JPS63281160A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve the sharpness and color reproducibility of the titled material by incorporating a two equivalent magenta polymer coupler in a green sensitive silver halide emulsion layer, and a specified compd. in a red sensitive silver halide emulsion layer and/or a blue sensitive silver halide emulsion layer, respectively. CONSTITUTION:The titled material comprises one or more layers of the red sensitive silver halide emulsion layer, the green sensitive silver halide emulsion layer and the blue sensitive silver halide emulsion layer mounted on a supporting body, and at least one kind of the two equivalent magenta polymer coupler is incorporated in at least one layer of the green sensitive silver halide emulsion layer, and the compd. shown by formula I is incorporated in at least one layer of the red sensitive silver halide emulsion layer and/or at least one layer of the blue sensitive silver halide emulsion layer. In formula I, A is a coupler residual group, R1 is an aromatic residual group having a hydroxy group at 2 or 4 position, counting from the bonding position of oxygen atom, Z is sulfur or oxygen atom, R2 is 2-7C substituting group, (n) is an integer of 1 or 2. Thus, the sharpness and the color reproducibility of the titled material are improved.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a silver halide color photographic light-sensitive material with excellent sharpness and color reproducibility. The present invention relates to a silver-no-rodanide color photographic light-sensitive material that achieves the above-mentioned improved performance by a novel development inhibitor-releasing compound that can be used in the present invention.

(Prior Art) Many studies have been conducted on color photographic materials for the purpose of improving sharpness and color reproducibility. One such technology is couplers that release development inhibitors. It is commonly referred to as a DIR coupler.

In recent years, useful IR couplers have been disclosed, for example, in U.S. Pat.
, 421,845, 4,438.193, and 4,477.563.

These known DIR couplers exhibit some desirable performance, but have been found to be limiting in their need for further performance improvements.

So recently, from the coupler's coupling,
Couplers that release photographically useful groups through a redox reaction with an oxidized developing agent have been disclosed in JP-A Nos. 60-185950, 61-233741, 61-238057, and 6.
No. 1-251847, No. 61-251848, No. 62
No. 24252 and No. 62-56962, etc., and these have significantly improved image quality such as sharpness, graininess, and color reproducibility.

However, the most important development inhibitor in these couplers, 5-mercapto-1-phenyltetrazole, is expensive, and these derivatives (e.g. 5-mercapto-1-phenyltetrazole) are expensive.
-Chlorothio-1-phenyltetrazole, etc.) has been found to have significant restrictions on coupler manufacturing conditions due to problems such as poor thermal stability, and is therefore inferior in manufacturing suitability. However, the 2-mercapto-1,3,4-thiadiazole derivatives and 2-mercapto-1,3゜4 of the present invention
- It has been found that oxadiazole derivatives are cheaper and have better thermal stability than 5-mercapto-1-phenyltetrazole, and are therefore more suitable for production.0 Compounds similar to the compounds of the present invention Already disclosed. For example, JP-A-60-185950 (Exemplary Compound (2)
, (25) and (27)), JP-A-61-251847
No. (Exemplary Compounds (1), (28)) and JP-A-61-
No. 251848 (exemplified compounds (1) and (28)) contains a compound that releases 2-mercapto-5-methylthio-1,3,4-thiadiazole, and JP-A-62-242
No. 52 (exemplified compound (42)) contains 2-mercapto-5
-Methyl-1,3,4-thiadiazole-releasing compounds have been disclosed, but these compounds have poor solubility in organic solvents, resulting in poor dispersion and not only failing to obtain the desired photographic performance, but also causing coating failure. It was also the cause.

In addition, in the case of the exemplified compound (18) described in JP-A-60-185950, which uses the same 2-mercapto-1,3,4-thiadiazole as a development inhibitor, the development inhibitor has poor solubility in the developer. Therefore, it did not function sufficiently as a development inhibitor, and therefore image quality was not sufficiently improved. In addition, these 2-mercapto-1,3,4-thiadiazole derivatives have the disadvantage that, because they are not deactivated in the developer, they accumulate in the developer and deteriorate its performance.

Further, in JP-A No. 62-24252, a compound included in the compounds of the present invention is disclosed as an exemplary compound (41).
The couplers used together were different, and the sharpness and color reproducibility were not significantly improved as in the present invention.

On the other hand, attempts have been made to use polymer couplers, particularly 2-equivalent magenta polymer couplers, to reduce emulsion film thickness and improve sharpness.
No. 352, No. 61-189538, No. 61-23245
No. 5 and No. 62-54260. It is true that the sharpness has been significantly improved by these methods, but it has become clear that there is a problem in that the glabellar effect, especially the glabellar effect on the green-sensitive layer, is significantly reduced and color reproducibility is deteriorated.

Furthermore, an attempt has been made in JP-A-62-56962 to reduce the emulsion film thickness and further improve the sharpness by using the derivative compound of the present invention and a polymer coupler.

However, in this patent, there is only an example of a compound that releases only a mercaptotetrazole derivative with low synthesis suitability and insufficient solubility, and also does not clarify the problem of using a 2-equivalent magenta polymer coupler.

(Problems to be Solved by the Invention) The first object of the present invention is to solve the problem of using halogen with excellent color reproducibility even when using a 2-equivalent magenta polymer coupler which has the effect of improving sharpness but deteriorates color reproducibility. The second objective is to provide a silver halide color photographic light-sensitive material that is inexpensive, has excellent manufacturing suitability, and contains a development inhibitor-releasing compound that has excellent solubility in organic solvents. The third object is to provide a silver halide color photographic material that does not cause deterioration in the performance of the developer even when a large amount of the material is developed.

