is R ₄₁ CONH-
Groups are preferred. In the general formula (Cp-7), d is preferably 1. R ₆₁ is preferably an aliphatic group or an aromatic group.
In the general formula (Cp-8), e is preferably 0 or 1. R ₆₂ is R ₄₁ OCONH- group, R ₄₁ CONH-
Group or R ₄₁ SO ₂ NH— group is preferable, and the substitution position thereof is preferably the 5-position of the naphthol ring. General formula (Cp-
9), R ₆₃ is R ₄₁ CONH-group, R ₄₁ S
O ₂ NH- group, R ₄₁ R ₄₃ NSO ₂ - group, R ₄₁ SO ₂ -
Group, R ₄₁ R ₄₃ NCO— group, nitro group or cyano group is preferred, and e is preferably 1 or 2. General formula (Cp-1
0), R ₆₃ is (R ₄₃ ) ₂ NCO— group, R ₄₃ OC
O-group or R ₄₃ CO- group is preferable, and e is 1 or 2
Is preferred. In formula (Cp-11), R ₅₄ is preferably an aliphatic group, an aromatic group or an R ₄₁ CONH-group, and f ₅₄
Is preferably 1.

Next, typical examples of R _{51 to} R ₆₃ will be described. Examples of R ₅₁ include (t) -butyl group, 4-methoxyphenyl group, phenyl group, 3- {2 (2,4-di-t-amylphenoxy) butanamide} phenyl group, and methyl group. R ₅₂ and R ₅₃ include a phenyl group, a 2-chloro-5ethoxy group, a 2-chloro-5-dodecyloxycarbonylphenyl group, and a 2-chloro-5- group.
Hexadecyl sulfonamide phenyl group, 2-chloro-
5-tetradecanamidophenyl group, 2-chloro-5-
{4- (2,4-di-t-amylphenoxy) butanamide} phenyl group, 2-chloro-5- {2- (2,4-
Di-t-amylphenoxy) butanamide} phenyl group, 2-methoxyphenyl group, 2-methoxy-5-tetradecyloxycarbonylphenyl group, 2-chloro-5
-(1-ethoxycarbonylethoxycarbonyl) phenyl group, 2-pyridyl group, 2-chloro-5-octyloxycarbonylphenyl group, 2,4-dichlorophenyl group, 2-chloro-5- (1-dodecyloxycarbonylethoxycarbonyl) ) Phenyl group, 2-chlorophenyl group or 2-ethoxyphenyl group.

R ₅₄ is a butanoylamino group, 2-
Chloro-3-propanoylaminoanilino group, 3- {2
-(2,4-di-t-amylphenoxy) butanamide} benzamide group, 3- {4- (2,4-di-t-amylphenoxy) butanamide} benzamide group, 2-
Chloro-5-tetradecanamidoaniline group, 5-
(2,4-Di-t-amylphenoxyacetamide) benzamide group, 2-chloro-5-dodecenylsuccinimidoanilino group, 2-chloro-5- {2- (3-t-butyl-4-hydroxy) Phenoxy) tetradecanamide} anilino group, 2,2-dimethylpropanamide group,
2- (3-pentadecylphenoxy) butanamide group,
Examples thereof include a pyrrolidino group and an N, N-dibutylamino group. R ₅₅ is 2,4,6-trichlorophenyl group, 2-chlorophenyl group, 2,5-dichlorophenyl group, 2,3-dichlorophenyl group, 2,6-dichloro- group.
4-methoxyphenyl group, 4- {2- (2,4-di-t
-Amylphenoxy) butanamide} phenyl group or 2,6-dichloro-4-methanesulfonylphenyl group,
Is a preferred example. _Examples of R ₅₆ include a methyl group, an ethyl group, an isopropyl group, a methoxy group, an ethoxy group, a methylthio group, an ethylthio group, a 3-phenylureido group, or a 3- (2,4-di-t-amylphenoxy) propyl group. To be

R ₅₇ is a 3- (2,4-di-t-amylphenoxy) propyl group, 3- [4- {2- [4-
(4-Hydroxyphenylsulfonyl) phenoxy] tetradecanamido} phenyl] propyl group, methoxy group, methylthio group, ethylthio group, methyl group, 1-methyl-2- (2-octyloxy-5- [2-octyloxy-5 -(1,1,3,3-Tetramethylbutyl) phenyl sulfonamide] phenyl sulfonamide] ethyl group, 3- {4- (4-dodecyloxyphenyl sulfonamide) phenyl} propyl group, 1,1-dimethyl-
2- (2-octyloxy-5- (1,1,3,3-tetramethylbutyl) phenylsulfonamido] ethyl group or dodecylthio group is mentioned, and R ₅₈ is 2-chlorophenyl group, pentafluorophenyl group. , Heptafluoropropyl group, 1- (2,4-di-t-amylphenoxy) propyl group, 3- (2,4-di-t-amylphenoxy) propyl group, 2,4-di-t-amylmethyl group R ₅₉ is a chloro atom, a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, a 2- (2,4-di-t-amylphenoxy) butanamide group, or a 2- ( 2,4-di-t-amylphenoxy) hexanamide group, 2- (2,4-di-t-octylphenoxy) octanamide group, 2-
(2-chlorophenoxy) tetradecanamide group, 2-
{4- (4-hydroxyphenylsulfonyl) phenoxy} tetradecanamide group, or 2- {2- (2,4
-Di-t-amylphenoxyacetamido) phenoxy} butanamide group.

R ₆₀ is a 4-cyanophenyl group, 2-
Cyanophenyl group, 4-butylsulfonylphenyl group,
4-propylsulfonylphenyl group, 4-chloro-3-
Examples thereof include a cyanophenyl group, a 4-ethoxycarbonylphenyl group, and a 3,4-dichlorophenyl group.
R ₆₁ is a propyl group, a 2-methoxyphenyl group,
Dodecyl group, hexadecyl group, cyclohexyl group, 3-
(2,4-di-t-amylphenoxy) propyl group, 4
-(2,4-di-t-amylphenoxy) butyl group, 3
-Dodecyloxypropyl group, t-butyl group, 2-methoxy-5-dodecyloxycarbonylphenyl group, or 1-naphthyl group. Examples of R ₆₂ include an isobutyloxycarbonylamino group, an ethoxycarbonylamino group, a phenylsulfonylamino group, a methanesulfonamide group, a benzamide group, a trifluoroacetamide group, a 3-phenylureido group, a butoxycarbonylamino group, or an acetamide group. . R ₆₃ is 2,4-di-t-amylphenoxyacetamide group, 2- (2,4-di-t-amylphenoxy) butanamide group, hexadecylsulfonamide group, N-methyl-N-octadecylsulfa group. Moyl group, N, N-dioctylsulfamoyl group, 4-t-octylbenzoyl group, dodecyloxycarbonyl group, chlor atom, nitro group, cyano group, N- {4- (2,4-di-t-amyl) Phenoxy) butyl} carbamoyl group, N-3- (2,
4-di-t-amylphenoxy) propylsulfamoyl group, methanesulfonyl group or hexadecylsulfonyl group can be mentioned.

In the general formula (I), L ₁ preferably includes the following. (1) Group utilizing cleavage reaction of hemiacetal: For example, a group described in U.S. Pat. No. 4,146,396, JP-A-60-249148 and 60-249149 and represented by the following general formula. Here, the * symbol represents the position at which the compound represented by the general formula (I) is bonded to A, L ₁ or L _2, and **
The mark represents the position at which L ₁ , L ₂ or PUG is bonded.

[0029] The general formula (T-1) * - W -C (R 11) (R 12) t - **

In the formula, W is an oxygen atom, a sulfur atom or-
Represents a N (R ₁₃ )-group, R ₁₁ and R ₁₂ represent a hydrogen atom or a substituent, R ₁₃ represents a substituent, and t represents 1 or 2. When t is 2, two -W-C
_{(R 11) (R 12)} - represents the same or different. When R ₁₁ and R ₁₂ represent a substituent and R ₁₃
Representative examples of R ₁₅ group, R ₁₅ CO— group and R ₁₅ SO ₂ are, respectively.
- group, R ₁₅ R ₁₆ NCO- radical or R ₁₅ R ₁₆ NSO ₂ - group. Here, R ₁₅ represents an aliphatic group, an aromatic group or a heterocyclic group, and R ₁₆ represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group. R ₁₁ , R ₁₂ and R ₁₃ each represent a divalent group, and are linked to form a cyclic structure. Specific examples of the group represented by the general formula (T-1) include the following groups.

[0031]

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[0032]

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(2) Group that causes cleavage reaction utilizing intramolecular nucleophilic substitution reaction For example, a timing group described in US Pat. No. 4,248,292 can be mentioned. It can be represented by the following general formula.

General formula (T-2) * -Nu-Link-E-**

In the formula, Nu represents a nucleophilic group, an oxygen atom or a sulfur atom is an example of a nucleophilic species, E represents an electrophilic group, and is subjected to a nucleophilic attack from Nu to form a bond with **. Link is a cleavable group and represents a linking group that sterically links Nu and E so that they can undergo an intramolecular nucleophilic substitution reaction. Specific examples of the group represented by the general formula (T-2) are as follows.

