JP2559247B2 - Silver halide color photographic light-sensitive material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a color photographic light-sensitive material containing a novel compound capable of making a photographically useful group available during development processing.

(Prior Art) A lot of research has been conducted on color-reducing color photographic light-sensitive materials for the purpose of improving sharpness, improving graininess, improving color reproducibility, improving desilvering property or increasing sensitivity. Came.

One such technique is a coupler that releases a photographically useful group. Representative examples of the photographically useful group are a development inhibitor, a bleaching accelerator, a dye, a fogging agent and a developing agent.
In addition to a coupler that cleaves a photographically useful group from the coupling position of a coupler, recently, a compound that releases one or more groups capable of undergoing a cleavage reaction after leaving from the coupling position to release a photographically useful group has been proposed. Are known. For example, U.S. Patent Nos. 4,409,323, 4,248,962, and 4,698,
The compounds described in JP-A No. 297, JP-A-61-156127, or JP-A-63-37346 are known.

As yet another method, an example of releasing a coupler releasing a photographically useful group from the coupler is described in US Pat. No. 4,438,193.
And No. 4,310,618 are disclosed. As another method, an example in which a compound releasing a photographically useful group by a redox reaction is released from a coupler is disclosed in US Pat. No. 4,618,57.
1, JP-A-62-151850, JP-A-62-151847, JP-A-62-569
Nos. 62, 61-240240, and 61-231533 are disclosed.

Although these known compounds have a certain level of performance, further improvements have been desired.

(Object of the Invention) Accordingly, it is an object of the present invention to provide a color photographic light-sensitive material excellent in sharpness, graininess or color reproducibility or having high sensitivity.

(Structure of the Invention) The above-described object is to consume at least 3 developing agent oxidants in total through a multi-step reaction including at least 3 steps of reacting with an developing agent oxidant, thereby providing a photographically useful group. Achieved by a silver halide color photographic light-sensitive material characterized by containing a releasing compound.

Here, the meaning of reacting with an oxidized product of a developing agent includes a coupling reaction between an ordinary coupler and an oxidized product of a developing agent or a redox reaction between a reducing agent and an oxidized product of a developing agent. For example, in the case of a coupler, a leaving group is removed by reacting with an oxidized product of a developing agent, the released compound is a coupler, and further, it can react with an oxidized product of a developing agent, and such a reaction occurs at least three times. As a result, the photographically useful group is finally cleaved, and the desired photographic action is exhibited.

The effect of the present invention is obtained by the action of the photographically useful group being exerted strongly depending on the concentration of the oxidized product of the developing agent. That is, in a portion where a large amount of developing agent oxidant is generated by the development processing, the rate at which a photographically useful group is generated from the compound of the present invention is high, and conversely, development is not so active, and the developing agent oxidant is The generation of the photographically useful group is slight where the generation amount of is small. At least three oxidized forms of developing agents are required until the compound of the present invention is cleaved, and the photographically useful groups are eventually cleaved. After all, the production amount of the photographically useful groups largely depends on the concentration of the oxidized form of developing agents. It is considered that the effect of the present invention was obtained by this.

The compounds of the invention are preferably those mentioned below. That is, the compound has a group that is released by reacting with an oxidized product of a developing agent, and the leaving group is in a form capable of reacting with an oxidized product of a developing agent after the removal, which is a leaving group by reacting with an oxidized product of a developing agent. Is cleaved, and the leaving group is in a form capable of reacting with an oxidized product of a developing agent. It is a compound in which such a multi-step sequential reaction occurs at least 3 times, thereby consuming at least 3 developing agent oxidants in total and cleaving the photographically useful group in the final reaction.

Therefore, the compound of the present invention is preferably one represented by the following general formula.

General formula (I) In the formula, A represents a group in which a bond with a residue other than A is cleaved by reacting with an oxidized product of a developing agent, and L ₁ and L ₂ are each a bond on the right side after the bond on the left side represented by the above formula is cleaved. Represents a group capable of being cleaved, and B is in a form capable of reacting with an oxidized product of a developing agent only after the bond on the left side of B represented by the above formula is cleaved,
Represents a group in which the bond on the right side of B represented by the above formula is cleaved by reacting with an oxidized product of a developing agent, PUG represents a photographically useful group, v and w each represent 0 or 1, and a represents 2 or 3 Represents Here, a plurality of (L ₁ ) _v −B represent the same or different.

The reaction process in which the compound represented by the general formula (I) releases PUG during development is shown by, for example, the following reaction formula.

Hereafter, it is the same as when a = 2.

 Where T Represents an oxidized product of a developing agent, and other symbols
Has the same meaning as described in the general formula (I).

 As shown in the above equation, PUG is a multi-step T Reaction with
And is effectively released by PUG. An example
For example, when PUG is a development inhibitor, the edge effect is strong.
Sharpness and layering effect
To improve the color reproducibility, and
Mottle formed by overlapping pigment clouds
Improvement of graininess by inhibiting the formation of
Was made. In addition, since it is a multi-step reaction,
Of T When the generation amount of
The amount produced is extremely small, while T of
Since a large amount is generated, a large amount of development inhibitor is released.
And adjust the speed of development to the desired speed.
Is possible.

The compound represented by the general formula (I) is preferably a diffusion resistant compound. However, when the group represented by B is a coupler, it is preferable that at least one of them represents a coupler having no diffusion resistant group.

In formula (I), the diffusion resistant group is preferably contained in the group represented by A.

The binding of A, L ₁ , B, L ₂ and PUG in the general formula (I) will be described in detail below.

A is attached at a heteroatom contained in L _1, L ₁ is B
Attached at a heteroatom contained in, B is attached at a heteroatom contained in L _2, L ₂ is attached at a heteroatom contained in PUG. Here, the hetero atom is preferably a nitrogen atom, a sulfur atom or an oxygen atom.

In the general formula (I), it is preferable that at least one of a groups represented by B is a group which becomes a redox group after elimination.

Next, the compound represented by formula (I) will be described in detail.

In the general formula (I), A specifically represents a coupler residue or a redox group.

When A represents a coupler residue, known compounds can be used. For example, a yellow coupler residue (for example, an open-chain ketomethylene type coupler residue), a magenta coupler residue (for example, a 5-pyrazolone type, a pyrazoloimidazole type, or a pyrazolotriazole type coupler residue), a cyan coupler residue (for example, a phenol type residue). , Coupler residues such as naphthol type), and non-color coupler residues (eg coupler residues such as indanone type and acetophenone type) or US Pat. Nos. 4,315,070, 4,183,752, and 4,171,223.
No. 4,226,934 and the like.

When A represents a redox group, it is specifically a group represented by the following general formula (II).

Formula _{(II) A 1 -P- (X} = Y) n -Q-A ₂ wherein, P and Q each independently represents an oxygen atom or a substituted or unsubstituted imino radical, n number of X and Y At least one of-represents a methine group having-{(L ₁ ) _v -B} _a L ₂ ) _w -PUG as a substituent, and the other X and Y represent a substituted or unsubstituted methine group or a nitrogen atom. , N is 1
To 3 (n X's and n Y's are the same or different), and A ₁ and A ₂ are each a hydrogen atom or a group removable by an alkali. Here P, X, Y, Q, are also included when any two substituents of A ₁ and A ₂ form a bivalent group and linked cyclic structure Te summer. For example, (X = Y) _n forms a benzene ring, a pyridine ring, or the like.

The groups represented by L ₁ and L ₂ in the general formula (I) may or may not be used in the present invention. It is appropriately selected according to the purpose. Examples of the group represented by L ₁ and L ₂ include the following known linking groups.

(1) A group that utilizes the cleavage reaction of hemiacetal.

For example, U.S. Pat.No. 4,146,396, JP-A-60-249148
And the groups represented by the following general formula. Here, the symbol * represents a position bonding to the left side in the general formula (I), and the symbol ** represents a position bonding to the right side in the general formula (I).

