JPH077190B2 - Silver halide color photographic light-sensitive material - Google Patents

Description

TECHNICAL FIELD The present invention relates to a color photographic light-sensitive material excellent in sharpness and color reproducibility.

(Prior Art) Many studies have been conducted on color photographic light-sensitive materials for the purpose of improving sharpness and color reproducibility.

One such technology is a coupler that releases a development inhibitor, DI
R Coupler (Development Inhibitor Releasing Couple
r) is called.

DIR couplers are usually mixed with color image forming couplers. At that time, there is an idea that the hue of the dye formed by the DIR coupler need not necessarily match the hue of the dye formed by the color image forming coupler. If the DIR coupler is substantially colorless, has a low molecular extinction coefficient even if a dye is formed, or the dye formed is unstable and decomposes immediately, the DIR coupler should be added Greater freedom of choice. In such an idea, for example, U.S. Patent Nos. 3,958,993 and 3,961,959.
No. 4,174,969, 4,088,491, 4,183,752,
The compounds described in No. 4,171,223 or No. 4,315,070 are known. However, it has been found that all of these compounds release a development inhibitor from the coupling position of the coupler and have a limit in the sharpness improving effect.
Further, it has been found that the coupling speed is low and a sufficient effect cannot be obtained when used in combination with a recent high speed type color image forming coupler.

Further, JP-A-60-185950 describes an example of a compound which is an indanone type coupler mother nucleus as a color-free coupler mother nucleus and is oxidized as a leaving group to cleave a development inhibitor. Although this compound shows some performance, it was also found that the coupling rate was low and the practical value was low.

(Object of the Invention) An object of the present invention is to provide a color photographic light-sensitive material excellent in sharpness and color reproducibility.

(Structure of the Invention) The above object was achieved by a color photographic light-sensitive material containing a compound represented by the following general formula (I).

General formula (I) In the formula, Z ₂ and Z ₄ represent a -CO- group or a -SO ₂ -group, Z ₃ represents -N (R ₅ )-, a sulfur atom, an oxygen atom, -C (=
_{N-R 5) -, -} C (R 9) = C (R 10) - or -C (R ₉₎ = N
-, or a divalent group formed by combining any two of these, -N in the general formula _{= C (R 4) b -} , (Z 2)
_c , (Z ₄ ) _d and CH-PDI represent an organic atomic group for forming a 5-membered ring or a 6-membered ring, PDI is a group which is released after the compound reacts with an oxidized product of a developing agent, After elimination, it represents a group which forms a development inhibitor through a reaction with an oxidized product of a developing agent, and a, b, c and d each represent 0 or 1. R ₄ , R ₅ , R ₉ and R ₁₀ represent a hydrogen atom or a substituent. Furthermore, in the above general formula, When the ring represented by is a 5-membered ring, a represents 0,
c represents 1, b and d represent 0 or 1.

In addition, when the above-mentioned ring is a 6-membered ring, the case where a benzene ring can be formed by tautomerism is excluded.

Among the compounds represented by the general formula (I), preferred compounds are represented by the following general formula (II).

In the general formula _{(II) A- (L 1)} V -B- (L 2) W -DI formula, A is the general formula (I) means the same as the coupler residue obtained by removing PDI, oxidized developing agent By reaction with
(L ₁₎ represents a _V -B- (L _{2) W} -DI cleaving group, L ₁ represents a group which cleaves cleavage B- (L _{2) W} -DI than A, B is A
After cleavage from − (L ₁ ) _V , it reacts with the oxidized form of the developing agent.
(L ₂ ) represents a group that cleaves _W- DI, L ₂ represents a group that cleaves from B and then cleaves DI, and DI represents a development inhibitor.
v and w represent 0 or 1.

The reaction process in which the compound represented by the general formula (II) releases DI during development is represented by the following reaction formula.

Where A, L₁, B, L₂, DI, v and w are in the general formula (II)
Has the same meaning as explained, T Is the developing agent oxidant
Represents

In the above reaction formula, B- (L₂)_WFrom −DI (L₂)_W-Create DI
The resulting reaction characterizes the excellent effect of the present invention. Sanawa
Chico's reaction is T And B- (L₂)_W-Secondary reaction with DI
It That is, the reaction rate depends on each concentration.
Therefore T B- (L
₂)_W−DI is (L₂)_W-Generate DI immediately. In contrast
To T B- (L₂)_W
−DI is (L₂)_W-Generate DI slowly. Such a reaction process
Effectively expresses the action of DI in conjunction with the above reaction process
It

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

The group represented by B in the general formula (II) is described in detail in A-
A group which becomes a coupler after cleaving from (L ₁ ) _V or A- (L ₁ ) _V
It is a group that becomes a redox group after further cleavage. As a group which becomes a coupler, for example, in the case of a phenol type coupler, A- (L ₁ ) _{V at} the oxygen atom excluding the hydrogen atom of the hydroxyl group
Is combined with. Further, in the case of a 5-pyrazolone type coupler, it is bonded to A- (L ₁ ) _{V at} an oxygen atom obtained by removing a hydrogen atom from a hydroxyl group of a type tautomerized to 5-hydroxypyrazole. In these examples, a phenol type coupler or a 5-pyrazolone type coupler is not formed until they are separated from A- (L ₁ ) _V.
They have (L ₂ ) _W -DI at their coupling position. When B represents a group to be a redox group, it is preferably represented by the general formula (B-1).

General formula (B-1) In the formula, the * mark represents the position at which it bonds to A- (L ₁ ) _V in the general formula (II), and (L ₂ ) _W —DI has the same meaning as described in the general formula (II).

In the formula, P _b and Q _b each independently represent an oxygen atom or a substituted or unsubstituted imino group, and n number of X _b and Y _b
At least one of L ₂ ) represents a methine group having _{W 2} -DI as a substituent, other X _b and Y _b represent a substituted or unsubstituted methine group or a nitrogen atom, and n represents an integer of 1 to 3. (N X _b and n Y _b represent the same or different), and A _b represents a hydrogen atom or a group removable by an alkali. Where P _b , X _b , Y _b ,
It also includes the case where any two substituents of Q _b and A _b are connected to form a divalent group to form a cyclic structure. For example (X
_{This is the case where b} = Y _b ) _n forms a benzene ring, a pyridine ring or the like.

When P _b and Q _b 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 _b and Q _b are expressed as follows.

Here, the * mark represents the position of bonding to A- (L ₁ ) _V -or A _b, and the ** mark represents the position of bonding to one of the free bonds of-(X _b = Y _{b n} ).

In the formula, the group represented by G has 1 to 32 carbon atoms, preferably 1
~ 22 linear or branched, linear or cyclic, saturated or unsaturated, substituted or unsubstituted aliphatic group (for example, a methyl group,
An ethyl group, a benzyl group, a phenoxybutyl group, an isopropyl group, etc.), a substituted or unsubstituted aromatic group having 6 to 10 carbon atoms (for example, a phenyl group, a 4-methylphenyl group, 1-
A 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, 2-pyridyl group, 1-phenyl-4) -Imidazolyl group, 2-furyl group, benzothienyl group, etc.) are preferred examples.

When A _b represents a group that can be removed by an alkali (hereinafter referred to as a precursor group), it is preferably hydrolyzed such as an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an imidoyl group, an oxazolyl group, and a sulfonyl group. Uru, U.S. Patent No. 4,009,02
A precursor group of the type utilizing the reverse Michael reaction described in No. 9, a precursor group of the type 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. No. 3,932,480 or 3,993,661, the anion described in US Pat.No.4,335,200 by the electron transfer of the anion described in U.S. Pat. Precursor group that causes a cleavage reaction or U.S. Patent Nos. 4,363,865 and 4,410,6
Precursor groups utilizing the imidomethyl group described in No. 18 are mentioned.

In the general formula (B-1), P _b represents an oxygen atom and A _b represents a hydrogen atom.

More preferably in formula _{(B-1) X b,} Y b is a substituent (L _2), except where it is methine group having a _W -DI other X _b and Y _b is a substituted or unsubstituted It is when it is a methine group.

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

For example, U.S. Pat.No. 4,146,396, JP-A-60-249148,
And No. 60-249149, which are groups represented by the following general formula. Here, the * mark represents the position bonded to the left side in the general formula (I), and the ** mark represents the position bonded to the right side in the general formula (I).