[0036]

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[0037]

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(3) A group that causes a cleavage reaction by utilizing an electron transfer reaction along a conjugated system. For example, U.S. Pat.Nos. 4,409,323, 4,421,845, JP-A-57-188035, 58-98728, 58-209736,
No. 58-209737, No. 58-209738, etc., and is a group represented by the following general formula (T-3). General formula (T-
3)

[0039]

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In the formula, *, **, W, R ₁₁ , R ₁₂ and t have the same meanings as described for (T-1).
However, R ₁₁ and R ₁₂ may combine to form a benzene ring or a heterocyclic ring. Also, R ₁₁ or R ₁₂
And W may combine to form a benzene ring or a heterocycle. Z ₁ and Z ₂ each independently represent a carbon atom or a nitrogen atom, and x and y represent 0 or 1. Z
_{When 1} is a carbon atom, x is 1, and when Z ₁ is a nitrogen atom, x is 0. Relationship between Z ₂ and y is the same as the relationship between Z ₁ and x. Further, t represents 1 or 2, and t is 2
When two

[0041]

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May be the same or different. Specific examples of (T-3) will be given below.

[0043]

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[0044]

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[0045]

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(4) A group which utilizes a cleavage reaction by hydrolysis of an ester. For example, the following groups are the linking groups described in West German Published Patent No. 2,626,315. In the formulas, * and ** have the same meaning as described for the general formula (T-1). General formula (T-4) General formula (T-5) * -OC (= O)-***-S-C (= S)-** (5) Group which utilizes the cleavage reaction of 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)

[0047]

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In the formula, *, ** and W are general formulas (T
-1) has the same meaning as described above, and R ₁₄ is R
Has the same meaning as ₁₃ . Specific examples of the group represented by Formula (T-6) include the following groups.

[0049]

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L ₁ is preferably (T-1) to (T-
5), particularly preferably (T-1)
And (T-4). k is preferably 0 or 1. n is preferably 0 or 1, and particularly preferably 0. In formula (I), the group represented by L ₂ is 3
It represents the valence or more electron transfer type timing group, preferably represented by the following general formula (T-L _2). The general formula _(T-L 2)

[0051]

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In the formula, W, Z ₁ , Z ₂ , R ₁₁ , R ₁₂ ,
x, y and t have the same meanings as described for formula (T-3). Also, * indicates A- in the general formula (I).
The position at which (L ₁ ) _L − is bonded, the ** mark indicates-(L ₁ ) _n
-Indicates the position to be connected to PUG. However, at least one of a plurality of R ₁₁ or R ₁₂ is a substituted or unsubstituted methylene group and represents a group bonded to — (L ₁ ) _n -PUG. (T 1 L ₂ ) is preferably a case where W represents a nitrogen atom, and more preferably W and Z.
It is a case where ₂ is bonded to form a 5-membered ring, particularly preferably a case where an imidazole ring of imidazole or pyrazole is formed. Specific examples of (T-L ₂ ) are shown below, but the present invention is not limited thereto.

[0053]

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[0054]

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[0055]

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However, the groups exemplified in the examples here may further have a substituent, and as such a substituent, an alkyl group (methyl, ethyl, isopropyl, t-butyl, hexyl, methoxymethyl, Methoxyethyl, chloroethyl, cyanoethyl, nitroethyl, hydroxypropyl, carboxyethyl, dimethylaminoethyl, benzyl, phenethyl, etc.), aryl groups (phenyl, naphthyl, 4-hydroxyphenyl, 4-cyanophenyl, 4-nitrophenyl, 2-methoxy) Phenyl, 2,
6-dimethylphenyl, 4-carboxyphenyl, 4-
Sulfophenyl etc.), heterocyclic group (2-pyridyl, 4
-Pyridyl, 2-furyl, 2-thienyl, 2-pyrrolyl, etc.), halogen atom (chloro, bromo, etc.), nitro group, alkoxy group (methoxy, ethoxy, isopropoxy, etc.), aryloxy group (phenoxy, etc.), alkylthio Groups (methylthio, isopropylthio, t-butylthio, etc.), arylthio groups (phenylthio, etc.),
Amino group (amino, dimethylamino, diisopropylamino, etc.), acylamino group (acetylamino, benzoylamino, etc.), sulfonamide group (methanesulfonamide, benzenesulfonamide, etc.), cyano group, carboxyl group, alkoxycarbonyl group (methoxycarbonyl) , Ethoxycarbonyl, etc.), aryloxycarbonyl (phenoxycarbonyl, etc.), carbamoyl group (N-ethylcarbamoyl, N-phenylcarbamoyl, etc.) and the like.

Of these, preferably an alkyl group, a nitro group,
An alkoxy group, an alkylthio group, an amino group, an acylamino group, a sulfonamide group, an alkoxycarbonyl group, and a carbamoyl group.

The photographically useful group represented by PUG in the formula (I) is specifically a development inhibitor, a dye, a fogging agent, a developing agent, a coupler, a bleaching accelerator, a fixing accelerator and the like.
Examples of preferred photographically useful groups are the photographically useful groups described in U.S. Pat. No. 4,248,962 (represented by the general formula PUG in the patent) and the dyes described in JP-A-62-49353. In the description, the part of the leaving group released from the coupler), the development inhibitor described in U.S. Pat. No. 4,477,563, and the bleaching accelerator described in JP-A-61-201247 and JP-A-2-55, etc. In the specification, the part of the leaving group released from the coupler) is mentioned. In the present invention,
Particularly preferred as a photographically useful group is a development inhibitor.

As the development inhibitor, the following general formula (I
It is a group represented by NH-1) to (INH-13).

[0060]

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[0061]

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[0062]

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In the formula, * represents the position of bonding with the residue of the general formula (I) excluding PUG. Also, ** represents a position at which the substituent is bonded, and examples of the substituent include an aliphatic group, an aryl group, and a heterocyclic group.

Specific examples of the aliphatic group include alkoxycarbonyl groups (ethoxycarbonyl, 1,4-dioxo-
2,5-dioxadecyl, 1,4-dioxo-2,5-
Dioxa-8-methylnonyl etc.), aryloxycarbonyl group (phenoxycarbonyl etc.), alkylthio group (methylthio, propylthio etc.), alkoxy group (methoxy, propyloxy etc.), sulfonyl group (methanesulfonyl etc.), carbamoyl group (ethylcarbamoyl). Etc.), sulfamoyl group (ethylsulfamoyl etc.), cyano group, nitro group, acylamino group (acetylamino etc.), alkyl group (methyl, ethyl, propyl, butyl, hexyl, decyl, isobutyl, t-butyl, 2- Ethylhexyl, benzyl, 4-methoxybenzyl, phenethyl, propyloxycarbonylmethyl, 2- (propyloxycarbonyl) ethyl, butyloxycarbonylmethyl, pentyloxycarbonylmethyl, 2-cyanoethyl Le butyloxycarbonylmethyl, 2,
2-dichloroethyloxycarbonylmethyl, 3-nitropropyloxycarbonylmethyl, 4-nitrobenzyloxycarbonylmethyl, or 2,5-dioxo-3,6-dioxadecyl).

As the aryl group, phenyl, naphthyl, 4-methoxycarbonylphenyl, 4-ethoxycarbonylphenyl, 3-methoxycarbonylphenyl,
4- (2-cyanoethyloxycarbonyl) -phenyl and the like can be mentioned.

As the heterocyclic group, 4-pyridyl, 3
-Pyridyl, 2-pyridyl, 2-furyl, 2-tetrahydropyranyl, and the like.

Of these, the substituent is preferably a substituted or unsubstituted alkoxycarbonyl group, aryloxycarbonyl group, alkyl group or aryl group. More preferably, an alkoxycarbonyl group having a substituent, an unsubstituted alkyl group having 2 to 7 carbon atoms, and 2 carbon atoms.
To 10 substituted alkyl groups or substituted or unsubstituted phenyl groups.

Of these, INH is preferably (INH
-1), (INH-2), (INH-3), (INH-4), (INH-9) and
(INH-12), particularly preferably (INH-1), (INH-2) and (INH-3).

Specific examples of the compound of the present invention are shown below.
The present invention is not limited by these.

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The compound of the present invention can be synthesized by the same method as the synthetic route described in JP-A-60-218645 and JP-B-63-39889. (Synthesis Example 1) Synthesis of Exemplified Compound (1)

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60 of 1a (3.40 g) in thionyl chloride (30 ml)
After reacting for 1 hour at ℃, excess thionyl chloride was distilled off under reduced pressure. This residue was dissolved in 1b (7.48 g) and diisopropylethylamine (10.5 ml) in dimethylformamide (0 ° C).
Was stirred for 1 hour. Thereafter, this solution was poured into water (500 ml) and the resulting crystals were collected by filtration to obtain 9.8 g of 1c as crude crystals. The structure was confirmed by NMR.

1c (3.20 g) and 1d (1.38 g) were reacted in 1,2-dichloroethane (30 ml) for 1 hour. there,
A solution of 1e (3.20 g) in ethyl acetate (20 ml) was added under water cooling,
Subsequently, diisopropylethylamine (4.5 ml) was added and the mixture was stirred for 1 hour. The reaction was stopped with 1N hydrochloric acid, and chloroform (30 ml) was added to dilute the reaction solution. After that, the reaction solution was washed with water three times, and the organic layer was dried over sodium sulfate.
The oily substance obtained by distilling off the organic solvent was purified by silica gel chromatography (ethyl acetate-hexane = 1: 5) to obtain 1.20 g of Exemplified compound (1). mp.13
2.5 ° C to 135.0 ° C The structure was confirmed by NMR.

Synthesis Example 2 Synthesis of Exemplified Compound (47) Synthesis was carried out in the same manner as in Synthesis Example 1 to obtain an oily substance. ¹ HNMR (δ): 0.9 (9H), 1.1-1.45 (28H), 1.7 (6H), 3.1 (1
H), 3.9-4.2 (6H), 4.55 (4H), 5.0 (4H), 6.85-7.2 (3H), 7.
4 (1H), 7.5 −8.1 (3H), 8.3 −8.7 (3H), 13.3 (1H) ppm. The compounds of the present invention release multiple PUGs during development processing. The putative reaction mechanism is shown below by taking the case of releasing two molecules of PUG as an example.