In the formula, W is an oxygen atom, a sulfur atom, or A group (R ₃ represents an organic substituent), R ₁ and R ₂ represent a hydrogen atom or a substituent, t represents 1 or 2, and when t is ₂ , each of _two R ₁ and R ₂ is represented. May be the same or different, and the case where any _{two of} R ₁ , R ₂ and R ₃ are linked to form a cyclic structure is also included.

 Specific examples include the following groups.

(2) A group that causes a cleavage reaction using an intramolecular nucleophilic substitution reaction.

For example, certain timing groups described in U.S. Pat. No. 4,248,962 can be mentioned. It can be represented by the following general formula.

* -Nu-Link-E-** (T-2) In the formula, an asterisk (*) indicates a position bonding to the left side in the general formula (I), and ** a position bonding to the right side in the general formula (I). Nu represents a nucleophilic group, an oxygen atom or a sulfur atom is an example, and E represents an electrophilic group.
Link is a group that can cleave the bond with ** by nucleophilic attack from Nu, and Link represents a linking group that links Nu and E sterically so that they can undergo an intramolecular nucleophilic substitution reaction. (T
Specific examples of the group represented by -2) are as follows.

(3) A group that causes a cleavage reaction by utilizing an electron transfer reaction along a conjugated system.

For example, it is a group represented by the following general formula described in U.S. Pat. No. 4,409,323 or 4,421,845.

In the formulas, *, **, R ₁ , R ₂ and t have the same meanings as described for (T-1). Specific examples include the following groups.

(4) A group that 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 (T-1).

In the general formula (I), the group represented by B is detailed in A
-(L ₁ ) a group which becomes a coupler after cleavage from _v or A-
(L ₁ ) a group that becomes an oxidation-reduction group after being cleaved from _v . Examples of the group serving as a coupler include, for example, in the case of a phenol type coupler, A
— (L ₁ ) is bonded to _v . Further, in the case of a 5-pyrazolone type coupler, the coupler is bonded to A- (L ₁ ) _{v at} an oxygen atom obtained by removing a hydrogen atom from a hydroxyl group of a tautomer type of 5-hydroxypyrazole. In each of these examples A- and (L _{1) v} released from the first phenol type coupler or 5-pyrazolone type couplers. (L ₂ ) _w − at those coupling positions
It has a PUG. When B represents a group to be a redox group, it is preferably represented by the general formula (B-1).

In the general formula (B-1) * -P- (X '= Y') _n -QA _{2 In the} formula, an asterisk (*) indicates a position bonding to A- (L ₁ ) _v ;
A ₂ , P, Q and n have the same meanings as described in the general formula (II), and at least one of n X ′ and Y ′ has methine having (L ₂ ) _w -PUG as a substituent. And other X'and Y'represent a substituted or unsubstituted methine group or a nitrogen atom. Where A ₂ , P,
It also includes the case where any two substituents of Q, X'and Y'become a divalent group to form a cyclic structure.

Examples of the photographically useful group represented by PUG in the general formula (I) include a development inhibitor, a development accelerator, a nucleating agent, a coupler, a diffusible or non-diffusible dye, a desilvering accelerator and a desilvering inhibitor. , Silver halide solvent, competing compound, developer, auxiliary developer, fixing accelerator, fixing inhibitor, image stabilizer, color image stabilizer, photographic dye, desensitizer, complexed with metal ions Examples thereof include dye-forming ligands, fluorescent brighteners, and precursors thereof.

 Typical of the above are development inhibitors.

Examples of the development inhibitor include tetrazolylthio group, benzimidazolylthio group, benzothiadiazolylthio group, benzoxazolylthio group, benzotriazolyl group, bezoindazolyl group, triazolylthio group, imidazolylthio group, thiadiazolylthio group, thioether. A substituted triazolyl group (for example, a development inhibitor described in U.S. Pat. No. 4,579,816) or an oxadiazolylthio group may be optionally substituted. Representative examples include the following examples. In the following examples, the total carbon number is preferably 20 or less. Halogen atom, aliphatic group, nitro group, acylamino group, aliphatic oxycarbonyl group, aromatic oxycarbonyl group, imide group, sulfonamide group, aliphatic oxy group, aromatic oxy group, amino group, imino group, cyano group , Aromatic group, acyloxy group, sulfonyloxy group, aliphatic thio group, aromatic thio group, aromatic oxysulfonyl group, aliphatic oxysulfonyl group, aliphatic oxycarbonylamino group, aromatic oxycarbonylamino group, aliphatic Examples include an oxycarbonyloxy group, a heterocyclic oxycarbonyl group, a heterocyclic oxy group, a sulfonyl group, an acyl group, a ureido group, a heterocyclic group, a hydroxyl group, and the like.

For example, tetrazolylthio group (for example, 1-phenyltetrazolylthio group, 1- (4-methoxycarbonylphenyl) tetrazolylthio group, 1-ethyltetrazolylthio group, 1-butyltetrazolylthio group, 1- (2-methoxycarbonyl) Ethyl) tetrazolylthio group or 1-
(4-hydroxyphenyl) tetrazolylthio group, etc.), 1,3,4-thiadiazolylthio group (eg 5-methylthio-1,3,4-thiadiazolylthio group, 5-butylthio-1,3,4) -Thiadiazolylthio group, 5- (1-methoxycarbonylethylthio) -1,3,4-thiadiazolylthio group, or 5- (2-methoxycarbonylethylthio) -1,3,4-thiadia Azolylthio group), 1,3,4-oxadiazolylthio group (for example, 5-methyl-1,3,4-oxadiazolylthio group, 5-phenyl-1,3,4-oxadiazolylthio group) Etc.), benzothiazolylthio group, benzoxazolylthio group, benzotriazolyl group (for example, 5-phenoxycarbonylbenzotriazolyl group, 5,
6-dimethylbenzotriazolyl group, 5-bromobenzotriazolyl group and the like), benzoindazolyl group and the like.

For examples and functions of development inhibitors and other PUGs, see US Pat. Nos. 4,248,962, 4,409,323, 4,47.
No. 7,563, No. 4.390,618, No. 4,518,682, No. 4,555,477
Issue, Research Disclosure, 1973 Item No.1144
No. 9 and JP-A No. 61-201247.

Next, more preferable ranges among the compounds of the present invention will be described.

In the general formula (I), preferred examples of A are the following general formulas (Cp-1), (Cp-2), (Cp-3), (Cp-4),
This is when it is a coupler residue represented by (Cp-5), (Cp-6), (Cp-7), (Cp-8) or (Cp-9). These caps have a high coupling speed and are preferable.

The free bond derived from the coupling position in the above formula represents the coupling position of the coupling-off group.

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 or R ₆₃ contains a diffusion-resistant group, it has from 8 total carbon number 40, is preferably selected to be from 10 30, otherwise The total number of carbon atoms is preferably 15 or less. In the case of a bis-type, telomer-type or polymer-type coupler, any of the above substituents represents a divalent group and connects repeating units and the like. In this case, the range of the carbon number may be out of the range.

Hereinafter, R _{51 to} R ₆₃ , d and e will be described in detail. In the following, R ₄₁ represents an aliphatic group, an aromatic group or a heterocyclic group, R ₄₂ represents an aromatic group or a heterocyclic group, R ₄₃ ,
R ₄₄ and R ₄₅ represent a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group.