In the formula, W is an oxygen atom, a sulfur atom, or (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 They 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.
Each of R ₁ , R ₂ and R ₃ is preferably an aliphatic group, an aromatic group, a sulfonyl group, an acyl group, a carbamoyl group, an alkoxycarbonyl group or a hydrogen atom. Specific examples of the group represented by (T-1) are shown below.

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

Examples include the timing groups described in US Pat. No. 4,248,962. It can be represented by the following general formula.

* -Nu-Link-E-** (T-2) In the formula, the * mark represents the position bonded to the left side in the general formula (I), and the ** mark represents the position bonded 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.
A carbonyl group is a typical example, which is a group capable of cleaving the bond with ** by a more nucleophilic attack, and Link is steric so that Nu and E can undergo an intramolecular nucleophilic substitution reaction. Represents a linking group associated with. Specific examples of the group represented by (T-2) are as follows.

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

Examples are groups described in US Pat. Nos. 4,409,323 or 4,421,845 and represented by the following general formula.

In the formula, *, **, 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 (II), DI is specifically tetrazolylthio group, benzimidazolylthio group, benzothiadiazolylthio group, benzoxazolylthio group, benzotriazolyl group, benzoindazolyl group, triazolylthio group, imidazolylthio group, thiadia Examples thereof include a azolylthio group, a thioether-substituted triazolyl group (for example, a development inhibitor described in US Pat. No. 4,579,816), an oxadiazolylthio group, and the like, which may have a suitable substituent. The following examples are mentioned as a typical substituent. 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 thereof include an oxycarbonyloxy group, a heterocyclic oxycarbonyl group, a heterocyclic oxy group, a sulfonyl group, an acyl group, a ureido group, a heterocyclic group and a hydroxyl group.

The groups represented by L ₁ and L ₂ in the general formula (II) 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.

In the general formula (II), when any two groups represented by A, L ₁ , B, L ₂ and DI have a bond in addition to the bond represented by the general formula (II), the present application Include. The effect of the present invention can be obtained even if this second bond is not cut during development. Examples of such couplings are, for example:

The compound represented by the general formula (II) of the present invention may be a polymer. That is, it is derived from a monomer compound represented by the following general formula (PI),
A polymer having a repeating unit represented by I) or a non-color-forming monomer containing at least one ethylene group which has no ability to couple with an oxidation product of an aromatic primary amine developing agent. It is a copolymer with one or more kinds.
Here, two or more kinds of monomers may be polymerized at the same time.

General formula (P-I) General formula (P-2) In the formula, R is a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms,
Or represents a chlorine atom, A ₁ is -CONH-, -NHCONH-,
-NHCOO -, - COO -, - SO 2 -, - CO -, - NHCO -, - S
_{O 2 NH -, - NHSO 2} -, - OCO -, - OCONH -, - S -, - N
Represents H- or -O-, A ₁ represents -CONH- or -COO-, A ₃ represents an unsubstituted or substituted alkylene group having 1 to 10 carbon atoms, an aralkylene group or an unsubstituted or substituted arylene group. The alkylene group may be linear or branched.

(Examples of alkylene groups include methylene, methylmethylene, dimethylmethylene, dimethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, decylmethylene, aralkylene groups such as benzylidene, arylene groups such as phenylene, naphthylene, etc.) Represents a compound residue represented by the general formula (II),
It may be bound at any of A, L ₁ , B and L ₂ .

i, j, and k represent 0 or 1, but i, j,
And k cannot be 0 at the same time.

Here, the substituent of the alkylene group, aralkylene group or arylene group represented by A ₃ is an aryl group (for example, a phenyl group), a nitro group, a hydroxyl group, a cyano group, a sulfo group, an alkoxy group (for example, a methoxy group), an aryloxy group. (Eg phenoxy group), acyloxy group (eg acetoxy group), acylamino group (eg acetylamino group), sulfonamide group (eg methanesulfonamide group), sulfamoyl group (eg methylsulfamoyl group), halogen atom (eg fluorine group) Element, chlorine, bromine, etc.), a carboxy group, a carbamoyl group (eg, methylcarbamoyl group), an alkoxycarbonyl group (eg, methoxycarbonyl group, etc.), and a sulfonyl group (eg, methylsulfonyl group). When there are two or more substituents, they may be the same or different.

Next, as the non-color-forming, ethylene-like monomer that does not couple with the oxidation product of the aromatic primary amino developing agent, acrylic acid, α-chloroacrylic acid, α-alkylacrylic acid and these acrylic acids are derived. Examples include esters or amides, methylenebisacrylamide, vinyl esters, acrylonitrile, aromatic vinyl compounds, maleic acid derivatives, vinyl pyridines and the like. The non-color-forming ethylenically unsaturated monomers used here may be used in combination of two or more.

Next, more preferable compounds among the compounds represented by formula (II) will be described.

The group represented by A is preferably one represented by the following general formula.

In the formula, PDI, Z ₁ , Z ₂ , Z ₃ and Z ₄ have the same meanings as described for the general formula (I), R ₄ represents a hydrogen atom or a substituent, and —Z ₅ —Z ₆ — Has the same meaning as Z ₃ described for formula (I), but Z ₆ represents an oxygen atom, a sulfur atom or an N—R ₅ group. Here, R ₅ represents a hydrogen atom or a substituent. However, general formulas (A-2) and (A-
5) and (A-6), Z ₃ represents an atomic group for forming a 5-membered ring or a 6-membered ring, and in the general formulas (A-1) and (A-3), Z ₃ represents a 6-membered ring. Represents an atomic group for constituting, and in the general formula (A-4), Z ₅ represents an atomic group for constituting a 6-membered ring.

General formula (A-1), (A-2), (A-3) and (A
In R), when R ₄ represents a substituent, preferred examples of the substituent are R ₂₁ group, R ₂₁ O- group, Cyano group, carboxyl group, sulfo group, or R ₂₁ OSO ₂
-Groups and the like. Here, R ₂₁ represents an aliphatic group, an aromatic group or a heterocyclic group, R ₂₂ and R ₂₃ are hydrogen atoms,
It represents an aliphatic group, an aromatic group or a heterocyclic group. R ₂₁ , R ₂₂
And when R ₂₃ represents an aliphatic group, it has 1 to 3 carbon atoms
2, preferably 1 to 18 saturated or unsaturated cyclic or chain, linear or branched, substituted or unsubstituted aliphatic hydrocarbon groups. As a typical example,
Methyl, ethyl, propyl, butyl, t-butyl, cyclohexyl, s-butyl, allyl, hexyl, dodecyl, tetradecyl, hexadecyl, 1,1,3,3-tetramethyl Examples thereof include a butyl group, an octadecyl group and a 1-hexyl-nonyl group. R ₂₁ , R ₂₂
And when R ₂₃ represents an aromatic group, has 6 to 18 carbon atoms,
Preferably, 6 to 10 substituted or unsubstituted phenyl groups or substituted or unsubstituted naphthyl groups are mentioned. When R ₂₁ , R ₂₂ and R ₂₃ each represent a heterocyclic group, it has 1 to 18 carbon atoms, preferably 1 to 7 carbon atoms, and is a 4- to 8-membered ring selected from a nitrogen atom, a sulfur atom or an oxygen atom as a hetero atom. It is a substituted or unsubstituted heterocyclic group. 2-pyridyl group and 3 are typical examples of the heterocyclic group.
-Pyridyl group, 4-imidazolyl group, 3-pyrazolyl group, 1,2,4-triazol-3-yl group, 1,3,4-thiadiazol-2-yl group, 2-furyl group, 2-thienyl group, A 3-imidazolidinyl group, a diazinyl group, etc. are mentioned. When the aliphatic group, aromatic group and heterocyclic group have a substituent, examples of the substituent include the substituents listed for R ₄ , a hydroxyl group, or a nitro group. In the substituent containing R ₂₁ and R ₂₂ or R ₂₂ and R ₂₃ at the same time, they may be bonded to each other to form a ring.

General formula (A-1), (A-2), (A-3) and (A
-4), preferred examples of R ₄ include a hydrogen atom and the above-listed substituents R ₂₁ group, R ₂₁ O- group, R ₂₁ S- group, Is.