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In the formula, PUG has the same meaning as in formula (I).
T ⁺ represents an oxidized product of a developing agent. Nuc represents a nucleophilic agent contained in the development processing solution, and specifically, hydroxyl ion, sulfite ion, hydroxylamine and the like. As shown in the above reaction scheme, the compound of the present invention releases a plurality of PUGs from one molecule of the compound. That is, the compounds of the present invention dramatically enhance the photographic properties by doubling the action of the photographically useful groups in principle.

The compound represented by formula (I) of the present invention may be used in any layer in the light-sensitive material, but it is preferably added to the light-sensitive silver halide emulsion layer and / or its adjacent layer. It is more preferable to add it to the photosensitive silver halide emulsion layer. The total amount of these compounds added to the light-sensitive material is usually 1 × 10 ^{−7 to} 5 × 10 ⁻⁴ mol / m ² , and more preferably 1 × 10 ⁻⁶ to 2 × 10 ⁻⁴ mol / m ^2. Is 5 ×
It is 10 ⁻⁶ to 1 × 10 ⁻⁴ mol / m ² . General formula (I) of the present invention
The compound represented by can be added in the same manner as in ordinary couplers as described below.

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. A typical example is a silver halide photographic light-sensitive material having at least one light-sensitive layer comprising a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities on a support. Wherein the photosensitive layer is blue light, green light,
And a unit light-sensitive layer having color sensitivity to any of red light and a multilayer silver halide color photographic light-sensitive material. In general, the arrangement of the unit light-sensitive layers is, in order from the support side, a red light-sensitive layer, The color-sensitive layer and the blue-sensitive layer are provided in this order. However, depending on the purpose, the order of installation may be reversed, or the order of installation may be such that different photosensitive layers are sandwiched between layers of the same color sensitivity. Non-light-sensitive layers such as various intermediate layers may be provided between the silver halide light-sensitive layers and as the uppermost layer and the lowermost layer. The intermediate layer, JP-A-61-43748, 59-113
No. 438, No. 59-113440, No. 61-20037, No. 61-20038 may contain a coupler, a DIR compound and the like, and a color mixing inhibitor may be used as is usually used. May be included. The plurality of silver halide emulsion layers constituting each unit light-sensitive layer preferably employ a two-layer structure of a high-speed emulsion layer and a low-speed emulsion layer as described in German Patent No. 1,121,470 or British Patent No. 923,045. be able to. Usually, it is preferable to arrange them so that the light sensitivity decreases sequentially toward the support, and a non-photosensitive layer may be provided between the respective halogen emulsion layers. In addition,
57-112751, 62-200350, 62-206541, 62-2
As described in JP-A-06543 and the like, a low-speed emulsion layer may be provided on the side remote from the support, and a high-speed emulsion layer may be provided on the side near the support. As a specific example, from the side farthest from the support,
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) / In the order of the low-sensitivity red photosensitive layer (RL), or in the order of BH / BL / GL / GH / RH / RL, or BH / BL / GH /
They can be installed in the order of GL / RL / RH. Also Tokunoaki
As described in JP-A-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. JP-A-56-25738, 62-63936
As described in the specification, the layers may be arranged in the order of blue-sensitive layer / GL / RL / GH / RH from the side farthest from the support. Also, as described in JP-B-49-15495, the upper layer is the most sensitive silver halide emulsion layer, the middle layer is the less sensitive silver halide emulsion layer, and the lower layer is more sensitive than the middle layer. An arrangement in which a silver halide emulsion layer having a low degree of sensitivity is arranged, and three layers having different sensitivities are sequentially reduced in sensitivity toward a support, may be mentioned. Even in the case of comprising three layers having different sensitivities, as described in JP-A-59-202464, a medium-speed emulsion is provided in the same color-sensitive layer from the side away from the support. Layers / high-speed emulsion layers / low-speed emulsion layers. In addition, the layers 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. The arrangement may be changed as described above even in the case of four or more layers. In order to improve color reproducibility, U.S. Pat.Nos. 4,663,271 and 4,705,
Nos. 744 and 4,707,436, JP-A-62-160448 and 63-63
It is preferred that a donor layer (CL) having a multilayer effect having a spectral sensitivity distribution different from that of the main photosensitive layers such as BL, GL, and RL described in JP-A-89850 is adjacent to or adjacent to the main photosensitive layer. As described above, various layer configurations and arrangements can be selected according to the purpose of each photosensitive material.

The preferred silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention contains about 30 mol% or less of silver iodide, silver iodobromide, silver iodochloride, or iodochlorobromide. It is silver. Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mol% to about 10 mol% silver iodide. Silver halide grains in photographic emulsions include those having regular crystals such as cubic, octahedral and tetradecahedral, those having irregular crystal forms such as spheres and plates, twin planes, etc. Or a composite form thereof. The grain size of silver halide is about
It may be fine particles of 0.2 μm or less or large-sized grains having a projected area diameter of up to about 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion. Silver halide photographic emulsions usable in the present invention include, for example, Research Disclosure (RD) N
o. 17643 (December 1978), pp. 22-23, "I. Emulsion Production (Emu
lsion preparation and types) ”, and the same No.18716
(November 1979), 648 pages, No.307105 (November 1989), 863
865 pages, and Grafkid, "Physics and Chemistry of Photography", published by Paul Montell (P. Glafkides, Chemie et P
hisique Photographique, PaulMontel, 1967), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (GF D
uffin, Photographic Emulsion Chemistry (Focal Pres
s, 1966)), "Production and Coating of Photographic Emulsions", by Zelikman et al., Published by Focal Press (VL Zelikman et al.,
Making and Coating Photographic Emulsion, Focal Pr
ess, 1964).

Monodisperse emulsions described in US Pat. Nos. 3,574,628 and 3,655,394 and British Patent 1,413,748 are also preferable. Tabular grains having an aspect ratio of about 3 or more can also be used in the present invention. Tabular grains are described by Gatoff, Photographic Science and Engineering (Gutoff, PhotographicScience
and Engineering), Vol. 14, pp. 248-257 (1970);
U.S. Pat.Nos. 4,434,226, 4,414,310, 4,433,0
No. 48, 4,439,520 and British Patent No. 2,112,157. The crystal structure may be uniform, the inside and the outside may be composed of different halogen compositions, may have a layered structure, and even if silver halides having different compositions are joined by epitaxial junction. Also, it may be bonded to a compound other than silver halide such as, for example, silver rhodan or lead oxide. Also, a mixture of particles of various crystal forms may be used. The above emulsion may be either a surface latent image type in which a latent image is mainly formed on the surface, an internal latent image type in which the latent image is formed inside the grains, or a type having a latent image on both the surface and the inside. It is necessary to be. Among the internal latent image type emulsions, core / shell type internal latent image type emulsions described in JP-A-63-264740 may be used. A method for preparing this core / shell type internal latent image type emulsion is described in JP-A-59-133542. The thickness of the shell of this emulsion varies depending on the development process and the like, but is preferably 3 to 40 nm, particularly preferably 5 to 20 nm.

The silver halide emulsion is usually one which has been physically ripened, chemically ripened and spectrally sensitized. Additives used in such a process are described in Research Disclosure No. 17643, No. 18716 and No. 307105, and the relevant portions are summarized in the table below. The light-sensitive material of the present invention comprises two or more types of emulsions having at least one characteristic different from one another in the grain size, grain size distribution, halogen composition, grain shape, and sensitivity of the photosensitive silver halide emulsion.
It can be used by mixing in the same layer. U.S. Patent No.
No. 4,082,553, silver halide grains having a fogged surface, U.S. Pat. It can be preferably used for a silver emulsion layer and / or a substantially light-insensitive hydrophilic colloid layer. The term “silver halide particles having a fogged inside or surface” refers to silver halide grains that can be uniformly (non-imagewise) developed regardless of unexposed portions and exposed portions of the photosensitive material. . A method for preparing silver halide grains having the inside or the surface of the grains fogged is described in U.S. Pat.
No. 9-214852. The silver halides forming the internal nuclei of the core / shell type silver halide grains whose insides are fogged may have the same halogen composition or different halogen compositions. As the silver halide having the inside or surface of the grain fogged, any of silver chloride, silver chlorobromide, silver iodobromide and silver chloroiodobromide can be used. There is no particular limitation on the grain size of these fogged silver halide grains, but the average grain size is
It is preferably from 0.01 to 0.75 μm, particularly preferably from 0.05 to 0.6 μm. Also,
The grain shape is not particularly limited, and may be regular grains or polydisperse emulsions, but may be monodispersed (at least 95% of the weight or the number of silver halide grains is within ± 40% of the average grain size). Having a particle size of 1).

In the present invention, it is preferable to use a non-photosensitive fine grain silver halide. Non-photosensitive fine grain silver halide is silver halide fine grains that are not exposed during imagewise exposure to obtain a dye image and are not substantially developed in the developing process, and are preferably not fogged in advance. . The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and may contain silver chloride and / or silver iodide, if necessary. Preferably, it contains 0.5 to 10 mol% of silver iodide. Fine grain silver halide has an average grain size (average value of circle equivalent diameter of projected area)
Is preferably 0.01 to 0.5 μm, more preferably 0.02 to 0.2 μm. Fine grain silver halide can be prepared by the same method as that for ordinary photosensitive silver halide. In this case, the surface of the silver halide grains does not need to be optically sensitized, and no spectral sensitization is required. However, prior to adding this to the coating solution, it is preferable to add a known stabilizer such as a triazole-based, azaindene-based, benzothiazolium-based, or mercapto-based compound or a zinc compound in advance. Colloidal silver can be preferably contained in the layer containing fine silver halide grains. Coated silver amount of the light-sensitive material of the present invention is preferably 6.0 g / m ² or less, 4.5 g / m ² or less is most preferred.