R ₅₁ has the same meaning as R ₄₁ . R ₅₂ and R ₅₃ are each R
_{Has the} same meaning as ₄₂ . R ₅₄ has the same meaning as R ₄₁ , R ₄₁ S-group, R ₄₃ O-group, R ₄₁ OOC-group, Alternatively, it represents an N≡C-group. R ₅₅ represents a group having the same meaning as R ₄₁ . R ₅₆ and R ₅₇ are each a group having the same meaning as the R ₄₃ group, R ₄₁
S-group, R ₄₃ O-group, Represents R ₃₈ has the same meaning as R ₄₁ . R ₅₉ is R ₄₁
A group with the same meaning as R ₄₁ O- group, R ₄₁ S- group, halogen atom or Represents d represents 0 to 3. When d is plural, plural R _59's represent the same substituent or different substituents.
Further, each R ₅₉ may be connected as a divalent group to form a cyclic structure. Examples of divalent groups for forming a cyclic structure are Or Is mentioned. Here, f represents an integer of 0 to 4, and g represents an integer of 0 to 2. R ₆₀ has the same meaning as R ₄₁ . R ₆₁ represents a group having the same meaning as R ₄₁ . R ₆₂ is R ₄₁
R ₄₁ CONH- group, R ₄₁ OCONH- group, R ₄₁ SO ₂ N
H-group, R ₄₃ O- group, R ₄₁ S- group, halogen atom or Represents R ₆₃ has the same meaning as R ₄₁ , It represents an R ₄₁ SO ₂ — group, an R ₄₃ OCO— group, an R ₄₃ O—SO ₂ — group, a halogen atom, a nitro group, a cyano group or an R ₄₃ CO— group. e
Represents an integer of 0 to 4. When there are plural R ₆₂ or R _63, they represent the same or different.

In the above, the aliphatic group is a saturated or unsaturated, chain or cyclic, linear or branched, substituted or unsubstituted aliphatic hydrocarbon group having 1 to 32 carbon atoms, preferably 1 to 22 carbon atoms.
Representative examples include methyl, ethyl, propyl, isopropyl, butyl, (t) -butyl,
(I) -butyl group, (t) -amyl group, hexyl group, cyclohexyl group, 2-ethylhexyl group, octyl group,
Examples thereof include a 1,1,3,3-tetramethylbutyl group, a decyl group, a dodecyl group, a hexadecyl group, and an octadecyl group.

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

The heterocyclic group is a substituted or unsubstituted heterocyclic group having 1 to 20 carbon atoms, preferably 1 to 7 carbon atoms, preferably selected from nitrogen atom, oxygen atom or sulfur atom as a hetero atom, and preferably having 3 to 8 members. Is. Typical examples of the heterocyclic group are 2-pyridyl group, 4-pyridyl group, 2-thienyl group, 2-furyl group, 2-imidazolyl group, pyrazinyl group, 2-pyrimidinyl group, 1-imidazolyl group, 1- Indolyl group, phthalimido group, 1,3,4-thiadiazol-2-yl group, benzoxazol-2-yl group, 2-
Quinolyl group, 2,4-dioxo-1,3-imidazolidine-5
-Yl group, 2,4-dioxo-1,3-imidazolidine-3-
Yl group, succinimide group, phthalimide group, 1,2,4-
Examples thereof include a triazol-2-yl group and a 1-pyrazolyl group.

Representative substituents when the aliphatic hydrocarbon group, the aromatic group and the heterocyclic group have a substituent, a halogen atom, R ₄₇ O- group, R ₄₆ S- group, R ₄₆ SO ₂ -group, R ₄₇ OCO-group, A group having the same meaning as R ₄₆ , R ₄₆ COO − group, R ₄₇ OSO ₂ — group, cyano group or nitro group can be mentioned. 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,
It represents an aromatic group, a heterocyclic group or a hydrogen atom. The meaning of an aliphatic group, an aromatic group or a heterocyclic group has the same meaning as previously defined.

Next, preferred ranges of R _{51 to} R ₆₃ , d and e will be described.

R ₅₁ is preferably an aliphatic group or an aromatic group. R ₅₂ , R ₅₃
And R ₅₅ is preferably an aromatic group. R ₅₄ is R ₄₁ CONH- group,
Or Is preferred. R ₅₆ and R ₅₇ are preferably an aliphatic group, R ₄₁ O— group, or R ₄₁ S— group. 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 1
Or 2 is preferable. R ₆₀ is preferably an aromatic group. In formula (Cp-7), R ₅₉ is preferably R ₄₁ CONH-group. 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. R ₆₃
As R ₄₁ CONH- group, R ₄₁ SO ₂ NH- group, R ₄₁ SO ₂ — group, A nitro group or a cyano group is preferred.

Next, typical examples of R _{51 to} R ₆₃ will be described.

R ₅₁ is (t) -butyl group, 4-methoxyphenyl group, phenyl group, 3- {2- (2,4-di-t-amylphenoxy) butanamide} phenyl group, 4-octadecyloxyphenyl group Alternatively, a methyl group can be used. R ₅₂
And R ₅₃ is 2-chloro-5-dodecyloxycarbonylphenyl group, 2-chloro-5-hexadecylsulfonamidophenyl group, 2-chloro-5-tetradecanamidephenyl 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-tetra Decyloxycarbonylphenyl 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)
A phenyl group, a 2-chlorophenyl group or a 2-ethoxyphenyl group is exemplified. As R ₅₄ , 3- {2-
(2,4-di-t-amylphenoxy) butanamide} benzamide group, 3- {4- (2,4-di-t-amylphenoxy) butanamide} benzamide group, 2-chloro-
5-tetradecanamide anilino group, 5- (2,4-di-
t-amylphenoxyacetamido) benzamide group,
2-chloro-5-dodecenylsuccinimide anilino group, 2-chloro-5- {2- (3-t-butyl-4-hydroxyphenoxy) tetradecanamide} anilino group, 2,2-dimethylpropane Examples thereof include an imide group, a 2- (3-pentadecylphenoxy) butanamide group, a pyrrolidino group and an N, N-dibutylamino group. R ₅₅ includes a 2,4,6-trichlorophenyl group, a 2-chlorophenyl group, a 2,5-dichlorophenyl group, a 2,3-dichlorophenyl group, and a 2,6-dichloro-4-methoxyphenyl group. Base, 4-
{2- (2,4-Di-t-amylphenoxy) butanamide} phenyl or 2,6-dichloro-4-methanesulfonylphenyl is a preferred example. R ₅₆ represents 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, a 3-butylureido group, or a 3- (2,4
-Di-t-amylphenoxy) propyl group. R ₅₇ represents a 3- (2,4-di-t-amylphenoxy) propyl group, a 3- [4- {2- [4- (4-hydroxyphenylsulfonyl) phenoxy] tetradecanamido} phenyl] propyl group, a methoxy group; Group, ethoxy group, methylthio group, ethylthio group, methyl group, 1-methyl-2- {2-octyloxy-5- [2-octyloxy-5- (1,1,3,3-tetramethylbutyl) phenyl Enylsulfonamido) phenylsulfonamidoethyl group,
3- {4- (4-dodecyloxyphenylsulfonamido) phenyl} propyl group, 1,1-dimethyl-2- {2
-Octyloxy-5- (1,1,3,3-tetramethylbutyl) phenylsulfonamidoethyl group, or a dodecylthio group. R ₅₈ is 2-chlorophenyl, pentafluorophenyl, heptafluoropropyl, 1- (2,4-di-t-amylphenoxy) propyl, 3- (2,4-di-t-amylphenoxy) propyl Group, a 2,4-di-t-amylmethyl group, or a furyl group. R ₅₉ is a chloro atom, a methyl group,
Ethyl group, propyl group, butyl group, isopropyl group, 2
-(2,4-di-t-amylphenyl) butanamide group,
2- (2,4-di-t-amylphenoxy) hexanamide group, 2- (2,4-di-t-octylphenoxy) octanamide group, 2- (2-chlorophenoxy) tetradecanamide group, 2,2-dimethylpropanamide group, 2-
{4- (4-hydroxyphenylsulfonyl) phenoxy} tetradecanamide group, or 2- {2- (2,4-
Di-t-amylphenoxyacetamide) phenoxy}
A butanamide group may be mentioned. As R ₆₀ , 4-cyanophenyl group, 2-cyanophenyl group, 4-butylsulfonylphenyl group, 4-propylsulfonylphenyl group,
Examples thereof include a 4-ethoxycarbonylphenyl group, a 4-N, N-diethylsulfamoylphenyl group, a 3,4-dichlorophenyl group and a 3-methoxycarbonylphenyl group. R ₆₁ is a dodecyl group, hexadecyl group, cyclohexyl group, butyl group, 3- (2,4-di-t-amylphenoxy) propyl group, 4- (2,4-di-t-amylphenoxy) butyl group, 3- Dodecyloxypropyl group, 2-tetradecyloxyphenyl group, t-butyl group, 2- (2-hexyldecyloxy) phenyl group, 2
Examples include -methoxy-5-dodecyloxycarbonylphenyl group, 2-butoxyphenyl group and 1-naphthyl group. R ₆₂ is isobutyloxycarbonylamino group, ethoxycarbonylamino group, phenylsulfonylamino group, methanesulfonamide group, butanesulfonamide group, 4-methylbenzenesulfonamide group, benzamide group, trifluoroacetamide group, 3-phenylureido Group, butoxycarbonylamino group, or acetamido group. R ₆₃ is 2,4-di-
t-amylphenoxyacetamide group, 2- (2,4-di-t-amylphenoxy) butanamide group, hexadecylsulfonamide group, N-methyl-N-octadecylsulfamoyl group, N, N-dioctylsulfaure group Moyle group,
Examples thereof include a dodecyloxycarbonyl group, a chlor atom, a fluorine atom, a nitro group, a cyano group, an N-3- (2,4-di-t-amylphenoxy) propylsulfamoyl group, a methanesulfonyl group and a hexadecylsulfonyl group.