Preferred compounds in formula (A-1) are as follows.

Preferred compounds in formula (A-2) are as follows.

Preferred compounds in formula (A-3) are as follows.

Preferred compounds in formula (A-4) are as follows.

Preferred compounds in formula (A-5) are shown below.

Preferred compounds in formula (A-6) are shown below.

In the above general formula, R ₄ , PDI, Z ₁ , Z ₂ and Z ₄ have the same meaning as described above.

R ₅ , R ₆ , R ₉ , R ₁₀ , R ₁₁ and R ₁₂ represent a hydrogen atom or a substituent. Preferred examples of these substituents will be described below. In the examples below, R ₂₁ , R ₂₂ and R ₂₃ have the same meaning as explained above.

R ₅ is R ₂₁ group, R ₂₁ CO-- group, or Is a preferred example.

R ₆ is preferably a group having the same meaning as R ₅ .

As R ₉ , R ₂₂ group, R ₂₂ O- group, R ₂₁ S- group, R ₂₁ SO ₂ — group, R ₂₁ OCO— group, or a halogen atom are preferable examples.

R ₁₀ is preferably a group having the same meaning as R ₉ .

A preferable example of R ₁₁ is a group having the same meaning as R ₅ .

As R ₁₂ , R ₂₂ group, R ₂₁ O- group, R ₂₁ S- group, Is a preferred example.

In the general formulas (A-2-4) and (A-4-5), R ₉ and R ₁₀ may each represent a divalent group to form a ring. The general formulas (A-4-1) and (A-4-3)
In, R ₆ and R ₁₁ may each represent a divalent group to form a ring.

Particularly preferred examples of the general formula are (A-1-1),
(A-2-2), (A-2-5), (A-3-1),
(A-3-2), (A-4-1), (A-5-1),
It is represented by (A-6-1) and (A-6-2).

The group represented by B in the general formula (II) is preferably the group represented by the general formula (B-1) described above, and among them, particularly preferable one is the following general formula (B-2) or (B -3).

In the formula, * marks represent the bonding position of A- (L ₁ ) _v −, and Q _b
Represents the same meaning as described in the general formulas (N-1) and (N-2), R ₁₅ represents a substituent, and q represents 0.
Represents an integer of 3 to 3.

When q is 2 or more, two or more R _15's may be the same or different, and when two R _15's are substituents on adjacent carbons, they are linked to form a divalent group to form a cyclic structure. It also includes the case of representing. In that case, it becomes a benzene condensed ring, for example, naphthalene, benzonorbornene, chroman, indole, benzothiophene, quinoline, benzofuran, 2,3-dihydrobenzofuran,
It becomes a ring structure such as indans or indenes, which may further have one or more substituents. Examples of preferred substituents having a substituent on these condensed rings,
And preferred examples of R ₁₅ when R ₁₅ does not form a condensed ring are those listed below. 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 atom, bromo atom), alkoxy group (eg methoxy group, hexadecyloxy group), Alkylthio group (eg methylthio group, dodecylthio group, benzylthio group), aryloxy group (eg phenoxy group, 4-t-octylphenoxy group, 2,4-di-t-amylphenoxy group), arylthio group (eg 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 −
A di-t-amylphenoxy) propylcarbamoyl group,
N-methyl-N-octadecylcarbamoyl group), alkoxycarbonyl group (eg methoxycarbonyl group, 2
-Cyanoethoxycarbonyl group, ethoxycarbonyl group, dodecyloxycarbonyl group, 3- (2,4-di-t
-Amylphenoxy) propoxycarbonyl group), aryloxycarbonyl group (eg phenoxycarbonyl group, 4-nonylphenoxycarbonyl group), sulfonyl group (eg methanesulfonyl group, benzenesulfonyl group, p-toluenesulfonyl group), sulfamoyl Group (for example, N-propylsulfamoyl group, N-methyl-
N-octadecylsulfamoyl group, N-phenylsulfamoyl group, N-dodecylsulfamoyl group), acylamino group (for example, acetamide group, benzamide group,
Tetradecanamide 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 (eg methanesulfonamide group, benzenesulfonamide group, hexadecylsulfonamide 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 (nitrogen as a hetero atom) atom,
A 4- to 6-membered heterocyclic group selected from an oxygen atom and a sulfur atom. For example, 2-furyl group, 2-pyridyl group,
1-imidazolyl group, 1-morpholino group), hydroxyl group, carboxyl group, alkoxycarbonylamino group (for example, methoxycarbonylamino group, phenoxycarbonylamino group, dodecyloxycarbonylamino group), sulfo group, amino group, arylamino Group (for example, anilino group, 4-methoxycarbonylanilino group, aliphatic amino group (for example, N, N-diethylamino group, dodecylamino group), sulfinyl group (for example, benzenesulfinyl group, propylsulfinyl group), sulfone Phamoylamino group (for example, 3-phenylsulfamoylamino group), thioacyl group (for example, thiobenzoyl group), thioureido group (for example, 3-phenylthioureido group), heterocyclic thio group (for example, thiadiazolylthio group) ), An imide group (for example, a succinimide group, Taruimido group, octadecenyl imido group) or a heterocyclic amino group (e.g., 4-imidazolylmethyl group, 4-pyridylamino group).

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

When the partial structure of the above-mentioned substituent has an aromatic group moiety, it has 6 to 10 carbon atoms, preferably a substituted or unsubstituted phenyl group.

Particularly preferred among R ₁₅ listed above are an aliphatic group, an alkoxy group, an alkylthio group, a carbamoyl group, an alkoxycarbonyl group, a hydroxyl group, or a heterocyclic thio group.

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

Particularly preferred DI in the general formula (II) is a compound having a development inhibitory property when cleaved as DI, but a compound that 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, No. 60-233,650, or No. 61-11,7
The development inhibitor described in No. 43 can be mentioned, preferably the following general formulas (D-1), (D-2), (D-3) and (D-
4), (D-5), (D-6), (D-7), (D-
8), (D-9), (D-10) or (D-11).

In the formula, the * mark represents the position at which it is bonded to AL ₁ ) _v- B- (L ₂ ) _w- in formula (II), R ₁₆ represents a hydrogen atom or a substituent, and e represents 1 or 2. , L ₃ represents a group containing a chemical bond which is cleaved in the developing solution, and Y _i represents a substituent which exerts a development inhibiting action and represents an aliphatic group, an aromatic group or a heterocyclic group.

The development inhibitor _{A- (L 1) v -B- (} L 2) w - to spread the photographic layers while showing a development inhibiting effect after cleavage from, flows to a part color developing 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 _i is cleaved to become a highly water-soluble compound having a small development inhibitory property, and the development inhibitory action is substantially eliminated.

R ₁₆ is preferably a hydrogen atom, but 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 ( For example, methoxy group, ethoxy group), halogen atom (for example, chloro atom,
A typical example is a bromo atom), a nitro group, or a sulfonamide group (for example, 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 those listed 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 bond mode shown in the above table is directly linked to the portion of the heterocycle constituting the development inhibitor or via an alkylene group and / or a phenylene group, and directly linked to Y _i . When connecting via an alkylene group or a phenylene group, the intervening divalent group may include an ether bond, an amide bond, a carbonyl group, a thioether bond, a sulfone group, a sulfonamide bond and a urea bond.

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

When Y _i 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 heterocycle, pyridyl group, imidazolyl group, furyl group, pyrazolyl group, oxazolyl group, thiazolyl group, thiadiazolyl group, triazolyl group, diazolidinyl group,
Alternatively, a diazinyl group and the like can be mentioned.

When the aliphatic hydrocarbon group, aromatic group and 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, An alkanesulfonyl group having 1 to 10 carbon atoms,
Arylsulfonyl group having 6 to 10 carbon atoms, alkaneamide group having 1 to 10 carbon atoms, anilino group, benzamide group, alkylcarbamoyl group having 1 to 10 carbon atoms, carbamoyl group,
Arylcarbamoyl group having 6 to 10 carbon atoms, 1 to 10 carbon atoms
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,
Benzothiazolyl group, alkylamino group having 1 to 10 carbon atoms, alkanoyl group having 1 to 10 carbon atoms, benzoyl group, alkanoyloxy group having 1 to 10 carbon atoms, 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 to 6 carbon atoms
10 arylsulfamoyl group, morpholino group, aryl group having 6 to 10 carbon atoms, pyrrolidinyl group, ureido group, urethane group, alkoxycarbonyl group having 1 to 10 carbon atoms, aryloxycarbonyl group having 6 to 10 carbon atoms, Examples thereof include an imidazolidinyl group and an alkylideneamino group having 1 to 10 carbon atoms.