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. Additive type RD17643 RD18716 RD307105 1. Chemical sensitizer page 23, page 648, right column, page 866 2. Sensitivity enhancer 648, right column 3. Spectral sensitizer, page 23-24, page 648, right column, pages 866-868 Color sensitizer 〜page 649 right column 4. Brightening agent page 24 page 647 right column page 868 5. Fogging prevention page 24-25 page 649 right column 868-870 agent, stabilizer 6.Light absorber, 25- Page 26 649 Right column Page 873 Filter ~ Page 650 Left column Dye, UV absorber 7.Stain 25 Page Right column 650 Page Left column 872 Inhibitor ~ Right column 8. Dye image 25 Page 650 Page Left column 872 Stabilizer 9. Hardener page 26 page 651 left column 874-875 10. Binder page 26 page 651 left column 873-874 11. Plasticizer, page 27 page 650 right column page 876 Lubricant 12. Coating aid Pp. 26-27 650 right column 875-876 Surfactant 13. Stat. 27 page 650 right column 876-877 Inhibitor 14. Matsuto 878-879

Further, in order to prevent deterioration of photographic performance due to formaldehyde gas, it is preferable to add to the light-sensitive material a compound capable of reacting with formaldehyde described in US Pat. Nos. 4,411,987 and 4,435,503. . U.S. Pat.No. 4,740,454
No. 4,788,132, JP-A-62-18539, JP-A-1-28
It is preferable to include a mercapto compound described in No. 3551. In the light-sensitive material of the present invention, compounds described in JP-A-1-06052, which release a fogging agent, a development accelerator, a silver halide solvent or a precursor thereof irrespective of the amount of developed silver produced by development processing Is preferably contained. In the light-sensitive material of the present invention, International Publication WO88 / 04794, dyes dispersed by the method described in JP-A-1-502912 or
EP 317,308A, U.S. Pat.No. 4,420,555, JP-A 1-2593
The dye described in No. 58 is preferably contained. Various color couplers can be used in the present invention, and specific examples thereof are described in Research Disclosure No. 1764, supra.
No. 307105, VII-CG, and VII-CG
The patent is described in US Pat. As the yellow coupler, for example, U.S. Pat.
No. 2,620, No. 4,326,024, No. 4,401,752, No.
No. 4,248,961, Japanese Patent Publication No. 58-10739, British Patent No. 1,425,
No. 020, No. 1,476,760, U.S. Pat.No. 3,973,968,
Nos. 4,314,023 and 4,511,649, European Patent 24
Those described in 9,473A and the like are preferred.

As the magenta coupler, 5-pyrazolone compounds and pyrazoloazole compounds are preferable, and US Pat. Nos. 4,310,619, 4,351,897 and European Patent 73,63 are preferred.
6, U.S. Pat.Nos. 3,061,432 and 3,725,067,
Research Disclosure No.24220 (June 1984
), JP-A-60-33552, Research Disclosure No.24230 (June 1984), JP-A-60-43659, 61-7
No. 2238, No. 60-35730, No. 55-118034, No. 60-185951
No. 4,500,630, U.S. Pat.No. 4,540,654, U.S. Pat.
Those described in 4,556,630, International Publication WO88 / 04795 and the like are particularly preferred. Cyan couplers include phenolic and naphthol couplers and are described in U.S. Pat.
52,212, 4,146,396, 4,228,233, and
4,296,200, 2,369,929, 2,801,171,
No. 2,772,162, No. 2,895,826, No. 3,772,002
No. 3, No. 3,758,308, No. 4,334,011, No. 4,32
7,173, West German Patent Publication No. 3,329,729, European Patent No. 12
No. 1,365A, No. 249,453A, U.S. Pat.No. 3,446,622
No. 4,333,999, 4,775,616, 4,45
No. 1,559, No. 4,427,767, No. 4,690,889, No.
Preferred are those described in 4,254,212, 4,296,199 and JP-A-61-42658. Further, JP-A-64-553,
Pyrazoloazole couplers described in JP-A Nos. 64-554, 64-555 and 64-556, and imidazole couplers described in U.S. Pat. No. 4,818,672 can also be used. Typical examples of polymerized dye-forming couplers are described in U.S. Pat.
No. 3,451,820, No. 4,080,211 and No. 4,367,282,
Nos. 4,409,320, 4,576,910, UK Patent 2,1
02,137 and EP 341,188A.

Examples of couplers in which the color forming dye has an appropriate diffusibility include US Pat. No. 4,366,237 and British Patent 2,125,
No. 570, European Patent No. 96,570, German Patent (public) No. 3,
Those described in No. 234,533 are preferred. Colored couplers to correct unwanted absorption of colored dyes are
No. 30743, Disclosure No. 17643, No. 30710
5, VII-G, U.S. Pat.No. 4,163,670, JP-B-57-3
No. 9413, U.S. Pat.Nos. 4,004,929, 4,138,258,
Those described in British Patent No. 1,146,368 are preferred. Further, a coupler that corrects unnecessary absorption of a coloring dye by a fluorescent dye released at the time of coupling described in U.S. Pat. It is also preferable to use a coupler having a precursor group as a leaving group. Of the compounds that release a photographically useful residue upon coupling, compounds other than the compound of the present invention can be preferably used. DIR couplers that release development inhibitors are described above.
Patents described in RD 17643, Item VII-F and No. 307105, Item VII-F, JP-A-57-151944 and 57-154234.
And Nos. 60-184248, 63-37346, 63-37350, and U.S. Pat. Nos. 4,248,962 and 4,782,012 are preferred. RD No. 11449, 24241, JP-A-61-20124
The bleaching accelerator releasing coupler described in No. 7, etc. is effective for shortening the time of a processing step having bleaching ability,
The effect is great when it is added to a photosensitive material using the above-mentioned tabular silver halide grains. As the coupler capable of releasing a nucleating agent or a development accelerator imagewise during development, those described in British Patent Nos. 2,097,140 and 2,131,188, JP-A-59-157638 and JP-A-59-170840 are preferable. Further, by a redox reaction with an oxidant of the developing agent described in JP-A-60-107029, JP-A-60-252340, JP-A-1-44940 and 1-45687, a fogging agent and a development accelerator. Compounds that release a silver halide solvent or the like are also 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 and US Pat. Nos. 4,283,472 and 4,3.
Nos. 38,393, 4,310,618, etc., multi-equivalent couplers described in JP-A-60-185950, DIR redox compound releasing couplers described in JP-A-62-24252, etc., DIR coupler releasing couplers, DIR coupler releasing redox compounds Or a DIR redox-releasing redox compound, a coupler releasing a dye capable of recoloring after detachment described in European Patent Nos. 173,302A and 313,308A, a ligand releasing coupler described in U.S. Pat. -75747 Leuco dye releasing couplers, U.S. Pat.
No. 181 which emits a fluorescent dye.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods. Examples of high boiling point solvents used in the oil-in-water dispersion method are described in U.S. Pat. No. 2,322,027. Specific examples of high-boiling organic solvents having a boiling point at normal pressure of 175 ° C. or higher used in the oil-in-water dispersion method include phthalic 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, tributoxyethyl phosphate, trichloropropyl phosphate, dichloropropyl
-2-Ethylhexylphenylphosphonate, etc., Benzoic acid esters (2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), Amides (N, N-diethyldodecaneamide, N, N-diethyllauryl) Amides, N-tetradecylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol, 2,4-di-tert-amylphenol, etc.), aliphatic carboxylic acid esters (bis (2-ethylhexyl) sebacate, dioctylazese) Rate, glycerol tributyrate, isostearyl lactate,
Trioctyl citrate), aniline derivatives (N, N-
Dibutyl-2-butoxy-5-tert-octylaniline); and hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.). As the auxiliary solvent, the boiling point is about 30 ℃ or more, preferably 50 ℃
An organic solvent having a temperature of about 160 ° C. or less can be used, and typical examples include ethyl acetate, butyl acetate, ethyl propionate,
Examples include methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide and the like. The steps and effects of the latex dispersion method and specific examples of the latex for impregnation are described in U.S. Pat. No. 4,199,363 and 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-62-272248,
And JP-A-1-80941, 1,2-benzisothiazolin-3-one, n-butyl p-hydroxybenzoate,
It is preferable to add various preservatives or fungicides such as phenol, 4-chloro-3,5-dimethylphenol, 2-phenoxyethanol, and 2- (4-thiazolyl) benzimidazole. The present invention can be applied to various color light-sensitive materials. Typical examples include color negative films for general use or movies, 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 include, for example, the aforementioned R
D. No. 17643, page 28, No. 18716, page 647, right column, 648
No. 307105, page 879. In the light-sensitive material of the present invention, the total thickness of all the hydrophilic colloid layers on the side having the emulsion layer is preferably 28 μm or less, more preferably 23 μm or less, still more 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 means a film thickness measured under humidity control at 25 ° C. and a relative humidity of 55% (2 days), and the film swelling rate T _1/2 can be measured according to a method known in the art. For example, Photographic Science and Engineering (Photog) by A. Green et al.
r.Sci.Eng.), Vol. 19, No. 2, pp. 124-129, can be measured by using a serometer (swelling meter), and T _1/2 is 30 ° C. in a color developing solution. 90% of the maximum swollen film thickness reached when the treatment is performed for 3 minutes and 15 seconds is defined as the saturated film thickness, and is defined as the time required to reach 1/2 of the saturated film thickness. Film swelling speed T
_{The 1/2} can be adjusted by adding a hardening agent to gelatin as a binder or by changing the aging conditions after coating. The swelling rate is preferably 150 to 400%. The swelling ratio can be calculated from the maximum swelling film thickness under the conditions described above according to the formula: (maximum swelling film thickness-film thickness) / film thickness. In the light-sensitive material of the present invention, a hydrophilic colloid layer (referred to as a back layer) having a total dry film thickness of 2 μm to 20 μm is preferably provided on the side opposite to the side having the emulsion layer.
In this back layer, the above-mentioned light absorber, filter dye,
It is preferable to contain an ultraviolet absorber, an antistatic agent, a hardener, a binder, a plasticizer, a lubricant, a coating aid, a surfactant, and the like. The swelling ratio of this back layer is 150 ~ 500
% Is preferred.