The preferred range when A in the general formula (I) is represented by the general formula (II) will be described below.

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.

 At this time, P and Q are expressed as follows.

Here, the * mark represents the position at which it binds to A ₁ or A _2, and *
The * mark represents the position at which one of the free bonds of-(X = Y _n is bonded.

In the formula, the group represented by G is a linear or branched, chain or cyclic, saturated or unsaturated, substituted or unsubstituted aliphatic group having 1 to 32, preferably 1 to 22 carbon atoms (eg, methyl group, ethyl group) Group, benzyl group, phenoxybutyl group, isopropyl group, etc.), substituted or unsubstituted aromatic group having 6 to 10 carbon atoms (for example, phenyl group, 4-methylphenyl group,
A 1-naphthyl group, a 4-dodecyloxyphenyl group, etc.) or a 4- to 7-membered heterocyclic group selected from a nitrogen atom, a sulfur atom or an oxygen atom as a hetero atom (for example, a 2-pyridyl group, a 1-phenyl group) -4-imidazolyl group, 2-furyl group, benzothienyl group, etc.) are preferable examples.

A group in which A ₁ and A ₂ can be removed by an alkali (hereinafter,
When referred to as a precursor group), preferably a hydrolyzable group such as an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an imidoyl group, an oxazolyl group and a sulfonyl group, the reverse described in U.S. Patent No. 4,009,029. Precursor group of the type utilizing the Michael reaction, a type of precursor group utilizing the anion generated after the ring opening reaction described in U.S. Pat.No. 4,310,612 as an intramolecular nucleophilic group, U.S. Pat.No. 3,674,478,
3,932,480 or 3,993,661 the anion described in the anionic electron transfer via a conjugated system precursor group to cause a cleavage reaction, thereby causing a cleavage reaction by electron transfer of the reacted anion after ring cleavage described in U.S. Pat. Precursor base or U.S. Pat. No. 4,363,865
No. 4,410,618, and precursor groups utilizing an imidomethyl group are mentioned.

In the general formula (II), P is preferably an oxygen atom and A ₂ is a hydrogen atom.

More preferably in the general formula (II), X and Y
Is a methine group having-{(L _{1 v} B} _a L _{2 w} PUG as a substituent, except when X and Y are a substituted or unsubstituted methine group.

Among the groups represented by the general formula (II), particularly preferable groups are represented by the following general formula (III) or (IV).

General formula (III) General formula (IV) In the formula, the * mark represents the bonding position of {L _{1 v} B} _a L ₂ ) − _w PUG, and P, Q, A ₁ and A ₂ have the same meanings as described in the general formula (II). , R represents a substituent, and q represents an integer of 0, 1 to 3. When q is 2 or more, two or more Rs may be the same or different, and when two Rs are a substituent on an adjacent carbon, they are linked to each other as a divalent group to represent a cyclic structure. Is also included. In that case, it becomes a benzene condensed ring and becomes a ring structure such as naphthalenes, benzonorbornenes, chromans, indoles, benzothiophenes, quinolines, benzofurans, 2,3-dihydrobenzofurans, indanes, or indenes, These may further have one or more substituents. Preferred examples of the substituent when these condensed rings have a substituent and preferable examples of R when R does not form a condensed ring are as follows. That is, an aliphatic group (eg, methyl group, ethyl group, allyl group, benzyl group, dodecyl group), aromatic group (eg, phenyl group, naphthyl group, 4-phenoxycarbonylphenyl group), halogen atom (eg, chloro group). Atoms, bromo atoms), alkoxy groups (eg methoxy groups,
Hexadecyloxy group), alkylthio group (for example, methylthio group, dodecylthio group, benzylthio group), aryloxy group (for example, phenoxy group, 4-t-octylphenoxy group, 2,4-di-t-amylphenoxy group), Arylthio group (for example, phenylthio group, 4-dodecyloxyphenylthio group), carbamoyl group (for example, N-ethylcarbamoyl group, N-propylcarbamoyl group, N
-Hexadecylcarbamoyl group, Nt-butylcarbamoyl group, N-3- (2,4-di-t-amylphenoxy) propylcarbamoyl group, N-methyl-N-octadecylcarbamoyl group), alkoxycarbonyl group (eg methoxy) Carbonyl group, 2-cyanoethoxycarbonyl group, ethoxycarbonyl group, dodecyloxycarbonyl group, 3- (2,4-di-t-amylphenoxy) propoxycarbonyl group), aryloxycarbonyl group (for example, phenoxycarbonyl group, 4 -Nonylphenoxycarbonyl group), sulfonyl group (e.g. methanesulfonyl group, benzenesulfonyl group, p-toluenesulfonyl group), sulfamoyl group (e.g. N-propylsulfamoyl group, N-methyl-N-octadecylsulfamoyl group) Group, N-phenylsulfur Amoiru group, N- dodecyl sulfamoylamino group), an acylamino group (e.g. acetamido group, benzamido group, tetradecanamido group, 4-
(2,4-di-t-amylphenoxy) butanamide group,
2- (2,4-di-t-amylphenoxy) butanamide group, 2- (2,4-di-t-amylphenoxy) tetradecanamide group), sulfonamide group (for example, methanesulfonamide group, benzenesulfonamide group, hexa) Decylsulfonamide group), acyl group (eg acetyl group,
Benzoyl group, myristoyl group, palmitoyl group), nitroso group, acyloxy group (for example, acetoxy group, benzoyloxy group, lauryloxy group), ureido group (for example, 3-phenylureido group, 3- (4-cyanophenylureido group)), Nitro group, cyano group, heterocyclic group (4-membered to 6-membered heterocyclic group selected from nitrogen atom, oxygen atom or sulfur atom as hetero atom. For example, 2-furyl group, 2-pyridyl group, 1-imidazolyl group. , 1-morpholino group), hydroxyl group, carboxyl group, alkoxycarbonylamino group (eg, methoxycarbonylamino group, phenoxycarbonylamino group, dodecyloxycarbonylamino group), sulfo group, amino group, arylamino group (eg, anilino group). Group, 4-methoxycarbonylanilino group, fat Group amino group (eg, N, N-diethylamino group, dodecylamino group), sulfinyl group (eg, benzenesulfinyl group, propylsulfinyl group), sulfamoylamino group (eg, 3-phenylsulfamoylamino group) ), A thioacyl group (for example, thiobenzoyl group), a thioureido group (for example, 3-phenylthioureido group), a heterocyclic thio group (for example, thiadiazolylthio group), an imide group (for example, a succinimide group, a phthalimido group, octadecese group). And a heterocyclic amino group (eg, 4-imidazolylamino group, 4-pyridylamino group) and the like.

When there is an aliphatic group moiety in the partial structure of the above substituent,
It has 1 to 32 carbon atoms, preferably 1 to 20 carbon atoms, and is a linear or cyclic, linear or branched, saturated or unsaturated, substituted or unsubstituted aliphatic group.