The compound represented by formula (I) of the present invention is a multilayer multicolor photographic material having at least three different spectral sensitivities on a support, mainly for the purpose of improving sharpness, improving color reproducibility or improving graininess. Applicable. 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 can be arbitrarily selected as required. The compounds of the invention can be added to any of these layers. It can be used not only in the light-sensitive emulsion layer but also in the adjacent layer, for example, the intermediate layer. The compounds of the invention are preferably used in blue or green sensitive emulsion layers or interlayers. Further, the compound of the present invention can be added to a layer having any sensitivity such as a high sensitivity layer and a low sensitivity layer.

The amount of the compound of the general formula (I) added varies depending on the structure of the compound, but is preferably silver 1 present in the same layer or an adjacent layer.
1 × 10 ⁻⁶ to 0.5 mol per mol, particularly preferably 1 × 1
It is 0 ⁻⁵ to 1 × 10 ⁻¹ mol.

When the compound of the general formula (I) and the coupler for color image formation are mixed and used, the molar ratio thereof is 0.01 / 99.99 to 50/5.
0/99 to 30/70 (the compound of the present invention / color image-forming coupler) is preferable.

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

Synthesis Example (1) Synthesis of Exemplified Compound (2) The compound was synthesized by the following synthesis route.

Step 1 Synthesis of Intermediate Compound 1 , 50 g was dissolved in 500 ml of acetonitrile and 28.4 g of 1-phenyltetrazolyl 5-sulfenyl chloride ( 2 ) was dissolved.
Was added dropwise at room temperature. After dropping 1
After reacting for a time, ethyl acetate 1 was added, and the mixture was transferred to a separating funnel and washed with water. The oil layer was taken, the solvent was distilled off under reduced pressure, and the residue was recrystallized from a mixed solvent of ethyl acetate and hexane to obtain 48.9 g of the desired compound 3 .

48.9 g of Synthesis 3 of Step Intermediate Compound 5 and 12.2 g of potassium carbonate were added to 300 ml of N, N-dimethylformamide, and 21.7 g of ethyl α-chloroacetoacetate ( 4 ) was added at room temperature with stirring. The reaction was carried out at 50 ° C for 2 hours. After cooling to room temperature, ethyl acetate 1 was added and the mixture was transferred to a separating funnel and washed with water. The oil layer was taken, the solvent was distilled off, and the residue was recrystallized from a mixed solvent of ethyl acetate and hexane to obtain 35.9 g of the target compound 5 .

Synthesis of Intermediate Compound 7 35.9 g of compound 5 obtained above and N-3- (2,4-di-
20 g of t-amylphenoxy) propylsulfuryldiamide ( 6 ) was added to 200 ml of N, N-dimethylformamide and 60
Heat at ℃ for 30 minutes, add 1g of triethylamine and add 2
The reaction was carried out at 60 ° C for a time. After cooling to room temperature, ethyl acetate
After adding 500 ml, the mixture was transferred to a separating funnel and washed with water. After distilling off the solvent, the residue was recrystallized from ethyl acetate and hexane to obtain 29.3 g of the target compound 7 .

Synthesis of Step Exemplified Compound (2) 29.3 g of the compound 7 obtained above was added to 300 ml of methanol,
Hydrochloric acid 15 ml was added. The mixture was heated to reflux and reacted for 2 hours. After cooling to room temperature, ethyl acetate 1 was added and the mixture was transferred to a separating funnel and washed with water. After distilling off the solvent, the residue was recrystallized from ethyl acetate and hexane to obtain 15.8 g of the desired exemplified compound (2).

Synthesis Example (2) Synthesis of Exemplified Compound (13) The compound was synthesized by the following synthetic route.

It was synthesized in the same manner as steps in Synthesis Example (1) using a synthetic 4 25 g, 8 50 g and potassium carbonate 14g stage intermediate compound 9. 38 g of 9 was obtained.

Synthesis of Intermediate Compound 10 9 , 38 g and guanidine carbonate 5.5 g ethanol 500 ml
And heated to reflux for 8 hours. 10 after post-treatment by conventional method
18g was obtained.

Synthesis of Step Example Compound (13) 18 g of 10 was added to 200 ml of acetonitrile. Under heating to reflux 2
1-1.8 g of-(2,4-di-t-amylphenoxy) hexanoyl chloride was added dropwise. The oily substance obtained by post-treatment by a conventional method was crystallized from ethyl acetate and hexane to obtain 15.8 g of Exemplified compound (13).

Synthesis Example (3) Synthesis of Exemplified Compound (14) The compound was synthesized by the following synthetic route.

Synthesis of Intermediate Compound 13 , 11 , 41.1 g, 12 , 69.5 g and 10 g of triethylamine were mixed with 200 ml of acetonitrile and mixed at room temperature for 1 hour and at 50 ° C.
And reacted for 30 minutes. Post-processing by conventional method 13 of 8
Obtained 4.5 g. Crystallization was performed using a mixed solvent of chloroform and hexane.

Synthesis 13 stage intermediate compound 14, 84.5 g, and N- bromosuccinimide, and the 14 .7G are mixed to react for 2 hours in chloroform 300 ml. Post-treatment was carried out by a conventional method to obtain 76.2 g of 14. Used in the next step without purification.

Step Synthesis of Intermediate Compound 15 and Synthesis of Exemplified Compound (14) 76.2 g of 14 and 4-amino-3-in 500 ml of ethanol
8 g of mercapto-1,2,4-triazole and 8 g were added and the mixture was heated under reflux for 1 hour. After cooling to room temperature, ethyl acetate 1 was added and the mixture was transferred to a separating funnel and washed with water. The oil layer was taken and the solvent was distilled off under reduced pressure. The residue was recrystallized with a mixed solvent of chloroform and hexane to obtain 51.3 g of the desired exemplary compound (15).

Any silver halide of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride may be used in the photographic emulsion layer of the photographic light-sensitive material used in the present invention. A preferred silver halide is silver iodobromide 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.

The silver halide grains in the photographic emulsion may be so-called Regular grains having regular crystal bodies such as cubes, octahedra and tetradecahedrons, and those having irregular crystal shapes such as spheres, It may have 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 0.1 micron or less or large size grains having a projected area diameter of up to about 10 microns, and it may be a monodisperse emulsion having a narrow distribution or a polydisperse emulsion having a wide distribution. Good.

The silver halide photographic emulsion which can be used in the present invention can be produced by a known method, for example, Research Disclosure (RD), No. 17643 (December 1978), pp. 22-23, "I. Emulsion Production (Emulsion preparation and types) ”and the same,
No. 18716 (November, 1979), p.648 can be followed.

The photographic emulsion used in the present invention is described in "Physics and Chemistry of Photography" by Graphide, published by Paul Montel (P.Glafkides, Chim.
ie et Physique Photographique Paul Montel, 1967),
Duffin, "Photoemulsion Chemistry", published by Forcal Press, Inc. (GFDuffin, Photographic Emulsion Chemistry (Foca
Press, 1966), "Manufacturing and coating of photographic emulsions" by Zelikman et al., published by Forcal Press (VLZelikman et al, Maki
ng and Coating Photographic Emulsion, Focal Press, 1
964) and the like. That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and a method of reacting a soluble silver salt and a soluble halogen salt may be a one-sided mixing method, a simultaneous mixing method or a combination thereof. Good. A method of forming grains in the presence of excess silver ions (so-called reverse mixing method) can also be used. As one form of the simultaneous mixing method, a method of keeping pAg in a liquid phase where silver halide is formed constant, that is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a substantially uniform grain size can be obtained.

Two or more kinds of silver halide emulsions formed separately may be mixed and used.