The color photographic light-sensitive material according to the present invention has the RD. No. 17643, pages 28 to 29, No. 18716, page 651, left column to right column, and No. 307105, pages 880 to 881, can be used for development. The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution mainly containing an aromatic primary amine color developing agent. As the color developing agent,
Aminophenol compounds are also useful, but p-phenylenediamine compounds are preferably used, and typical examples thereof are 3-methyl-4-amino-N, N-diethylaniline and 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 sulfates, hydrochlorides or p-toluenesulfonates thereof. Among these, in particular, 3-methyl-4-amino-N
-Ethyl-N-β-hydroxyethylaniline sulfate is preferred. These compounds can be used in combination of two or more depending on the purpose. The color developing solution is an alkali metal carbonate,
PH buffers such as borates or phosphates, and development inhibitors or antifoggants such as chlorides, bromides, iodides, benzimidazoles, benzothiazoles or mercapto compounds. General. Also, as required, hydroxylamine, diethylhydroxylamine, sulfite, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazide, triethanolamine, various preservatives such as catecholsulfonic acid, ethylene glycol, Organic solvents such as diethylene glycol, benzyl alcohol,
Development accelerators such as polyethylene glycol, quaternary ammonium salts, amines, dye-forming couplers, competitive couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity-imparting agents, aminopolycarboxylic acids, aminopolyphosphones Acids, alkylphosphonic acids, various chelating agents represented by phosphonocarboxylic acids, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene- 1,1-diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid,
As representative examples, ethylenediamine-N, N, N, N-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and salts thereof can be mentioned.

When the reversal processing is carried out, black and white development is usually carried out and then color development is carried out. In this black-and-white developer, 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 these color developing solutions and black-and-white developing solutions is generally 9 to 12. The replenishment 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. You can also. When the replenishment rate is reduced, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the contact area of the processing tank with the air. The contact area between the photographic processing solution and air in the processing tank can be represented by the aperture ratio defined below. That is, aperture ratio = [contact area between processing solution and air (cm ² )] ÷ [volume of processing solution (cm ³ )] The opening ratio is preferably 0.1 or less, more preferably 0.001 to 0.05. It is. As a method of reducing the aperture ratio in this manner, in addition to providing a shield such as a floating lid on the photographic processing liquid surface of the processing tank, a method using a movable lid described in JP-A-1-82033, 63-216050 can be mentioned. Reducing the aperture ratio is not only a step of color development and a step of black-and-white development, but also various subsequent steps, for example, bleaching, bleach-fixing,
It is preferably applied in all steps such as fixing, washing and stabilization. The amount of replenishment can also be reduced by using means for suppressing the accumulation of bromide ions in the developer. The time for the color development processing is usually set between 2 and 5 minutes, but the processing time can be further shortened by using a high temperature and high pH and using a high concentration of the color developing agent.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. In order to further speed up the processing, a processing method of performing bleach-fixing after bleaching may be used. Further, processing in two successive bleach-fixing baths, fixing before bleach-fixing, or bleaching after bleach-fixing can be arbitrarily performed according to the purpose. As the bleaching agent, compounds of polyvalent metals such as iron (III), peracids, quinones, nitro compounds and the like are used. Typical bleaching agents include organic complex salts of iron (III) 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 a bleaching solution and a bleach-fixing solution. The pH of a bleaching solution or a bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is usually 4.0 to 8, but a 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 bleach accelerators are described in the following specification: US Pat. No. 3,893,858, West German Patent 1,290,812.
No. 2,059,988, JP-A-53-32736, JP-A-53-57831
Nos. 53-37418, 53-72623, 53-95630, 53
-95631, 53-104232, 53-124424, 53-141
No. 623, No. 53-28426, Research Disclosure
Compounds having a mercapto group or a disulfide group described in No. 17129 (July, 1978);
No. 45-8506, JP-A-52-20832 and JP-A-53-32735, U.S. Pat. No. 3,706,561
No. 1,127,715, thiourea derivatives described in US Pat.
Iodide salts described in JP-A-58-16,235; West German Patent No. 966,
Polyoxyethylene compounds described in Nos. 410 and 2,748,430; polyamine compounds described in JP-B No. 45-8836; and other JP-A Nos. 49-40,943, 49-59,644 and 53-94,92.
No. 7, 54-35,727, 55-26,506, 58-163,940
Compounds described in (1); bromide ions and the like can be used. Among them, a compound having a mercapto group or a disulfide group is preferable from the viewpoint of a large accelerating effect, and particularly, US Pat.
3,858, West German Patent 1,290,812, JP-A-53-95,630
Are preferred. Further, U.S. Pat.
The compounds described in 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 photographic material for photography. The bleaching solution and the bleach-fixing solution preferably contain an organic acid in order to prevent bleaching stain in addition to the above compounds. Particularly preferred organic acids have an acid dissociation constant (pKa) of 2
-5, specifically, acetic acid, propionic acid,
Hydroxyacetic acid and the like are preferred. Examples of the fixing agent used in the fixing solution or the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas, a large amount of iodides, and the like. In particular, ammonium thiosulfate can be used most widely. It is also preferable to use a combination of a thiosulfate and a thiocyanate, a thioether-based compound, thiourea, or the like. Examples of preservatives for the fixing solution and the bleach-fixing solution include sulfites, bisulfites, carbonyl bisulfite adducts and EP No. 294.
The sulfinic acid compounds described in 769A are preferred. Furthermore,
It is preferable to add various aminopolycarboxylic acids or organic phosphonic acids to the fixing solution or the bleach-fixing solution for the purpose of stabilizing the solution. In the present invention, the fixing solution or the bleach-fixing solution contains pH.
For the adjustment, a compound having a pKa of 6.0 to 9.0, preferably imidazoles such as imidazole, 1-methylimidazole, 1-ethylimidazole, and 2-methylimidazole is used.
It is preferable to add 1 to 10 mol / l.

The total time of the desilvering process is preferably as short as possible so long as no desilvering failure occurs. Preferred time is 1 minute to 3
Minutes, more preferably 1 to 2 minutes. The processing temperature is from 25 ° C to 50 ° C, preferably from 35 ° C to 45 ° C. In a preferable temperature range, the desilvering speed is improved, and generation of stain after processing is effectively prevented. In the desilvering step, it is preferable that the stirring is strengthened as much as possible.
As a specific method of strengthening the stirring, a method of impinging a jet of a processing solution on an emulsion surface of a photosensitive material described in JP-A-62-183460, or a method of stirring using a rotating means described in JP-A-62-183461. A method for improving the effect, a method for moving the photosensitive material while bringing the wiper blade provided in the solution into contact with the emulsion surface, and making the emulsion surface turbulent to improve the stirring effect, and a circulation of the entire processing solution. There is a method of increasing the flow rate. Such a stirring improving means is effective for any of the bleaching solution, the bleach-fixing solution and the fixing solution. 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 consequently increases the desilvering speed. Further, the above-mentioned means for improving the stirring is more effective when a bleaching accelerator is used, and can significantly increase the accelerating effect or eliminate the fixing inhibiting effect of the bleaching accelerator. The automatic developing machine used for the light-sensitive material of the present invention is disclosed in JP-A-60-191257.
It is preferable to have the photosensitive material conveying means described in JP-A Nos. 60-191258 and 60-191259. Japanese Patent Laid-Open No. Sho 6
As described in Japanese Patent Application No. 0-191257, such a transport means can significantly reduce the carry-in of the processing liquid from the pre-bath to the post-bath, and is highly effective in preventing the performance of the processing liquid from deteriorating. Such an effect is particularly effective for reducing the processing time in each step and reducing the replenishing amount of the processing solution.