When an aromatic group is present in the partial structure of the substituent listed above, it has 6 to 10 carbon atoms, and is preferably a substituted or unsubstituted phenyl group.

The group represented by B in the general formula (I) is preferably the group represented by the general formula (B-1).

In the general formula (B-1), P preferably represents an oxygen atom, and Q is preferably an oxygen atom or the following. Here mark * represents a bond that binds to an _{(X '= Y') n} , ** mark represents a bond that binds to an A _2.

In the formula, G has the same meaning as described in formulas (N-1) and (N-2).

Further, when the group represented by B in the general formula (II) is represented by the following general formula (B-2) or (B-3), the effect of the present invention is particularly preferable.

General formula (B-2) General formula (B-3) Wherein * marks the A- (L _{1) v} - represents a bond that binds to, the mark ** - (L ₂₎ represents a bond that binds to an _w -DI, R, q, Q and A ₂ It has the same meaning as described in the general formula (III) or (IV).

Preferred examples of R in formulas (B-2) and (B-3) include the following. In the following examples, the total carbon number is preferably 15 or less. Aliphatic group (eg methyl group, ethyl group), alkoxy group (eg methoxy group, ethoxy group), alkylthio group (eg methylthio group, ethylthio group), alkoxycarbonyl group (eg methoxycarbonyl group, propoxycarbonyl group), aryloxy Carbonyl group such as phenoxycarbonyl group, carbamoyl group (for example, N-propylcarbamoyl group, Nt-butylcarbamoyl group, N-ethylcarbamoyl group), sulfonamide group (for example, methanesulfonamide group), acylamino group (for example, Acetamido group), heterocyclic thio group (eg tetrazolylthio group), hydroxyl group or aromatic.

In the general formula (I), when v and w are both 0, it is a preferable example.

The group represented by A in formula (I) is particularly preferably a coupler residue.

Further preferred embodiments of the present invention will be described below.

A particularly preferred PUG in the general formula (I) is a compound having a development-inhibiting property when cleaved as a PUG, but it does not substantially affect the photographic properties after it flows into a color developer. It is a development inhibitor having the property of being decomposed (or changed) into.

For example, U.S. Pat.No.4,477,563, JP-A-60-218,644
No. 60-221,750, 60-233,650, or 61-
The development inhibitors described in No. 11,743 are mentioned, preferably the following general formulas (D-1), (D-2), (D-3),
(D-4), (D-5), (D-6), (D-7),
(D-8), (D-9), (D-10) or (D-11)
Is represented by.

In the formula, * indicates in the general formula (I) X represents a hydrogen atom or a substituent, d represents 1 or 2, L ₃ represents a group containing a chemical bond which is cleaved in the developing solution, and Y represents a development inhibitory action. It is a substituent and represents an aliphatic group, an aromatic group or a heterocyclic group.

The development inhibitor is After further cleavage, it diffuses in the photographic layer while exhibiting a development-inhibiting effect, and partially flows out to the color development processing solution. The development inhibitor that has flowed out into the processing solution reacts with hydroxyl ions or hydroxylamine generally contained in the processing solution and rapidly decomposes at the chemical bond portion contained in L ₃ (for example, hydrolysis of ester bond). That is, the group represented by Y is cleaved to form a compound having high water solubility and low development inhibitory effect, and the development inhibitory effect is substantially lost.

Although X is preferably a hydrogen atom, it may represent a substituent, and the substituent may be an aliphatic group (eg, methyl group, ethyl group), an acylamino group (eg, acetamide group, propionamide group), an alkoxy group (eg, Methoxy group, ethoxy group), halogen atom (for example, chloro atom,
Representative examples include a bromo atom), a nitro group, and a sulfonamide group (eg, a methanesulfonamide group).

The linking group represented by L ₃ includes a chemical bond that is cleaved in the developing solution. Examples of such chemical bonds include the examples given in the table below. Each of these is cleaved by a nucleophile such as hydroxy ion or hydroxylamine which is a component in the color developing solution.

The chemical bonding modes shown in the above table are linked directly or via an alkylene group and / or a phenylene group to the heterocyclic moiety constituting the development inhibitor, and directly linked to Y. When connecting via an alkylene group or a phenylene group, the intervening divalent group may contain an ether bond, an amide bond, a carbonyl group, a thioether bond, a sulfone group, a sulfonamide bond, and a urea bond.

When Y represents an aliphatic group, it has 1 to 20 carbon atoms, preferably 1
To 10 saturated or unsaturated, linear or branched, chained or cyclic, substituted or unsubstituted hydrocarbon groups, particularly preferably substituted hydrocarbon groups.

When Y represents an aromatic group, it is a substituted or unsubstituted phenyl group or a substituted or unsubstituted naphthyl group.

When Y represents a heterocyclic group, it is a 4- to 8-membered heterocyclic group containing a sulfur atom, an oxygen atom or a nitrogen atom as a hetero atom.

As the heterocyclic ring, for example, a pyridyl group, an imidazolyl group,
Examples thereof include a furyl group, a pyrazolyl group, an oxazolyl group, a thiazolyl group, a thiadiazolyl group, a triazolyl group, a diazolidinyl group, and a diazinyl group.

When the aliphatic hydrocarbon group, the aromatic group, and the heterocyclic group have a substituent, the substituent is a halogen atom, a nitro group, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, Alkanesulfonyl group having 1 to 10 carbon atoms, arylsulfonyl group having 6 to 10 carbon atoms, 1 to 1 carbon atoms
10, alkanamide group, anilino group, benzamide group,
Alkylcarbamoyl group having 1 to 10 carbon atoms, carbamoyl group, arylcarbamoyl group having 6 to 10 carbon atoms, 1 carbon atom
~ 10 alkylsulfonamide group, C6-10 arylsulfonamide group, C1-10 alkylthio group, C6-10 arylthio group, phthalimide group, succinimide group, imidazolyl group, 1,2, 4-triazolyl group, pyrazolyl group, benztriazolyl group, furyl group, benzthiazolyl group, alkylamino group having 1 to 10 carbon atoms, alkanoyl group having 1 to 10 carbon atoms, benzoyl group, alkanoyloxy having 1 to 10 carbon atoms Group, benzoyloxy group, perfluoroalkyl group having 1 to 5 carbon atoms, cyano group, tetrazolyl group, hydroxy group mercapto group,
Amino group, sulfamoyl group having 1 to 10 carbon atoms, 6 carbon atoms
~ 10 arylsulfamoyl group, morpholino group, C6-10 aryl group, pyrrolidinyl group, ureido group,
Urethane group, alkoxycarbonyl group having 1 to 10 carbon atoms,
Examples thereof include an aryloxycarbonyl group having 6 to 10 carbon atoms, an imidazolidinyl group, an alkyldenamino group having 1 to 10 carbon atoms, and the like.

(Examples of Compound) Specific examples of the compound of the present invention are shown below, but the invention is not limited thereto.

The compound of the general formula (I) of the present invention can be applied to a multilayer multicolor photographic material having at least two different spectral sensitivities on a support, mainly for improving graininess, sharpness, color reproducibility and sensitivity. It can be applied for any purpose. Multilayer natural color photographic materials usually have at least one red-sensitive emulsion layer, one green-sensitive emulsion layer and one blue-sensitive emulsion layer on a support. The order of these layers is arbitrarily selected as needed. The compound of the present invention can be used in any layer such as a high-sensitivity layer, a low-sensitivity silver layer or a medium-sensitivity layer, and can be used in a light-sensitive silver halide emulsion layer or a layer adjacent thereto.

The addition amount of the compound of the present invention varies depending on the structure and use of the compound, but is preferably 1 × 10 ⁻⁷ to 0.5 mol, and particularly preferably 1 × 10 ⁻⁶ to 1 mol per mol of silver present in the same layer or an adjacent layer. × 10 ^-1 mol.