The silver halide emulsion composed of the above-mentioned regular grains can be obtained by controlling pAg and pH during grain formation. For details, see, for example, Photographic Science and Engineering.
eering) Vol. 6, pp. 159-165 (1962); Journal of Photo.
graphic Science, 12: 242-251 (1964), U.S. Pat. No. 3,655,394 and British Patent 1,413,748.

Monodisperse emulsions are silver halide grains having an average grain diameter of greater than about 0.1 micron, at least about 95
Emulsions are typically such that the weight percentage is within ± 40% of the average grain diameter. An average particle diameter of about 0.25 to 2 microns, at least about 95% by weight or at least about 95% in quantity
An emulsion in which the above silver halide grains are within the range of average grain diameter ± 20% can be used in the present invention. Methods for making such emulsions are described in U.S. Pat. Nos. 3,574,628, 3,655,394 and British Patent 1,413,748. Further, JP-A-48-8600, 51-39027, 51-83097, 53
-137133, 54-48521, 54-99419, 58-37
Monodisperse emulsions such as those described in 635 and 58-49938 can also be preferably used in the present invention.

Further, tabular grains having an aspect ratio of about 5 or more can be used in the present invention. Tabular grains are described by Gatov, Gutoff, Photographic Science and Engineering,
Volume 14, Pages 248-257 (1970); U.S. Pat. No. 4,434,226
No. 4,414,310, No. 4,433,048, No. 4,439,520, and British Patent No. 2,112,157, and the like. When tabular grains are used,
The advantages of the sensitizing dye such as improvement of color sensitization efficiency, improvement of graininess and increase of sharpness are described in detail in US Pat. No. 4,434,226 cited above.

The crystal structure may be uniform, may have different halogen compositions inside and outside, or may have a layered structure. These emulsion grains are described in British Patent No. 1,027,146,
U.S. Pat.Nos. 3,505,068, 4,444,877 and Japanese Patent Application No. 58
-248469 and the like. Further, silver halides having different compositions may be joined by epitaxial joining, or may be joined with compounds other than silver halides such as silver rhodanide and lead oxide. These emulsion grains are described in U.S. Patent Nos. 4,094,684, 4,142,900 and
4,459,353, British Patent 2,038,792, U.S. Patent 4,34
9,622, 4,395,478, 4,433,501, 4,463,087
No. 3,656,962, No. 3,852,067, JP-A-59-162540
No., etc.

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

The emulsion of the present invention is usually used after physical ripening, chemical ripening and spectral sensitization. Additives used in such a process are described in Research Disclosure No. 17643 and No. 18716, and the corresponding parts are summarized in the table below.

Known photographic additives that can be used in the present invention are also described in the above-mentioned two research disclosures, and the locations described in the table below are shown.

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 dye-forming coupler, a coupler that gives the three primary colors of the subtractive method (that is, yellow, magenta and cyan) by color development is important,
Specific examples of the equivalent or 2-equivalent coupler are RD17643, VII described above.
-In addition to the couplers described in the patents of C and D,
The following can be preferably used in the present invention.

A typical example of the yellow coupler that can be used in the present invention is a hydrophobic acylacetamide coupler having a ballast group. A specific example is U.S. Pat.
No. 7,210, No. 2,875,057 and No. 3,265,506. In the present invention, it is preferable to use a two-equivalent yellow coupler, and US Pat.Nos. 3,408,194 and 3,4
No. 47,928, No. 3,933,501 and No. 4,022,620 oxygen atom desorption type yellow couplers described in JP-B-58-10739, U.S. Pat.No. 4,401,752, No. 4,
326,024, RD18053 (April 1979), British Patent 1,425,
No. 020, West German Application Publication No. 2,219,917, No. 2,261,361
No. 2,329,587, No. 2,433,812 and the like, nitrogen atom-releasing yellow couplers described in JP-A No. 2,329,587 and No. 2,433,812 are typical examples. The α-pivaloyl acetanilide type couplers are excellent in the fastness of color forming dyes, especially the light fastness, while the α-benzoyl acetanilide type couplers can obtain a high color density.

Examples of magenta couplers that can be used in the present invention include hydrophobic indazolone or cyanoacetyl, preferably 5-pyrazolone and pyrazoloazole couplers having a ballast group. The 5-pyrazolone-based coupler is preferably a coupler in which the 3-position is substituted with an arylamino group or an acylamino group, from the viewpoint of the hue and color density of the color forming dye, and a typical example thereof is U.S. Pat.
1,082, 2,343,703, 2,600,788, 2,9
No. 08,573, No. 3,062,653, No. 3,152,896 and No. 3,936,015. As a leaving group for a 2-equivalent 5-pyrazolone-based coupler, US Pat. No. 4,310,
Nitrogen atom leaving groups described in 619 or U.S. Pat.
The arylthio groups described in 51,897 are particularly preferred.
Further, it has a ballast group described in European Patent No. 73,636. 5
-Pyrazolone couplers provide high color density. As the pyrazoloazole coupler, U.S. Pat.
432 pyrazolobenzimidazoles, preferably pyrazolo [5,1−, described in U.S. Pat.No. 3,725,067
c] [1,2,4] triazoles, Research Disclosure 24220 (June 1984), and pyrazolotetrazoles and Research Disclosure 24230 (Japanese Patent Laid-Open No. 60-33552 24230 (June 1984) Month) and JP-A-60-4
Pyrazolopyrazoles described in 3659 can be mentioned. The imidazo [1,2-b] pyrazoles described in U.S. Pat.No. 4,500,630 are preferable in view of low yellow side absorption of a coloring dye and light fastness, and pyrazolo [1,5 in U.S. Pat. -B] [1,2,4] triazole is particularly preferred.

Cyan couplers that can be used in the present invention include hydrophobic and diffusion-resistant naphthol-based and phenol-based couplers, and the naphthol-based couplers described in U.S. Pat.No. 2,474,293, preferably U.S. Pat.Nos. 4,052,212 and 4 , 1
Representative examples thereof include oxygen atom elimination type two-equivalent naphthol couplers described in Nos. 46,396, 4,228,233 and 4,296,200. Further, specific examples of the phenol-based coupler are described in U.S. Patent Nos. 2,369,929 and 2,801,171.
No. 2,772,162, No. 2,895,826 and the like.

A coupler capable of forming a cyan dye that is fast against humidity and temperature is preferably used in the present invention, and typical examples thereof include an alkyl group having an ethyl group or higher at the meta position of the phenol nucleus described in U.S. Pat.No. 3,772,002. A phenolic cyan coupler having a group, U.S. Pat.No. 2,772,162,
No. 3,758,308, No. 4,126,396, No. 4,334,011
No. 4,327,173, West German Patent Publication No. 3,329,729 and European Patent No. 121,365, and the like, 2,5-diacylamino-substituted phenol-based couplers, U.S. Pat.No. 3,446,62.
No. 2, No. 4,333,999, No. 4,451,559 and No. 4,4
Nos. 27,767 and the like include phenol couplers having a phenylureido group at the 2-position and an acylamino group at the 5-position. The cyan couplers described in European Patent No. 161,626A in which the 5-position of naphthol is substituted with a sulfonamide group, an amide group, etc. are also excellent in the fastness of a color image and can be preferably used in the present invention.

In order to correct the unnecessary absorption of the chromophore, it is preferable to mask the color sensitive material for photographing with a colored coupler. U.S. Patent No. 4,163,670 and Japanese Patent Publication No. 57
Typical examples are yellow colored magenta couplers described in -39413 and the like, or magenta colored cyan couplers described in U.S. Pat. Nos. 4,004,929 and 4,138,258 and British Patent 1,146,368. Other colored couplers are described in RD17643, Item VII-G above.

The graininess can be improved by using a coupler in which the color forming dye has an appropriate diffusibility. Such couplers are
Specific examples of magenta couplers are described in U.S. Pat. No. 4,366,237 and British Patent 2,125,570, and specific examples of yellow, magenta or cyan couplers are described in European Patent No. 96,570 and West German Patent Publication No. 3,234,533.

The dye-forming coupler and the above-mentioned special coupler may form a dimer or higher polymer. Typical examples of polymerized dye forming couplers are described in US Pat. Nos. 3,451,820 and 4,080,211. Specific examples of polymerized magenta couplers are described in British Patent No. 2,102,173 and U.S. Patent No. 4,367,282.