The silver halide color photographic light-sensitive material of the present invention is generally washed with water and / or stabilized after the desilvering treatment. The amount of rinsing water in the rinsing step depends on the characteristics of the photosensitive material (for example, the material used such as a coupler), the use, the rinsing water temperature, the number of rinsing tanks (number of stages), the replenishment method such as countercurrent, forward flow, and other various conditions. Can be set widely.
Of these, the relationship between the number of washing tanks and the amount of water in the multi-stage countercurrent method is described in the Journal-al of the Society of Motion Picture a.
nd Television Engineers Vol. 64, pp. 248-253 (195
May, 2005). According to the multi-stage countercurrent method described in the above-mentioned document, the amount of washing water can be greatly reduced.However, due to an increase in the residence time of water in the tank, bacteria are propagated, and the generated suspended matter adheres to the photosensitive material. Problem arises. In the processing of the color light-sensitive material of the present invention, as a solution to such a problem, the method of reducing calcium ions and magnesium ions described in JP-A-62-288838 can be used very effectively. Also, isothiazolone compounds and thiabendazoles described in JP-A-57-8,542, chlorine-based disinfectants such as chlorinated sodium isocyanurate, and other benzotriazoles, etc., written by Hiroshi Horiguchi, "Bactericidal and Fungicide Chemistry" (1986)
Sankyo Publishing, Sanitary Technology Association, "Sterilization, sterilization, and fungicide technology for microorganisms" (1982) Industrial Technology Association, Fungicide described in "Encyclopedia of fungicides and fungicides" (ed. 1986) Can also be used. PH of washing water in processing the photosensitive material of the present invention
Is 4 to 9, preferably 5 to 8. Washing water temperature and washing time can also be set variously depending on the characteristics of the photosensitive material, the application, etc.
A range of 30 seconds to 5 minutes at 25-40 ° C is selected. Further, the light-sensitive material of the present invention can be processed directly with a stabilizing solution instead of the above-mentioned washing. In such a stabilization treatment, any of the known methods described in JP-A-57-8543, JP-A-58-14834 and JP-A-60-220345 can be used. Further, after the water washing treatment, a stabilization treatment may be further carried out. As an example, a stabilizing bath containing a dye stabilizer and a surfactant, which is used as a final bath of a color light-sensitive material for photography, is exemplified. be able to. As a dye stabilizer,
Aldehydes such as formalin and glutaraldehyde,
Examples thereof include N-methylol compounds, hexamethylenetetramine and aldehyde sulfite adducts.
Various chelating agents and fungicides 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 developing machine or the like, when each of the above processing solutions is concentrated by evaporation,
It is preferable to correct the concentration by adding water. The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up the processing. In order to incorporate the color developing agent, it is preferable to use various precursors of a color developing agent. For example, indoaniline-based compounds described in U.S. Pat. Described metal salt complex, JP-A-53-135
Urethane compounds described in No. 628 can be mentioned.
The silver halide color light-sensitive material of the present invention may contain various 1-phenyl-3-
Pyrazolidones may be incorporated. Typical compounds are described in JP-A-56-64339, JP-A-57-144547 and JP-A-58-115438. Various processing solutions in the present invention are 10 ° C
Used at 5050 ° C. Usually, a temperature of 33 ° C to 38 ° C is standard, but a higher temperature promotes the processing and shortens the processing time, and conversely, lowers the temperature to achieve the improvement of the image quality and the stability of the processing solution. be able to. Further, the silver halide light-sensitive material of the present invention is disclosed in U.S. Pat.No. 4,500,626,
The invention can also be applied to a photothermographic material described in European Patent No. 210,660A2.

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EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.

Example 1 On a subbed cellulose triacetate film support,
Sample 101, which is a multilayer color photographic material composed of each layer 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 dyes are shown in terms of moles per mole of silver halide in the same layer. First layer (antihalation layer) Black colloidal silver 0.15 Gelatin 1.90 ExM-8 2.0 × 10 ^-2

Second Layer (Intermediate Layer) Gelatin 2.10 UV-1 3.0 × 10 ^-2 UV-2 6.0 × 10 ^-2 UV-3 7.0 × 10 ^-2 ExF-1 4.0 × 10 ^-3 Solv-2 7.0 × 10 ^-2 Third layer (low-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 2 mol%, internal high AgI type, sphere equivalent diameter 0.25 μm, sphere equivalent diameter) Variation coefficient of 15%, normal crystal, twin crystal mixed particles, diameter / thickness ratio 1.2) Silver coating amount 0.50 Gelatin 1.50 ExS-1 1.0 × 10 ⁻⁴ ExS-2 3.0 × 10 ⁻⁴ ExS-3 1.0x10 ^-5 ExC-3 0.22 ExC-4 3.0x10 ^-3 Solv-1 0.15x10 ^-3

Fourth Layer (Medium Sensitivity Red Sensitive Emulsion Layer) Silver iodobromide emulsion (AgI 4 mol%, internal high AgI type, spherical equivalent diameter 0.55 μm, variation coefficient of spherical equivalent diameter 18%, normal crystal, twin Crystal mixed particles, diameter / thickness ratio 1.0) Silver coating amount 0.85 Gelatin 2.00 ExS-1 1.0 × 10 ^-4 ExS-2 3.0 × 10 ^-4 ExS-3 1.0 × 10 ^-5 ExC-2 8.0 × 10 ⁻² ExC-3 0.33 ExY-13 2.0 × 10 ⁻² ExY-14 1.0 × 10 ⁻² Cpd-10 1.0 × 10 ⁻⁴ Solv-10 .10

Fifth Layer (High Sensitivity Red Sensitive Emulsion Layer) Silver iodobromide emulsion (AgI 10 mol%, internal high AgI type, spherical equivalent diameter 0.60 μm, variation coefficient of spherical equivalent diameter 20%, twin mixed particles, Diameter / thickness ratio 5.5) Silver coating amount 0.70 Gelatin 1.60 ExS-1 1.0x10 ^-4 ExS-2 3.0x10 ^-4 ExS-3 1.0x10 ^-5 ExC- 5 7.0 × 10 ^-2 ExC-6 8.0 × 10 ^-2 Solv-1 0.15 Solv-2 8.0 × 10 ^-2

Sixth Layer (Intermediate Layer) Gelatin 1.10 P-2 0.17 Cpd-1 0.10 Cpd-4 0.17 Solv-1 5.0 × 10 ^-2

Seventh Layer (Low Sensitivity Green Sensitive Emulsion Layer) Silver iodobromide emulsion (AgI 2 mol%, internal high AgI type, sphere equivalent diameter 0.3 μm, variation coefficient of sphere equivalent diameter 28%, normal crystal, twin Crystal mixed particles, diameter / thickness ratio 2.5) Silver coating amount 0.30 Gelatin 0.50 ExS-4 5.0 × 10 ^-4 ExS-5 2.0 × 10 ^-4 ExS-6 0.3 × 10 ^-4 ExM-8 3.0 × 10 ^-2 ExM-9 0.20 ExY-13 3.0 × 10 ^-2 Cpd-11 7.0 × 10 ^-3 Solv-1 0.20

Eighth Layer (Medium Sensitivity Green Sensitive Emulsion Layer) Silver iodobromide emulsion (AgI 4 mol%, internal high AgI type, sphere equivalent diameter 0.55 μm, variation coefficient of sphere equivalent diameter 20%, normal crystal, twin Crystal mixed particles, diameter / thickness ratio 4.0) Silver coating amount 0.70 Gelatin 1.00 ExS-4 5.0 × 10 ^-4 ExS-5 2.0 × 10 ^-4 ExS-6 3.0 × 10 ^-5 ExM-8 3.0 × 10 ⁻² ExM-9 0.25 ExM-10 1.5 × 10 ⁻² ExY-13 4.0 × 10 ⁻² Cpd-11 9.0 × 10 ⁻³ Solv-10 .20

Ninth layer (high-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (AgI 10 mol%, internal high AgI type, sphere equivalent diameter 0.55 μm, variation coefficient of sphere equivalent diameter 18%, diameter / thickness ratio 7 .5) Silver coating amount 0.50 Gelatin 0.90 ExS-4 2.0x10 ^-4 ExS-5 2.0x10 ^-4 ExS-6 2.0x10 ^-5 ExS-7 3.0x 10 ⁻⁴ ExM-8 2.0 × 10 ⁻² ExM-11 6.0 × 10 ⁻² ExM-12 2.0 × 10 ⁻² Cpd-2 1.0 × 10 ⁻² Cpd-9 2.0 × 10 ⁻⁴ Cpd-10 2.0 × 10 ⁻⁴ Solv-1 0.20 Solv-2 5.0 × 10 ⁻²

10th layer (yellow filter layer) Gelatin 0.90 Yellow colloidal silver 5.0 × 10 ^-2 Cpd-1 0.20 Solv-1 0.15 11th layer (low-sensitivity blue-sensitive emulsion layer) Odor Silver halide emulsion (AgI 4 mol%, internal high AgI type, sphere equivalent diameter 0.5 μm, variation coefficient of sphere equivalent diameter 15%, octahedral grains) Silver coating amount 0.40 Gelatin 1.00 ExS-8 2.0 × 10 ^-4 ExY-13 9.0 × 10 ^-2 ExY-15 0.90 Cpd-2 1.0 × 10 ^-2 Solv-1 0.30

Twelfth layer (high-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion (AgI 10 mol%, internal high AgI type, spherical equivalent diameter 1.3 μm, variation coefficient of spherical equivalent diameter 25%, normal crystal, twin Crystal mixed particles, diameter / thickness ratio 4.5) Silver coating amount 0.50 Gelatin 0.60 ExS-8 1.0 × 10 ^-4 ExY-15 0.12 Cpd-2 1.0 × 10 ^-3 Solv-14 0.0 × 10 ^-2 13th layer (first protective layer) Fine grain silver iodobromide (average particle size 0.07 μm, AgI 1 mol%) 0.20 Gelatin 0.80 UV-2 0.10 UV-3 0.0. 10 UV-4 0.20 Solv-3 4.0 × 10 ^-2 P-2 9.0 × 10 ^-2

14th layer (second protective layer) Gelatin 0.90 B-1 (diameter 1.5 μm) 0.10 B-2 (diameter 1.5 μm) 0.10 B-3 2.0 × 10 ^-2 H-1 0.40 Further, in order to improve storage stability, processability, pressure resistance, antifungal / antibacterial property, antistatic property, and coating property, the following Cpd-
3, Cpd-5, Cpd-6, Cpd-7, Cpd-
8, P-1, W-1, W-2 and W-3 were added.