The compound of the present invention may be used alone in one layer, or may be used in combination with a known coupler. When used in combination with another color image-forming coupler, the molar ratio of the compound of the present invention to the other color image-forming coupler (the compound of the present invention / the other color image-forming coupler) is 0.1 / 99.9 to 90/10, preferably 1/99
~ 50/50.

The compound of the present invention can be easily synthesized by combining known methods. For example, known methods include U.S. Patent Nos. 4,618,571, 4,248,962, and 4,421,
845, JP-A-61-278852, JP-A-61-231553, and US Pat. No. 4,438,193.

Synthesis Example 1 Synthesis of Exemplified Compound (1) It was synthesized by the following synthesis route.

1, 12.1 g, 2, acetonitrile 150ml and 16.2g and triethylamine 2.5g, was heated to reflux for 2 hours in a nitrogen atmosphere. After allowing to cool to room temperature, pour into 500 ml of water and add 500 ml of ethyl acetate.
It was extracted with. The oil layer was taken, washed with dilute hydrochloric acid and then washed with water until it became neutral. The oil layer was taken and the solvent was distilled off under reduced pressure. A mixed solvent of ethyl acetate and hexane was added to the residue, and the solidified crystal was collected by filtration to obtain 13.8 g of Exemplified Coupler 1 . In addition, 2 used as the raw material was one synthesized by the synthesis route described in US Pat. No. 4,618,571.

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 silver iodobromide containing from about 2 mol% to about 25 mol% silver iodide.

Silver halide grains in photographic emulsions are cubic, octahedral,
It may have a regular crystal such as a tetradecahedron, an irregular crystal form such as a sphere or a plate, a crystal defect such as a twin plane, or a composite form thereof.

The grain size of silver halide may be fine grains of about 0.2 μm or less, or large grains having a projected area diameter of up to about 10 μm, 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 (RD), No. 17643 (1978).
December 23, p. 22-23, "I. Emulsion production (Emulsion prepara
and types) ”, and No. 18716 (November 1979)
Mon), p.648, Grafkid, "Physics and Chemistry of Photography", published by Paul Montell (P. Glafkides, Chemic et Phisique P
hotographique Paul Montel, 1967), Duffin Miyako "Photoemulsion Chemistry", published by Focal Press (GFDuffin, Photo
graphic Emulsion Chemistry (Focal Press, 1966)),
"Production and coating of photographic emulsions" by Zelikman et al., Published by Focal Press (VLZelikman et al. Making and Coating
It can be prepared by the method described in Photographic Emulsion, Focal Pres, 1964) and the like.

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 5 or more can also be used in the present invention. Tabular grains are described in Gutoff, Photographic Science and Engineerin.
g), Vol. 14, pp. 248-257 (1970); U.S. Pat. No. 4,43.
4,226, 4,414,310, 4,433,048, 4,439,520
It can be easily prepared by the method described in Japanese Patent No. 2,112,157 and the like.

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. Alternatively, it may be bonded to a compound other than silver halide such as rotan silver and lead oxide.

 Also, a mixture of particles having various crystal forms may be used.

As the silver halide emulsion, those which are physically ripened, chemically ripened and spectrally sensitized are usually used. The additive used in such a process is Research Disclosure No. 1
7643 and No. 18716, the relevant parts are summarized in the table below.

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

Various color couplers can be used in the present invention, specific examples of which are described in the patents described in Research Disclosure (RD) No. 17643, VII-CG.

As the yellow coupler, for example, U.S. Pat.
No. 501, No. 4,022,620, No. 4,326,024, No. 4,40
1,752, Japanese Patent Publication No. 58-10739, British Patent No. 1,425,020
No. 1,476,760, etc. are preferable.

As the magenta coupler, 5-pyrazolone-based and pyrazoloazole-based compounds are preferable, and British Patent No. 4,310,
619, 4,351,897, European Patent 73,636, British Patent 3,061,432, 3,725,067, Research Disclosure No. 24220 (June 1984), JP-A-60-3355.
No. 2, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, British Patent No. 4,500,630,
Those described in No. 4,540,654 and the like are particularly preferable.

Examples of cyan couplers include phenol-based and naphthol-based couplers, and U.S. Pat.Nos. 4,052,212, 4,146,396, 4,228,233, and 4,296,200.
No. 2,369,929, No. 2,801,171, No. 2,772,162
No. 2, No. 2,895,826, No. 3,772,002, No. 3,758,30
No. 8, No. 4,334,011, No. 4,327,173, West German Patent Publication No. 3,329,729, European Patent No. 121,365A, U.S. Patent No.
Preferred are those described in 3,446,622, 4,333,999, 4,451,559, 4,427,767, EP 161,626A and the like.

Colored couplers to correct unwanted absorption of colored dyes are VII of Research Disclosure No. 17643.
-G, U.S. Pat. No. 4,163,670, Japanese Examined Patent Publication No. 57-39413,
U.S. Patent Nos. 4,004,929, 4,138,258, British Patent No.
Those described in No. 1,146,368 are preferable.

As a coupler in which the coloring dye has an appropriate diffusibility,
Those described in U.S. Pat. No. 4,366,237, British Patent No. 2,125,570, European Patent No. 96,570 and West German Patent (Publication) No. 3,234,533 are preferable.

Typical examples of polymerized dye-forming couplers are U.S. Pat.Nos. 3,451,820, 4,080,211 and 4,367,282.
And U.S. Pat. No. 2,102,173.

Couplers that release a photographically useful residue upon coupling can also be preferably used in the present invention. DIR couplers that release development inhibitors are RD17643, VII-F described above.
Patents described in paragraphs, JP-A-57-151944 and JP-A-57-1542
The compounds described in U.S. Pat. No. 34,60-184248 and U.S. Pat. No. 4,248,962 are preferable.

Examples of couplers that release a nucleating agent or a development accelerator imagewise during development include British Patent Nos. 2,097,140 and 2,1.
Those described in 31,188, JP-A-59-157638 and JP-A-59-170840 are preferable.

Other couplers that can be used in the light-sensitive material of the present invention include competitive couplers described in U.S. Pat.No. 4,130,427, U.S. Pat.Nos. 4,283,472, and 4,338,393.
No. 4,310,618, etc., multi-equivalent couplers, DIR redox compounds or DIR coupler-releasing couplers or DIR coupler-releasing couplers or redox, as described in JP-A-60-185950, JP-A-62-24252, and European Patent No. 173,
No. 302A, a coupler that releases a dye that recolors after being released, RD No. 11449, 24241, a bleaching accelerator releasing coupler described in JP-A No. 61-201247, and a ligand release described in U.S. Pat. Examples thereof include couplers.

Hereinafter, specific examples of the color coupler that can be used in the invention will be described, but the invention is not limited thereto.

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

Examples of high boiling point solvents used in the oil-in-water dispersion method are stored in US Pat. No. 2,322,027 and the like.

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 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 ester (Trifel phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-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 derivatives (N, N-dibutyl-2) -Butoxy-5-tert
-Octylaniline, etc.), hydrocarbons (paraffin,
Dodecylbenzene, diisopropylnaphthalene, etc.) and the like. The auxiliary solvent has a boiling point of about 30 ° C.
Above, preferably an organic solvent of 50 ℃ or more and about 160 ℃ or less can be used, as a typical example, ethyl acetate, butyl acetate,
Examples include ethyl propionate, 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, West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230.

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 are, for example, those mentioned above.
RD.No. 17643, page 28, and RD.No. 18716, page 647 From the right column
See page 648, left column.

The color photographic light-sensitive material according to the present invention has the above-mentioned RD.No.
17643, pages 28 to 29, and No. 18716, 651, left column to right column, can be developed by a usual method.

The color developer used for the development processing of the light-sensitive material of the present invention,
An alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component is preferred. Aminophenol compounds are also useful as the color developing agent, but p-
A phenylenediamine compound is preferably used, and typical examples thereof include 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-N-
Examples include β-methoxyethylaniline and their sulfates, hydrochlorides or p-toluenesulfonates. Two or more of these compounds can be used in combination depending on the purpose.