Couplers that release a photographically useful residue upon coupling are also preferably used in the present invention. As the DIR coupler releasing the development inhibitor, the couplers of the patents described in the above-mentioned RD17643, section VII-F are useful.

A preferred combination with the present invention is JP-A-57-15.
Developer inactivation type represented by 1944; U.S. Pat. No. 4,248,96
No. 2 and JP-A-57-154234, and particularly preferable ones are JP-A-57-151944 and JP-A-58-154234.
No. 217932, Japanese Patent Application Nos. 59-75474, 59-82214, and 59-
82214 and 59-90438 and the like, and developer type deactivating DIR couplers and Japanese Patent Application No. 59-39653 and the like reactive DIR couplers.

In the light-sensitive material of the present invention, a coupler capable of releasing a nucleating agent or a development accelerator or a precursor thereof imagewise during development can be used. Specific examples of such compounds are described in British Patent Nos. 2,097,140 and 2,131,188. A coupler which releases a nucleating agent having an adsorption effect on silver halide is particularly preferable, and specific examples thereof are described in JP-A-59-157638 and JP-A-59-170840.

The compound represented by formula (I) and the above-mentioned coupler which can be used in the present invention can be introduced into a light-sensitive material by various known dispersion methods, for example, solid dispersion method, alkali dispersion method, preferably latex dispersion method, More preferably, a typical example is an oil-in-water dispersion method. In the oil-in-water dispersion method, a high-boiling point organic solvent having a boiling point of 175 ° C. or higher and a low-boiling point so-called auxiliary solvent are dissolved in a single liquid or a mixed liquid of both, and then water or gelatin is added in the presence of a surfactant. Finely dispersed in an aqueous medium such as an aqueous solution. Examples of high boiling organic solvents are described in U.S. Pat.No. 2,322,027
No. etc. The dispersion may be accompanied by phase inversion, and if necessary, the auxiliary solvent may be removed or reduced by distillation, rinsing with water or ultrafiltration, and then used for coating.

The steps of the latex dispersion method, effects, and specific examples of the latex for impregnation are described in US Pat. No. 4,199,363, West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230.

Suitable supports that can be used in the present invention include, for example, the aforementioned R
Page 28 of D.No.17643 and page 647 of the same, No.18716 From right column 6
See page 48, left column.

The color photographic light-sensitive material according to the present invention has the above-mentioned RD, No. 1
Development can be carried out by a usual method described in pages 28 to 29 of 7643 and 651 left column to right column of No. 18716.

The color developing solution used for the development processing of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine type color developing agent as a main component. Although aminophenol compounds are also useful as the color developing agent, p-phenylenediamine compounds are preferably used, and typical examples thereof include 3-methyl-4-amino-N, N-diethylaniline and 3-methyl-4-amino-N, N-diethylaniline. Methyl-4-amino-N-ethyl-N-β
-Hydroxylethylaniline, 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. Salts of these diamines are generally more stable than those in the free state, and are preferably used.

The color developing solution is a pH buffering agent such as an alkali metal carbonate, borate or phosphate, a development inhibitor such as a bromide, an iodide, a benzimidazole, a benzothiazole or a mercapto compound, or an antifoggant. Etc. are generally included. If necessary, preservatives such as hydroxylamine or sulfite, organic solvents such as triethanolamine and diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, and dyes. Forming couplers, competitive couplers, nucleating agents such as sodium boron hydride, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, tackifiers, aminopolycarboxylic acids,
Various chelating agents typified by aminopolyphosphonic acid, alkylphosphonic acid, and phosphonocarboxylic acid, and antioxidants described in West German Patent Application (OLS) No. 2,622,950 may be added to the color developer.

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

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed at the same time as the fixing process, or may be performed individually. Further, in order to speed up the process, a bleach-fixing process may be performed after the bleaching process. Examples of bleaching agents include iron (III), cobalt (III), chromium (VI),
Compounds of polyvalent metals such as copper (II), peracids, quinones,
A nitrone compound or the like is used. Typical bleaching agents are ferriciyanides; dichromates; organic complex salts of iron (III) or cobalt (III), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, 1,3-diamino-2-propanoltetraacetic acid. Aminopolycarboxylic acids or complex salts of organic acids such as citric acid, tartaric acid and malic acid; persulfates; manganates; nitrosphenol and the like can be used. Of these, ethylenediaminetetraacetic acid iron (III) salt, diethylenetriaminepentaacetic acid iron (III) salt and persulfate are preferable from the viewpoint of rapid treatment and environmental pollution. Furthermore, the ethylenediaminetetraacetic acid iron (III) complex salt can be used in an independent bleaching solution.
It is also particularly useful in a one-bath bleach-fix solution.

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-53-32736, JP-A-53-57831, JP-A-37418,
53-65732, 53-72623, 53-95630, 53
-95631, 53-104232, 53-124424, 53-1
41623, 53-28426, Research Disclosure No. 17129 (July 1978) and the like having a mercapto group or a disulfide group; JP-A-50-1401
Thiazolidine derivatives as described in No. 29;
45-8506, JP-A-52-20832, JP-A-53-32735, and thiourea derivatives described in U.S. Pat.No. 3,706,561; West German Patent 1,127,715 and iodide described in JP-A-58-16235; Polyethylene oxides described in West German Patent Nos. 966,410 and 2,748,430; polyamine compounds described in JP-B-45-8836; other JP-A-49-42434, 49-59644,
53-94927, 54-35727, 55-26506 and 5
The compounds described in 8-163940 and iodine and bromine ions can also be used. Among them, compounds having a mercapto group or a disulfide group are preferable from the viewpoint of a large accelerating effect, and the compounds described in U.S. Pat. Further, the compounds described in US Pat. No. 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 light-sensitive material for photography.

Examples of the fixing agent include thiosulfates, thiocyanates, thioether compounds thioureas, and a large amount of iodides, but thiosulfate is generally used. As the bleach-fixing solution and the preservative for the fixing solution, sulfite, bisulfite or carbonyl bisulfite adduct is preferable.

After bleach-fixing treatment or fixing treatment, washing treatment and stabilizing treatment are usually carried out. Various known compounds may be added to the washing process and the stabilizing process for the purpose of preventing precipitation and saving water. For example, in order to prevent precipitation, hard water softeners such as inorganic phosphoric acid, aminopolycarboxylic acid, organic aminopolyphosphonic acid, organic phosphoric acid, bactericides and antibacterial agents that prevent the generation of various bacteria, algae and molds. An agent, a metal salt typified by a magnesium salt or an aluminum salt bismuth salt, a surfactant for preventing drying load or unevenness, and various hardeners can be added as necessary. Or by West Photographic Science and Engineering (LEWest, Phot.Sc
i.Eng.), Vol. 6, pp. 344-359 (1965), etc. may be added. It is particularly effective to add a chelating agent or an antifungal agent.

In the water washing step, it is general to carry out countercurrent water washing of two or more tanks to save water. Furthermore, instead of the washing step, it is disclosed in
You may implement the multistage countercurrent stabilization processing process as described in 8543. In the case of this step, a countercurrent bath of 2 to 9 tanks is required. In addition to the above-mentioned additives, various compounds are added to the stabilizing bath for the purpose of stabilizing an image. For example, various buffers (eg, pH 3-9) to adjust the membrane pH (eg, pH 3-9)
Borate, metaborate, borax, phosphate, carbonate,
Typical examples include aldehydes such as potassium hydroxide, sodium hydroxide, aqueous ammonia, monocarboxylic acid, dicarboxylic acid, polycarboxylic acid, etc.) and formalin. In addition, if necessary, chelating agents (inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphoric acid, organic phosphonic acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc.), bactericides (benzoisothiazolinone,
Irithiazolone, 4-thiazoline benzimidazole,
Various additives such as halogenated phenols, sulfanilamide, benzotriazole, etc.), surfactants, fluorescent brighteners, hardeners, etc. may be used, and two or more kinds of the same or different target compounds may be used. You may use together.

Further, it is preferable to add various ammonium salts such as ammonium chloride, ammonium nitrate, ammonium sulfate, and ammonium thiosulfate as a film pH adjuster after the treatment.