In addition to the above, n-butyl-p-hydroxybenzoate was added. B-4, F-1, F
-4, F-5, F-6, F-7, F-8, F-9, F-
10, F-11, F-13 and iron salt, lead salt, gold salt,
Contains platinum, iridium and rhodium salts.
Next, the chemical structural formulas or chemical names of the compounds used in the present invention are shown below.

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(Samples 102 to 111) Third Sample 101
Sample 102 was prepared by adding 0.0045 g / m ² of the layer and 0.0085 g / m ² of the coupler (1) of the present invention to the fourth layer. Samples 103 to 111 as shown in Table 1 were prepared by substituting the coupler (1) of the present invention in Sample 102 with another coupler of the present invention and a comparative coupler in an equal weight. (Samples 112 and 113) Samples 112 and 113 were prepared by adjusting the addition amount of the coupler for comparison so that the gradation was almost the same as that of the samples 102 to 105 using the coupler of the present invention.

These samples were exposed in a white image and subjected to the color development processing described below, and the slope of the straight line connecting the points of cyan density (fog + 0.2) and (fog + 1.2) was determined as gamma.
The sharpness was also measured in the same manner as in the conventional MTF method, and the cyan image 25 cycles / mm was obtained. In addition, after imagewise exposure through a red filter (Fujifilm SC-62), a green filter (Fujifilm BPN-45) was used to reduce the exposure to 0.
05CMS uniform exposure and development processing, cyan density 1.5
The value obtained by subtracting the magenta density in the cyan fog density from the magenta density in Table 1 is shown in Table 1 as the color turbidity.

Also, 500 μm × 4 cm and 15 μm × 4 cm
Soft X-rays were radiated through the aperture, and the cyan density ratio at each center was obtained as an edge effect. Further imagewise exposure as above, 50
After storing for 10 days under the condition of 80% relative humidity and 80% relative humidity, the same color development was performed, and the sensitivity change when the logarithm of the reciprocal of the exposure of cyan density (fog + 0.2) was taken as relative sensitivity is shown in Table 1.
Summarized in Color development processing was performed as follows by an automatic processor.

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[Table 1]

Step Processing time Processing temperature Color development 3 minutes 15 seconds 38 ° C. Bleach 6 minutes 30 seconds 38 ° C. Water wash 2 minutes 10 seconds 24 ° C. Settling 4 minutes 20 seconds 38 ° C. Water wash (1) 1 minute 05 seconds 24 ° C. Washing with water (2) 1 minute 00 seconds 24 ℃ Stability 1 minute 05 seconds 38 ℃ Dry 4 minutes 20 seconds 55 ℃

Next, the composition of the processing liquid will be described. (Color developer) (Unit: g) Diethylenetriaminepentaacetic acid 1.0 1-Hydroxyethylidene-1,1-diphosphonic acid 3.0 Sodium sulfite 4.0 Potassium carbonate 30.0 Potassium bromide 1.4 Potassium iodide 1. 5 mg hydroxylamine sulfate 2.4 4- [N-ethyl-N-β-hydroxyethylamino] -4.5 2-methylaniline sulfate Water was added to 1.0 liter pH 10.05

(Bleaching Solution) (Unit: g) Ethylenediaminetetraacetic acid sodium ferric trihydrate 100.0 Ethylenediaminetetraacetic acid disodium salt 10.0 Ammonium bromide 140.0 Ammonium nitrate 30.0 Ammonia water (27%) 6 Add 0.5 ml water and 1.0 liter pH 6.0

(Fixer) (Unit: g) Ethylenediaminetetraacetic acid disodium salt 0.5 Sodium sulfite 7.0 Sodium bisulfite 5.0 Ammonium thiosulfate aqueous solution (70%) 170.0 ml Water is added to 1.0 liter pH 6. 7

(Stabilizing Solution) (Unit: g) Formalin (37%) 2.0 ml Polyoxyethylene-p-monononylphenyl ether 0.3 (Average degree of polymerization 10) Ethylenediaminetetraacetic acid disodium salt 0.05 Water was added. 1.0 liter pH 5.0-8.0

It can be seen from Table 1 that the samples using the conventional coupler have little effect on the color turbidity and the sharpness when added in a small amount, and even if added in a large amount, the samples 102 to 105 in which a small amount of the coupler of the present invention is added are added. It is clear that the sharpness and color reproducibility are inferior, and the effectiveness of the coupler of the present invention is shown. Further, it is apparent that the coupler of the present invention has little variation in photographic property during the aging period from exposure to development.

Example 2 On a subbed cellulose triacetate film support,
A sample 201, which is a multilayer color photosensitive material composed of each layer 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 dyes are shown in terms of moles per mole of silver halide in the same layer. The symbols indicating the additives have the following meanings. However, when there are multiple utilities, only one of them is listed as a representative.

UV: UV absorber, Solv: High boiling organic solvent, ExF: Dye, ExS: Sensitizing dye, ExC: Cyan coupler, ExM: Magenta coupler, ExY: Yellow coupler, Cpd; Additive first layer (halation) Prevention layer) Black colloidal silver 0.15 Gelatin 2.33 ExM-6 0.11 UV-1 3.0x10 ^-2 UV-2 6.0x10 ^-2 UV-3 7.0x10 ^-2 Solv -1 0.16 Solv-2 0.10 ExF- 1 1.0 × 10 -2 ExF-2 4.0 × 10 -2 ExF-3 5.0 × 10 -3 Cpd-6 1.0 × 10 - ³

Second Layer (Low Sensitivity Red Sensitive Emulsion Layer) Silver iodobromide emulsion (AgI 4.0 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) coating silver amount 0.35 silver iodobromide emulsion (AgI 6.0 mol%, internal high AgI type with core-shell ratio 1: 2, sphere equivalent diameter 0.45 μm variation of sphere equivalent diameter Coefficient 23%, plate-like particles, diameter / thickness ratio 2.0) Silver coating amount 0.18 Gelatin 0.77 ExS-1 2.4 × 10 ^-4 ExS-2 1.4 × 10 ^-4 ExS-52 4. 3 × 10 ⁻⁴ ExS-7 4.1 × 10 ⁻⁶ ExC-1 0.17 ExC-2 4.0 × 10 ⁻² ExC-3 8.0 × 10 ⁻² Comparative coupler (a) 5. 0 x 10 ^-3

Third Layer (Medium Sensitivity Red Sensitive Emulsion Layer) Silver iodobromide emulsion (AgI 6.0 mol%, internal high AgI type with core-shell ratio 1: 2, equivalent sphere diameter 0.65 μm, variation in equivalent sphere diameter) Coefficient 23%, plate-shaped particles, diameter / thickness ratio 2.0) Coating amount of silver 0.80 Gelatin 1.46 ExS-1 2.4 × 10 ^-4 ExS-2 1.4 × 10 ^-4 ExS-5 2.4 × 10 ⁻⁴ ExS-7 4.3 × 10 ⁻⁶ ExC-1 0.38 ExC-2 2.0 × 10 ⁻² ExC-3 0.12 ExM-7 3.0 × 10 ⁻² UV -2 5.7x10 ^-2 UV-3 5.7x10 ^-2 Comparative coupler (a) 3.0x10 ^-3

Fourth Layer (High-Sensitivity Red-Sensitive Emulsion Layer) Silver iodobromide emulsion (9.3 mol% of AgI, multi-structured particles having a core-shell ratio of 3: 4: 2, AgI content of 24,0,6 from the inside). Mol%, equivalent sphere diameter 0.75 μm, variation coefficient of equivalent sphere diameter 23%, plate-like particles, diameter / thickness ratio 2.5) amount of coated silver 1.49 gelatin 1.38 ExS-1 2.0 × 10 ^{− 4} ExS-2 1.1 × 10 ⁻⁴ ExS-5 1.9 × 10 ⁻⁴ ExS-7 1.4 × 10 ⁻⁵ ExC-1 8.0 × 10 ⁻² ExC-4 9.0 × 10 ^{− 2} Comparative coupler (a) 2.0 × 10 ⁻³ Solv-1 0.20 Solv-2 0.53

Fifth layer (intermediate layer) Gelatin 0.62 Cpd-1 0.13 Polyethyl acrylate latex 8.0 × 10 ⁻² Solv-1 8.0 × 10 ⁻² Sixth layer (low-sensitivity green-sensitive emulsion) Layer) Silver iodobromide emulsion (AgI 4.0 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) coated silver amount 0.19 gelatin ^{0.44 ExS-3 1.5 × 10 -4} ExS-4 4.4 × 10 -4 ExS-5 9.2 × 10 -5 ExM-5 0.17 ExM-7 3.0 × 10 ^-2 Solv-1 0.13 Solv-4 1.0 x 10 ^-2

Seventh Layer (Medium-Sensitivity Green Sensitive Emulsion Layer) Silver iodobromide emulsion (AgI 4.0 mol%, uniform AgI type, sphere equivalent diameter 0.55 μm, variation coefficient of sphere equivalent diameter 15%, plate-like particles , Diameter / thickness ratio 4.0) amount of coated silver 0.24 gelatin 0.54 ExS-3 2.1 × 10 ^-4 ExS-4 6.3 × 10 ^-4 ExS-5 1.3 × 10 ^-4 ExM -5 0.15 ExM-7 4.0 × 10 -2 ExY-8 1.0 × 10 -2 Solv-1 0.13 Solv-4 1.0 × 10 -2