Color developing solutions include alkali metal carbonates, pH buffers such as borates or phosphates, bromide salts, iodide salts,
It is common to include a development inhibitor such as benzimidazoles, benzothiazoles or mercapto compounds, or an antifoggant. If necessary, hydroxylamine, diethylhydroxylamine, sulfite hydrazines, phenylsemicarbazides, triethanolamine, catecholsulfonic acids, triethylenediamine (1,4-diazabicyclo [2,2,2] octane) Various preservatives, organic solvents such as ethylene glycol and diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competitive couplers,
Fogging agent such as sodium boron hydride, 1
An auxiliary developing agent such as -phenyl-3-pyrazolidone,
Various chelating agents represented by viscosity imparting agents, aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, 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, ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid, ethylenediamine -Di (o-hydroxyphenylacetic acid) and salts thereof can be mentioned as representative examples.

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

The pH of these color developing solution and black-and-white developing solution is generally 9 to 12. The replenishment amount of these developers is
Although it depends on the color photographic light-sensitive material to be processed, it is generally 3 or less per 1 m 2 of the light-sensitive material and can be reduced to 500 ml or less by reducing the bromide ion concentration in the replenisher. 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. Further, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developing solution.

The photographic emulsion layer of the color developing solution is usually bleached. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. Further, in order to speed up the processing, a processing method of bleach-fixing processing after bleaching processing may be used. Further processing with two continuous bleach-fix baths,
The fixing treatment before the bleach-fixing treatment or the bleaching treatment after the bleach-fixing treatment can be optionally carried out according to the purpose.
Examples of bleaching agents include iron (III), cobalt (III),
Compounds of polyvalent metals such as chromium (VI) and copper (II), peracids, quinones, nitro compounds and the like are used. Typical bleaching agents are ferricyanide; dichromate; iron (II
I) or cobalt (III) organic complex salts such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3
-Aminopolycarboxylic acids such as diaminopropane tetraacetic acid and glycol ether diamine tetraacetic acid or complex salts such as citric acid, tartaric acid and malic acid; persulfates; bromates; permanganates; nitrobenzenes and the like can be used. it can. Of these, aminopolycarboxylic acid iron (II) including ethylenediaminetetraacetic acid iron (III) complex salts
I) Complex salts and persulfates are preferable from the viewpoint of rapid processing and prevention of environmental pollution. Furthermore, iron (III) aminopolycarboxylate
Complex salts are particularly useful in both bleaching solutions and bleach-fixing solutions. The pH of the bleaching solution or the bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is usually 5.5 to 8, but the processing can be carried out at a lower pH in order to speed 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 specifications: US Pat. No. 3,893,858, West German Patents 1,290,812, 2,059,98.
No. 8, JP-A-53-32,736, JP-A-53-57,831 and JP-A-53-37,
418, 53-72,623, 53-95,630, 53-95,63
No. 1, No. 53-10,4232, No. 53-124,424, No. 53-141,6
No. 23, No. 53-28,426, Research Disclosure
No. 17,129 (July 1978), etc., a compound having a mercapto group or a disulfide group; JP-A-50-140,
Thiazolidine derivatives described in No. 129; JP-B-45-8,506
No., JP-A-52-20832, JP-A-53-32,735, U.S. Pat.
Thiourea derivatives described in 3,706,561; West German Patent 1,12
No. 7,715, iodide salts described in JP-A-58-16,235; polyoxyethylene compounds described in West German Patent Nos. 966,410 and 2,748,430; polyamine compounds described in JP-B-45-8836; 49-42,434, 49-59,644,
53-94,927, 54-35,727, 55-26,506 58-
Compounds described in No. 163,940; bromide ion 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, U.S. Patent No. 3,893,858, West Patent No. 1,290,812, JP-A-53-
Compounds described in No. 95,630 are preferred. In addition, US Patent No.
The compounds described in 4,552,834 are also preferable. 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.

Examples of the fixing agent include thiosulfates, thiocyanates, thioether compounds, thioureas, and large amounts of iodide salts, but the use of thiosulfates is common,
In particular, ammonium thiosulfate can be used most widely. As a preservative for the bleach-fix solution, sulfite, bisulfite or carbonyl bisulfite adduct is preferable.

The silver halide color photographic light-sensitive material of the present invention generally undergoes a washing and / or stabilizing step after desilvering. The amount of rinsing water in the rinsing step depends on the characteristics of the light-sensitive material (for example, depending on the material used such as a coupler), the purpose, and the rinsing water temperature.
It can be set in a wide range depending on the number of washing tanks (the number of stages), a replenishment system such as countercurrent and forward flow, and various other conditions. Of these, the relationship between the number of washing tanks and the water volume in the multi-stage countercurrent system is described in the Journal of the Society of Motion Picture and T
It can be determined by the method described in elevision Engineers, Volume 64, P.248-253 (May 1955 issue).

According to the multi-stage countercurrent method described in the above-mentioned document, the amount of washing water can be greatly 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. Problem arises. In the processing of the color light-sensitive material of the present invention, as a solution to such a problem, calcium ions described in Japanese Patent Application No. 61-131,632,
The method of reducing magnesium ions can be used very effectively. Further, isothiazolone compounds and siabendazoles described in JP-A-57-8542, chlorinated germicides such as chlorinated sodium isocyanurate, and other benzotriazoles, etc., Hiroshi Horiguchi, "Chemistry of Antibacterial and Antifungal Agents" The sterilizing agents described in "Microbial Sterilization, Sterilization, and Antifungal Technologies" edited by the Society of Hygiene Technology and "Encyclopedia of Antibacterial and Antifungal Agents" edited by Japan Society for Antibacterial and Antifungal Agents can also be used.

The pH of washing water in the processing of the light-sensitive material of the present invention is 4-
9, preferably 5-8. The washing water temperature and washing time can be variously set depending on the characteristics of the light-sensitive material, application, etc., but in general, at 15-45 ° C for 20 seconds-10 minutes, preferably at 25-40 ° C.
A range of 30 seconds-5 minutes 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 a stabilizing process, the method disclosed in
All known methods described in 57-8,543, 58-14,834 and 60-220,345 can be used.

Further, there is a case where a stabilizing treatment is further performed after the water washing treatment, and an example thereof is a stabilizing bath containing formalin and a surfactant, which is used as a final bath of a color light-sensitive material for photographing. . 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.

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.
For incorporation, it is preferable to use various precursors of color developing agents. For example, indaniline compounds described in U.S. Pat.No. 3,342,597, No. 3,342,599, Schiff's base type compounds described in Research Disclosures 14,850 and 15,159, aldol compounds described in No. 13,924, metals described in U.S. Pat. Examples thereof include salt complexes and urethane compounds described in JP-A-53-135,628.

The silver halide color light-sensitive material of the present invention contains various 1-phenyl-containing compounds, if necessary, for the purpose of promoting color development.
You may incorporate 3-pyrazolidones. Typical compounds are JP-A Nos. 56-64,339, 57-144,547, and 58.
-115,438 etc. are described.

The various treatment liquids in the present invention are used at 10 ° C to 50 ° C. Normally, a temperature of 33 ° C to 38 ° C is standard, but a higher temperature accelerates the processing to shorten the processing time, and a lower temperature lowers the image quality to improve the stability of the processing liquid. be able to. Further, in order to save silver in the light-sensitive material, processing using cobalt intensification or hydrogen peroxide intensification described in West German Patent No. 2,226,770 or US Pat. No. 3,674,499 may be performed.

Further, the silver halide light-sensitive material of the present invention is described in US Pat.
500,626, JP-A-60-133449, 59-218443, 6
It can also be applied to the photothermographic materials described in 1-238056 and European Patent 210,660A2.

Example A sample 101, which is a multilayer color light-sensitive material having the following compositions, was prepared on an undercoated cellulose triacetate film support.

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.