Further, in the case of the color photosensitive material for photographing, the (washing-stabilizing) step after fixing which is usually performed can be replaced with the above-mentioned stabilizing step and the washing step (water saving processing). At this time, if the magenta coupler is 2 equivalents, the formalin in the stabilizing bath may be removed.

The washing and stabilizing treatment time of the present invention is usually 20 seconds to 10 minutes, preferably 20 seconds to 5 minutes, although it varies depending on the type of the photosensitive material and the processing conditions.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and accelerating the processing. For incorporation, it is preferable to use various precursors of color developing agents. For example, U.S. Pat.
Indoaniline compounds described in No. 7, No. 3,342,599,
Research Disclosure 14850 and Schiff base type compounds described in 15159, aldol compounds described in 13924, metal salt complexes described in US Pat. No. 3,719,492,
Starting with the urethane compounds described in JP-A-53-135628, JP-A-56-6235, JP-A-56-16133 and JP-A-56-59232
No. 56-67842, No. 56-83734, No. 56-83735,
56-83736, 56-89735, 56-81837, 56
-54430, 56-106241, 56-107236, 57-9
Various salt type precursors described in 7531 and 57-83565 can be mentioned.

The silver halide color light-sensitive material of the present invention may contain various 1-phenyl-3-pyrazolidones in order to accelerate color development, if necessary. Typical compounds are JP-A-56-64339, JP-A-57-144547, and JP-A-57-21114.
No. 7, No. 58-50532, No. 58-50536, No. 58-50533,
58-50534, 58-50535 and 58-115438.

The various treatment liquids in the present invention are used at 10 ° C to 50 ° C. A temperature of 33 ° C to 38 ° C is standard, but it is possible to raise the temperature to accelerate the treatment and shorten the treatment time, and conversely to lower the temperature to improve the image quality and improve the stability of the treatment liquid. it can. 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.

If necessary, a heater, a temperature sensor, a liquid level sensor, a circulation pump, a filter, a floating pig, a squeegee, etc. may be provided in each treatment bath.

In addition, in the case of continuous processing, a constant finish can be obtained by using a replenisher of each processing solution to prevent the composition of the solution from varying. The replenishment amount can be reduced to half or less than the standard replenishment amount for cost reduction.

(Examples) Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to these Examples.

Example-1 A multilayer color light-sensitive material sample comprising each layer having the following composition was prepared on a polyethylene terephthalate film support.

First layer: Anti-halation layer Gelatin layer containing black colloidal silver Second layer: Intermediate layer Gelatin layer containing emulsified dispersion of 2,5-di-t-octylhydroquinone Third layer: First red-sensitive emulsion layer Iodour Silver halide emulsion (silver iodide; 5 mol%) Silver coating amount: 1.6 g / m ² Sensitizing dye I: 4.5 × 10 ^-4 mol Sensitizing dye II: 1 mol of silver 1.5 × 10 ^-4 moles of coupler to silver 1 mole coupler EX-1 ..0.03 moles to 1 mole of silver coupler EX-3 ..0.003 moles to 1 mole of silver 4th layer; second red-sensitive emulsion layer Silver iodobromide emulsion (silver iodide; 10 mol%) ... Silver coating amount 1.4 g / m ² Sensitizing dye I: 3 × 10 ^-4 mol sensitizing dye per 1 mol of silver II ・ ・ ・ ・ ・ 1 × 10 ^-4 mol Coupler EX-1 for 1 mol of silver 0.002 mol Coupler EX-2 for 1 mol of silver Coupler EX-3 for 0.02 mol of 1 mol of silver ..To 1 mol of silver To 0.0016 mol fifth layer; sixth layer same as the intermediate layer a second layer; first green-sensitive emulsion layer Silver iodobromide emulsion (silver iodide: 6 mol%) ... silver coverage 1.8 g / m ² Sensitizing dye III ・ ・ ・ 5 × 10 ^-4 mol per 1 mol of silver Sensitizing dye IV ・ ・ ・ 2 × 10 ^-4 mol per mol of silver Coupler EX-4 ・ ・ Silver 0.05 mol to 1 mol Coupler EX-5 .. 0.008 mol to 1 mol silver Coupler EX-9 .. 0.0015 mol to 1 mol silver 7th layer; second green sensitive emulsion layer Silver iodobromide emulsion (Silver iodide; 8 mol%) ... Silver coating amount 1.3 g / m ² Sensitizing dye III: 3 × 10 ^-4 mol Sensitizing dye IV: 1 mol of silver・ 1.2 × 10 ^-4 mol coupler EX-7 for 1 mol silver ・ ・ 0.017 mol coupler EX-6 for 1 mol silver ・ ・ 0.003 mol for 1 mol silver 8th layer; yellow filter layer gelatin aqueous solution Yellow colloidal silver and 2,5-di Gelatin layer ninth layer comprising a emulsified dispersion of t- octyl hydroquinone; first blue-sensitive emulsion layer Silver iodobromide emulsion (silver iodide: 6 mol%) ----- silver coverage 0.7 g / m ² Coupler EX-8 ..0.25 mol to 1 mol of silver Coupler EX-9 ..0.015 mol to 1 mol of silver 10th layer; second blue-sensitive emulsion layer Silver iodobromide (silver iodide; 6 mol%) ) Silver coating amount 0.6 g / m ² coupler EX-8 .. 0.06 mol per 1 mol silver 11th layer; first protective layer silver iodobromide (silver iodide 1 mol%, average grain Diameter 0.07μ) ...
-Silver coating amount 0.5 g / m ² Gelatin layer containing emulsified dispersion of UV absorber UV-1 12th layer; 2nd protective layer A gelatin layer containing polymethylmethanoacrylate particles (diameter about 1.5μ) was coated.

In addition to the above composition, a gelatin hardening agent H-1 and a surfactant were added to each layer. The sample manufactured as described above was designated as Sample 101.

Preparation of Samples 102 to 111 Table 1 shows coupler EX-9 of the low green-sensitive emulsion layer of Sample 101.
The sample was prepared in the same manner as the sample 101 except that the above was changed.

When the samples 101 to 111 were subjected to a wet exposure with white light and the processing described later was performed, almost the same sensitivity and gradation were obtained. The sharpness of the green-sensitive layer of these samples was evaluated using a conventional MTF value.

The structural formulas of the compounds used are as follows.

Compound used to make the sample Development processing was carried out at 38 ° C. according to the following processing steps.

Color development 2 minutes 45 seconds Bleach 6 minutes 30 seconds Water washing 2 minutes 10 seconds Settling 4 minutes 20 seconds Water washing 3 minutes 15 seconds Stability 1 minute 05 seconds The treatment liquid composition used in each step is as follows. It was

Color developer Diethylenetriaminepentaacetic acid 1.0g 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0g Sodium sulfite 4.0g Potassium carbonate 30.0g Potassium bromide 1.4g Potassium iodide 1.3mg Hydroxylamine sulfate 2.4g 4- (N- Ethyl-N-β-hydroxyethylamino)
-2-Methylaniline sulfate 4.5g Add water 1.0l pH10.0 Bleaching solution Ethylenediaminetetraacetic acid ferric ammonium salt 100.0g Ethylenediaminetetraacetic acid disodium salt 10.0g Ammonium bromide 150.0g Ammonium nitrate 10.0g Add water 1.0l pH6.0 Fixer Ethylenediaminetetraacetic acid disodium salt 1.0g Sodium sulfite 4.0g Ammonium thiosulfate aqueous solution (70%) 175.0ml Sodium bisulfite 4.6g Water is added 1.0l pH6.6 Stabilizer Formalin (40%) 2.0 ml Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization ≈10) 0.3 g Water was added and 1.0 l The MTF values of 4 and 40 green-sensitive layers per 1 mm of the obtained sample were measured. The results are shown in Table-1.

From Table 1, it can be seen that the MTF value of the coupler using the coupler of the present invention is significantly higher than that of the ordinary DIR coupler.

Example 2 On a subbed cellulose triacetate film support,
A sample 301, which is a multi-layer color light-sensitive material having the following composition, was prepared.

(Composition of photosensitive layer) The coating amount of silver halide and colloidal silver is silver.
The amount represented in units of g / m ^2, also couplers, moles per 1 mol of silver halide in the same layer for the amount for the additives and gelatin represented in units of g / m ^2, also the sensitizing dye Indicated by.