Eighth Layer (High Sensitivity Green Sensitive Emulsion Layer) Silver iodobromide emulsion (multilayer structure grains having AgI of 8.8 mol%, silver amount ratio 3: 4: 2, AgI content of 24.0, 3 mol%, sphere equivalent diameter 0.75 μm, variation coefficient of sphere equivalent diameter 23%, plate-like particles, diameter / thickness ratio 1.6) Coating amount of silver 0.49 Gelatin 0.61 ExS-4 4.3 × 10 ^{-4 ExS-5 8.6 × 10 -5} ExS-8 2.8 × 10 -5 ExM-5 8.0 × 10 -2 ExM-6 3.0 × 10 -2 ExY-8 1.0 × 10 ^{-2 ExC-1 1.0 × 10 -2} ExC-4 1.0 × 10 -2 Solv-1 0.23 Solv-2 5.0 × 10 -2 Solv-4 1.0 × 10 -2 Cpd- 8 1.0 x 10 ^-2

Ninth layer (intermediate layer) Gelatin 0.56 Cpd-1 4.0 × 10 ^-2 Polyethyl acrylate latex 5.0 × 10 ^-2 Solv-1 3.0 × 10 ^-2 UV-4 3. ^{0x10 -2} UV-5 4.0x10 ^-2

10th layer (donor layer having a multilayer effect for the red-sensitive layer) Silver iodobromide emulsion (AgI 8.0 mol%, internal high AgI type having a core-shell ratio of 1: 2, spherical equivalent diameter 0.65 μm, spherical equivalent) Coefficient of variation of diameter 25%, tabular grains, diameter / thickness ratio 2.0) Coating silver amount 0.67 Silver iodobromide emulsion (AgI 4.0 mol%, uniform AgI type, equivalent spherical diameter 0.4 μm, Coefficient of variation of equivalent sphere diameter 30%, plate-shaped particles, diameter / thickness ratio 3.0) Silver coating amount 0.20 Gelatin 0.87 ExS-3 6.7 × 10 ^-4 ExM-10 0.12 Solv-1 0.30 Solv-6 3.0 × 10 ^-2 11th layer (yellow filter layer) Yellow colloidal silver 9.0 × 10 ^-2 Gelatin 0.84 Cpd-2 0.13 Solv-1 0.13 Cpd-1 8.0 × 10 ^-2 Cpd-6 2.0 × 10 ^-3 H-1 0.25

Twelfth Layer (Low Sensitivity Blue Sensitive Emulsion Layer) Silver iodobromide emulsion (AgI 4.5 mol%, uniform AgI type, sphere equivalent diameter 0.7 μm, variation coefficient of sphere equivalent diameter 15%, plate-like grain , Diameter / thickness ratio 7.0) coating silver amount 0.50 silver iodobromide emulsion (AgI 3.0 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) Amount of coated silver 0.30 Gelatin 2.18 ExS-6 9.0 × 10 ^-4 ExC-1 0.14 ExY-9 0.17 ExY-11 1.09 Solv- 1 0.54

13th layer (intermediate layer) Gelatin 0.40 ExY-12 0.10 Solv-1 0.19 14th layer (high-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion (AgI 10.0 mol%, internal high) AgI type, equivalent sphere diameter 1.0 μm, variation coefficient of equivalent sphere diameter 25%, multiple twin plate-like particles, diameter / thickness ratio 2.0) Coating amount of silver 0.40 Gelatin 0.49 ExS-6 2.6 × 10 ^-4 ExY-9 1.0 × 10 ^-2 ExY-11 0.20 ExC-1 1.0 × 10 ^-2 Solv-1 9.0 × 10 ^-2

Fifteenth Layer (First Protective Layer) Fine grain silver iodobromide emulsion (AgI 2.0 mol%, uniform AgI type, sphere equivalent diameter 0.07 μm) Silver coating amount 0.12 Gelatin 0.63 UV-4 0.11 UV-5 0.18 Solv-5 2.0 × 10 ^-2 Cpd-5 0.10 Polyethyl acrylate latex 9.0 × 10 ^-2 16th layer (second protective layer) Fine grain silver iodobromide emulsion (AgI 2.0 mol%, uniform AgI type, sphere equivalent diameter 0.07 μm) Coating silver amount 0.36 Gelatin 0.85 B-1 (diameter 1.5 μm) 8.0 × 10 ^-2 B-2 (diameter 1.5 μm) 8 0.0 x 10 ^-2 B-3 2.0 x 10 ^-2 W-4 2.0 x 10 ^-2 H-1 0.18

In addition to the above, the samples prepared in this way were
1,2-benzisothiazolin-3-one (200 ppm average for gelatin), n-butyl-p-hydroxybenzoate (about 1,000 ppm) and 2-phenoxyethanol (about 10,000 ppm) were added. B-4,
B-5, F-1, F-2, F-3, F-4, F-5, F
-6, F-7, F-8, F-9, F-10, F-11,
F-12, F-13 and iron salts, lead salts, gold salts, platinum salts,
Contains iridium and rhodium salts. In addition to the above components, each layer contains a surfactant W-1, W-2, W-3.
Was added as a coating aid or an emulsifying dispersant.

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(Samples 202 to 210) Samples 202 to 210 were prepared by replacing the comparative coupler (a) of Sample 201 with another coupler of equal weight as shown in Table 2. These samples were irradiated with the same soft X-rays as in Example 1 and the following color development was performed to determine the edge effect.

Color development process Process time Treatment temperature Replenishment amount Tank capacity Color development 3 minutes 15 seconds 38 ° C. 45 ml 10 liters Bleach 1 minute 00 seconds 38 ° C. 20 ml 4 liters Bleach fixing 3 minutes 15 seconds 38 ° C. 30 ml 8 liters Washing ( 1) 40 seconds 35 ℃ 4 liters from (2) to (1) Countercurrent piping system Washing with water (2) 1 minute 00 seconds 35 ℃ 30 ml 4 liters Stability 40 seconds 38 ℃ 20 ml 4 liters Dry 1 minute 15 seconds 55 ℃ replenishment amount is 35mm width 1m per length

Next, the composition of the processing liquid will be described. (Color developer) Mother liquor (g) Replenisher (g) Diethylenetriaminepentaacetic acid 1.0 1.1 1-Hydroxyethylidene-1,1-diphosphonic acid 3.0 3.2 Sodium sulfite 4.0 4.4 Potassium carbonate 30.0 37.0 Potassium bromide 1.4 0.7 Potassium iodide 1.5 mg -Hydroxylamine sulfate 2.4 2.8 4- [N-ethyl-N-β-hydroxyethyl 4.5 5.5 amino] -2-methylaniline sulfate Add water 1.0 liter 1.0 liter pH 10.05 10.10

(Bleaching solution) Common to mother liquor and replenisher (unit: g) Ethylenediaminetetraacetic acid ammonium ferric dihydrate 120.0 Ethylenediaminetetraacetic acid disodium salt 10.0 Ammonium bromide 100.0 Ammonium nitrate 10.0 Bleaching accelerator 0.005 mol

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Ammonia water (27%) 15.0 ml Water was added to 1.0 liter pH 6.3 (bleach-fixing solution) Common for mother liquor and replenisher (unit g) Ethylenediaminetetraacetic acid ammonium ferric dihydrate 50.0 Ethylenediaminetetraacetic acid disodium salt 5.0 Sodium sulfite 12.0 Ammonium thiosulfate aqueous solution (70%) 240.0 ml Ammonia water (27%) 6.0 ml Water is added to 1.0 liter pH 7.2

(Washing liquid) common to mother liquor and replenishing liquid Tap water was mixed with H type strongly acidic cationona exchange resin (Amberlite IR-120B manufactured by Rohm and Haas Co.) and OH type anion exchange resin (Amberlite IR-400). Water was passed through a packed mixed-bed column to adjust the concentration of calcium and magnesium ions to 3 mg / liter or less, and then 20 mg / liter of sodium isocyanurate dichloride and 0.15 g / liter of sodium sulfate were added. The pH of this solution was in the range of 6.5 to 7.5. (Stabilizer) Common for mother liquor and replenisher (Unit: g) Formalin (37%) 2.0 ml Polyoxyethylene-p-monononylphenyl ether 0.3 (Average degree of polymerization 10) Ethylenediaminetetraacetic acid disodium salt 0.05 Water added 1.0 liter pH 0.5-8.0

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[Table 2]

From Table 2, it is clear that the sample of the present invention has a large edge effect and is excellent in sharpness.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP 61-236550 (JP, A) JP 63-281160 (JP, A) JP 1-106056 (JP, A) JP 1- 219747 (JP, A) Japanese Patent Laid-Open No. 1-154057 (JP, A)

Claims (4)

(57) [Claims] 1. A support having at least one photosensitive silver halide emulsion layer on a support and releasing a photographically useful group or its precursor through a timing group by a coupling reaction with an oxidized product of a developing agent. A silver halide photographic light-sensitive material containing a coupler, comprising a plurality of photographically useful groups or precursors thereof on different atoms constituting the timing group. However, when a plurality of photographically useful groups have different functions, the timing group does not utilize intramolecular nucleophilic substitution. 2. The silver halide photographic light-sensitive material according to claim 1, wherein when it has a plurality of timing groups, at least one of them is an electron transfer type. 3. The silver halide photographic light-sensitive material according to claim 1, wherein at least one of the photographically useful groups is a development inhibitor. 4. The silver halide photographic light-sensitive material according to claim 3, wherein when a plurality of timing groups are included, at least one of them is an azole type.