First layer (antihalation layer) Black colloidal silver 0.2 Gelatin 1.3 ExM-9 0.06 UV-1 0.03 UV-2 0.06 UV-3 0.06 Solv-1 0.15 Solv-2 0.15 Solv-3 0.05 Second layer (intermediate layer) Gelatin 1.0 UV-1 0.03 ExC-4 0.02 ExF-1 0.004 Solv-1 0.1 Solv-2 0.1 Third layer (low-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion Coating amount 1.2 (AgI 4 mol%, uniform AgI type) , Sphere equivalent diameter 0.5 μm, variation coefficient of sphere equivalent diameter 20%, plate-like grain, diameter / thickness 3.0) Silver iodobromide emulsion coating amount 0.6 (AgI 3 mol%, uniform AgI type, sphere equivalent diameter 0.3 μm, 15% variation coefficient of equivalent spherical diameter, spherical particles, diameter / thickness 1.0) Gelatin 1.0 ExS-1 4 × 10 ^-4 ExS-2 5 × 10 ^-5 ExC-1 0.05 ExC-2 0.50 ExC-3 0.03 ExC-4 0.12 ExC-5 0.01 4th layer (high-sensitivity red sensitive emulsion layer) Silver iodobromide emulsion Coating amount 0.7 (AgI 6 mol%, internal high AgI type with 1: 1 core-shell ratio, sphere equivalent diameter 0.7 μm, sphere equivalent Diameter variation 15%, tabular grain, diameter / thickness ratio 5.0) Gelatin ^{1.0 ExS-1 3 × 10 -4} ExS-2 2.3 × 10 -5 ExC-6 0.11 ExC-7 0.05 ExC-4 0.05 Solv-1 0.05 Solv-3 0.05 Fifth layer (intermediate layer) Gelatin 0.5 Cpd-1 0.1 Solv-1 0.05 Sixth layer (low-sensitivity green emulsion layer) Silver iodobromide emulsion 0.35 (AgI 4 mol%, core-shell ratio of 1: 1) Surface high AgI type, equivalent sphere diameter 0.5 μm, variation coefficient of equivalent sphere diameter 15%, plate-like grain, diameter / thickness ratio 4.0) Silver iodobromide emulsion coating amount 0.20 (AgI 3 mol%, uniform AgI type, sphere) Equivalent diameter 0.3 μm, variation coefficient of spherical equivalent diameter 25%, spherical particles, diameter / thickness ratio 1.0) Gelatin 1.0 ExS-3 5 × 10 ^-4 ExS-4 3 × 10 ^-4 ExS-5 1 × 10 ^-4 ExM -8 0.45 ExM-9 0.02 ExM-10 0.01 ExY-13 0.03 Solv-1 0.3 Solv-4 0.05 7th layer (high sensitivity green emulsion layer) Silver iodobromide emulsion Silver coating amount 0.8 (AgI 4 mol%, core shell) Internal high AgI type with a ratio of 1: 3, sphere equivalent diameter 0.7 μm, sphere Variation coefficient of 20% of the equivalent diameter, the plate-like particles, diameter / thickness ratio 5.0) Gelatin ^{0.5 ExS-3 5 × 10 -4} ExS-4 3 × 10 -4 ExS-5 1 × 10 -4 ExM-8 0.13 ExM- 9 0.02 ExY-11 0.03 ExC-2 0.03 ExM-14 0.01 Solv-1 0.2 Solv-4 0.01 Eighth layer (intermediate layer) Gelatin 0.5 Cpd-1 0.05 Solv-1 0.02 Ninth layer (of the multilayer effect on the red-sensitive layer) Donor layer) Silver iodobromide emulsion Coating amount 0.35 (AgI 2 mol%, internal high AgI type with core-shell ratio 2: 1, equivalent sphere diameter 1.0 μm, variation coefficient of equivalent sphere diameter 15%, plate-like grain, diameter / Thickness ratio 6.0) Silver iodobromide emulsion Coating amount 0.20 (AgI 2 mol%, internal high AgI type with 1: 1 core-shell ratio, sphere equivalent diameter 0.4 μm, variation coefficient of sphere equivalent diameter 20%, tabular grain, diameter / Thickness ratio 6.0) Gelatin 0.5 ExS-3 8x10 ^-4 ExY-13 0.11 ExM-12 0.03 ExM-14 0.10 Solv-1 0.20 10th layer (yellow filter layer) Yellow colloidal silver 0.05 Gelatin 0.5 Cpd-2 0.13 Solv -1 0.13 Cpd-1 0.10 11th layer (low-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion Coating amount 0.3 (AgI 4.5 mol%, uniform AgI type, sphere equivalent diameter 0.7 μm, variation coefficient of sphere equivalent diameter 15%, plate Particles, diameter / thickness ratio 7.0) Silver iodobromide emulsion Coating amount 0.15 (AgI 3 mol%, uniform AgI type, sphere equivalent diameter 0.3 μm, variation coefficient of sphere equivalent diameter 25%, plate-like particles, diameter / thickness Ratio 7.0) Gelatin 1.6 ExS-6 2 × 10 ^-4 ExC-16 0.05 ExC-2 0.10 ExC-3 0.02 ExY-13 0.07 ExY-15 1.0 Solv-1 0.20 12th layer (high-sensitivity blue-sensitive emulsion layer) Iodour Silver halide emulsion Coating amount 0.5 (AgI 10 mol%, internal high AgI type, sphere equivalent diameter 1.0 μm, variation coefficient of sphere equivalent diameter 25%, multiple twin plate-like grains, diameter / thickness ratio
2.0) Gelatin 0.5 ExS-6 1 × 10 ^-4 ExY-15 0.20 ExY-13 0.01 Solv-1 0.10 13th layer (first protective layer) Gelatin 0.8 UV-4 0.1 UV-5 0.15 Solv-1 0.01 Solv-2 0.01 14th layer (2nd protective layer) Fine grain silver bromide emulsion 0.5 (AgI 2 mol%, uniform AgI type, spherical equivalent diameter 0.07 μm) Gelatin 0.45 Polymethylmethacrylate particles (diameter 1.5 μm) 0.2 H-1 0.4 CpD- 5 0.5 CpD-6 0.5 In addition to the above components, each layer contains an emulsion stabilizer Cpd-3.
(0.04 g / m ² ) surfactant Cpd-4 (0.02 g / m ² ) was added as a coating aid.

Solv-1 Tricresyl Phosphate Solv-2 Dibutyl Phthalate Preparation of Samples 102 to 109 Same as Sample 101 except that the couplers of the present invention shown in Table 1 were used in place of EXY-13 of the sixth layer, ninth layer, eleventh layer and twelfth layer in Sample 101. Was prepared.

The obtained samples 101 to 109 were cut into strips, exposed to a white light of 20 CMS through a continuous wedge, and passed through the processing step (I).

In addition, the development time 2
The change in photographic property was examined by changing the time from 45 minutes to 3 minutes and 15 seconds.

In the treatment step (I), a Super HR-100 film manufactured by Fuji Film was treated in advance for 500 m to obtain a running equilibrium state.

Next, the strips exposed through the MTF evaluation chart for sharpness evaluation were treated with the above treatment liquid.

In the above processing steps, stable, → →
The countercurrent method was adopted. The amount of fixer brought into the stability tank was 2 ml per meter.

Table 2 shows the change in gradation and MT when the development time is changed.
Showed F.

It can be seen that the sample using the coupler of the present invention has high sensitivity, high sharpness, and little gradation variation.

Claims (2)

(57) [Claims] 1. A compound which releases a photographically useful group by consuming a total of at least 3 developing agent oxidized products through a multi-step reaction including at least 3 steps of reacting with an oxidized developing agent. A silver halide color photographic light-sensitive material characterized in that 2. The compound has a group capable of leaving by reacting with an oxidized form of a developing agent, and the leaving group is in a form capable of reacting with an oxidized form of a developing agent after leaving, which reacts with an oxidized form of a developing agent. By cleaving the leaving group, and the leaving group becomes a form capable of reacting with the oxidized form of the developing agent, and such a multi-step sequential reaction occurs at least 3 times, so that a total of at least 3 oxidized form of the developing agent is formed. The silver halide color photographic light-sensitive material according to claim 1, which contains a compound which is consumed to cleave a photographically useful group in the final reaction.