1st layer (anti-halation layer) Black colloidal silver ………… 0.2 Gelatin ………… 1.3 Colored coupler C-1 …… 0.06 UV absorber UV-1 …… 0.1 Same as UV-2 ………… 0.2 Dispersion oil Oil-1 …… 0.01 Dispersion oil Oil-2 …… 0.01 0.01 2nd layer (intermediate layer) Fine grain silver bromide (average particle size 0.07μ) …… 0.15 Gelatin ………… 1.0 Colored coupler C-2 …… 0.02 Dispersed oil Oil-1 …… 0.1 0.1 Third layer (first red-sensitive emulsion layer) Silver iodobromide emulsion (2 mol% silver iodide, average grain size 0.3 μm) ) ……
…… Silver 0.4 Gelatin ………… 0.6 Sensitizing dye Ia ………… 1.0 × 10 ^-4 Sensitizing dye IIa ………… 3.0 × 10 ^-4 Sensitizing dye IIIa ………… 1 × 10 ^-5 Coupler C-3 ………… 0.06 Coupler C-4 ………… 0.06 Coupler C-2 ………… 0.03 Coupler C-8 ………… 0.005 Dispersed oil Oil-1 ………… 0.03 Same as above Oil-3… … 0.012 Fourth layer (second red-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide 5 mol%, average grain size 0.5 µ)
…… 0.7 Sensitizing dye Ia ………… 1 × 10 ^-4 Sensitizing dye IIa ………… 3 × 10 ^-4 Sensitizing dye IIIa ………… 1 × 10 ^-5 Coupler C-3 ………… 0.24 Coupler C-4 …… 0.24 Coupler C-2 …… 0.10 Dispersion oil Oil-1 …… 0.15 Same as above Oil-3 …… 0.02 Fifth layer (third red-sensitive emulsion layer) Iodine Silver bromide emulsion (silver iodide 10 mol%, average grain size 0.7μ)
…… Silver 1.0 Gelatin ………… 1.0 Sensitizing dye Ia ………… 1 × 10 ^-4 Sensitizing dye IIa ………… 3 × 10 ^-4 Sensitizing dye IIIa ………… 1 × 10 ^-5 Coupler C-6 ………… 0.05 Coupler C-7 ………… 0.1 Coupler C-2 ………… 0.05 Dispersed oil Oil-1 ………… 0.01 Same as above Oil-2 ………… 0.05 6th layer (intermediate) Layer) Gelatin …… 1.0 Compound Cpd-A ………… 0.03 Dispersion oil Oil-1 ………… 0.05 Seventh layer (first green emulsion layer) Silver iodobromide emulsifier (silver iodide 4 mol%) , Average particle size 0.3μ) ...
……… 0.30 Sensitizing dye IVa ………… 5 × 10 ^-4 Sensitizing dye VIa ………… 0.3 × 10 ^-4 Sensitizing dye Va ………… 2 × 10 ^-4 Gelatin ………… 1.0 Coupler C-9 …… 0.2 Coupler of the present invention (14) …… 0.03 Coupler C-1 …… 0.03 Dispersion oil Oil-1 …… 0.5 0.5 8th layer (2nd green-sensitive emulsion layer) Silver iodobromide emulsion (5 mol% silver iodide, average grain size 0.5μ)
…… 0.4 Sensitizing dye IVa ………… 5 × 10 ^-4 Sensitizing dye Va ………… 2 × 10 ^-4 Sensitizing dye VIa ………… 0.3 × 10 ^-4 Coupler C-9 ………… 0.25 Coupler C-1 …… 0.03 Coupler C-10 …… 0.015 Coupler of the present invention (14) …… 0.01 Dispersed oil Oil-1 …… 0.2 0.2 Ninth layer (third green-sensitive emulsion) Layer) Silver iodobromide emulsion (silver iodide 6 mol%, average grain size 0.7 μ) ..
...... Silver 0.85 Gelatin ………… 1.0 Sensitizing dye VIIa ………… 3.5 × 10 ^-4 Sensitizing dye VIIIa ………… 1.4 × 10 ^-4 Coupler C-11 ………… 0.01 Coupler C-12… ………… 0.03 Coupler C-13 ………… 0.20 Coupler C-1 ………… 0.02 Coupler of the present invention (8) ………… 0.02 Dispersion oil Oil-1 ………… 0.20 Same as above Oil-2 …… …… 0.05 10th layer (yellow filter layer) Gelatin ………… 1.2 Yellow colloidal silver ………… 0.08 Compound Cpd-B ………… 0.1 Dispersion oil Oil-1 ………… 0.3 11th layer (1st layer) Blue-sensitive emulsion layer) Monodisperse silver iodobromide emulsion (silver iodide 4 mol%, average grain size 0.3)
μ) Silver 0.4 Gelatin …… 1.0 Sensitizing dye IXa …… 2 × 10 ^-4 Coupler C-14 …… 0.9 Coupler of the present invention (15) ………… 0.07 Dispersion oil Oil-1 ………… 0.2 12th layer (2nd blue-sensitive emulsion layer) Silver iodobromide (Silver iodide 10 mol%, average grain size 1.5μ) …………
Silver 0.5 Gelatin …… 0.6 Sensitizing dye IXa ………… 1 × 10 ^-4 Coupler C-14 ………… 0.25 Dispersion oil Oil-1 …… 0.07 13th layer (1st protective layer) Gelatin ………… 0.8 UV absorber UV-1 ………… 0.1 Same as UV-2 ………… 0.2 Dispersion oil Oil-1 ………… 0.01 Dispersion oil Oil-2 ………… 0.01 14th layer (No. 2 Protective layer) Fine silver bromide (average particle size 0.07μ) ………… 0.5 Gelatin ………… 0.45 Polymethylmethacrylate particles (diameter 1.5μ) …………
0.2 Hardener H-1 ………… 0.4 Formaldehyde scavenger S-1 ………… 0.5 Formaldehyde scavenger S-2 ………… 0.5 In addition to the above components, each layer is coated with a surfactant. It was added as an auxiliary agent.

Next, the chemical structural formulas or chemical names of the compounds used in the examples are described.

Oil-1 Tricresyl phosphate Oil-2 Dibutyl phthalate Oil-3 Bis (2-ethylhexyl) phthalate The sample 301 thus prepared was cut into a width of 35 m / m, a standard subject was photographed outdoors, and the following processing was performed by an automatic processor.

In the above treatment step, the washing with water was a countercurrent washing method from to. Next, the composition of each processing liquid will be described.

<Color developer> The composition of the mother liquor and the replenisher of the color developer was as follows.

The pH was adjusted with potassium hydroxide or sulfuric acid.

Using the developed negative film thus obtained, a color print was prepared by printing on Fuji Color High-Tech 12 Paper (manufactured by Fuji Photo Film Co., Ltd.). There was little color turbidity, the color was vivid, and the color reproducibility was excellent.

Claims (1)

[Claims] 1. A color photographic light-sensitive material containing a compound represented by the following general formula. General formula In the formula, Z ₁ , Z ₂ and Z ₄ represent a —CO— group or a —SO ₂ — group, Z ₃ represents —N (R ₅ ) —, a sulfur atom, an oxygen atom, —C
_{(= N-R 5) -} , - C (R 9) = C (R 10) - or -C (R ₉₎ =
N-, or a divalent group formed by combining any two of these, -N in the general formula _{= C (R 4) b -} , (Z
₂ ) _c , (Z ₄ ) _d and CH-PDI represent an organic atomic group for forming a 5-membered ring or a 6-membered ring, and PDI is a group which is released after the compound reacts with an oxidized product of a developing agent. Yes,
After elimination, it represents a group which forms a development inhibitor through a reaction with an oxidized product of a developing agent, and a, b, c and d each represent 0 or 1. R ₄ , R ₅ , R ₉ and R ₁₀ represent a hydrogen atom or a substituent. Furthermore, in the above general formula, When the ring represented by is a 5-membered ring, a represents 0,
c represents 1, b and d represent 0 or 1. In addition, when the above-mentioned ring is a 6-membered ring, the case where a benzene ring can be formed by tautomerism is excluded.