(Means for Solving the Problems) These objects of the present invention are as follows (11 and/or (2))
This was achieved using the silver halide color photographic material shown in .

(1) A support has a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a blue-sensitive silver halide emulsion layer each having an IN or more, and at least IN of the green-sensitive silver halide emulsion layer. contains at least one 2-equivalent magenta polymer coupler, and at least one layer of the red-sensitive silver halide emulsion layer and/or at least IN of the blue-sensitive silver halide emulsion layer is represented by the following general formula [I]. A silver halide color photographic light-sensitive material, characterized in that it contains the compound shown below.

In the general formula [I] -S formula [I1, A represents a coupler residue, and R
1 represents an aromatic residue having a hydroxyl group at the 2nd or 4th position counting from the oxygen atom bonding position, Z represents a sulfur atom or an oxygen atom, R1 represents a substituent having 2 to 7 carbon atoms, n represents an integer of 1 or 2.

(2) A patented silver color photographic material characterized in that in the general formula [I1, the substituent represented by R2 has at least one ester bond (-Go-).

General formula used in the present invention [! The coupler represented by ] will be described in detail below.

A represents a coupler residue, and for example, the following known ones can be used. Yellow coupler residues (e.g., open-chain ketomethylene type coupler residues), magenta coupler residues (e.g., 5-pyrazolone type, virazoloimidazole type (virazolotriazole type, etc.) coupler residues), cyan coupler residues (e.g., phenol type, Naphthol type coupler residues), colorless coupler residues (e.g. indanone type, acetophenone type coupler residues, etc.), or U.S. Pat.
No. 4,171,223, No. 4.

Examples include coupler residues described in 226, 934 and the like.

R. The group represented by is preferably a benzene ring, and 2
In addition to having a hydroxyl group at the position or 4-position (based on the oxygen atom bonding position), it may also have one or more substituents. Preferred substituents include R, monogroup, R. OCO group, R4NGO group.

S R3 So□ one group, R4 NSOx one group. N=C- group.

■ Rs. Halogen atom, R4 Co group. One R40 unit.

R3 So□N one group, R, CON one group. R. S-group.

I R a R 4 R s R & R s R a R s R & get.
Here, R represents an aliphatic group, an aromatic group, or a heterocyclic group, and Ra, Rs, and R represent an aliphatic group, an aromatic group, or a heterocyclic group, respectively.
Represents a heterocyclic group or a hydrogen atom.

In the above, the aliphatic group is a saturated or unsaturated, chain or cyclic, straight chain or branched, substituted or unsubstituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms. Examples include methyl, ethyl, propyl, isopropyl, butyl, (1)-butyl, (1)
)-butyl group, (1)-amyl group, cyclohexyl group,
can be mentioned.

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

A heterocyclic group is a preferably 3- to 8-membered W-substituted or unsubstituted heterocyclic ring having 1 to 20 carbon atoms, preferably 1 to 7 carbon atoms, and the hetero atom selected from a nitrogen atom, an oxygen atom, or a sulfur atom. It is the basis.

Representative examples of the heterocyclic group include 2-pyridyl group, 2-chenyl group, 2-furyl group, 2-imidazolyl group, pyrrolidino group, 2-pyrimidinyl group, 1-imidazolyl group, succinimide group, phthalimide group, 1 , 3,4-thiadiazol-2-yl group, or tri7zolyl group.

When the aliphatic hydrocarbon group, aromatic group and heterocyclic group have a substituent, typical substituents include an aliphatic oxy group, an aliphatic thio group, an aliphatic carbonyloxy group, an aromatic carbonyloxy group, Examples thereof include a halogen atom, a cyano group, an aliphatic oxycarbonyl group, an aromatic oxycarbonyl group, and a heterocyclic group. The meanings of the aliphatic group, aromatic group and heterocyclic group herein are the same as explained above.

Specific examples of R include the following groups.

The * mark represents the bonding position with the oxygen atom in the general formula [I1, and the * mark represents the bonding position with the sulfur atom.

Representative examples of the group represented by Rt in the general formula [I1 include an R1- group and a RIS- group.

Rff Co-N- group, R,0CON- group.

Rs　　　　　　　　Rs R, so, N- group, RAN- group, R10- group.

Rs Rq R, NCON- group or Rff CO3- group may be mentioned.
9R111 will be. Here, R1 represents an aliphatic group, an aromatic group or a heterocyclic group, and Re, Re and R3° each represent an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom. aliphatic group,
Aromatic and heterocyclic groups have the same meanings as previously explained. However, the number of carbon atoms in Rt is 2 to 7,
Preferably it is 3-5.

In addition, at least one ester bond (-Co
-) is preferred, and a particularly preferred group among these is represented by the following general formula [■].

General formula [■] R++ O I II S (C)--COR+ s R1D In the general formula [■], R11 and Rff each independently represent a hydrogen atom or an aliphatic group having 1 to 4 carbon atoms, and R12 represents an aliphatic group having 1 to 5 carbon atoms, m
represents an integer of 1 to 3; however, the number of carbon atoms in the group represented by general formula [II] is 2 to 7, preferably 3 to 3.
When there is a plurality of 0m that is 5, Ro, R, and t may be the same or different.

Specific examples of R1 include the following groups. The mark * represents the bonding position in the general formula [I1.

Monkey 5CsHq * 5CaH * *
5CaHe(i) Book 5C4H9(S)*-3
CHtCO, CHs *-5CllzCHzCOx
CIIz *-3CHCO*C) Is *-C
4H9(t)■ CHs * 5CHtCOtCxHs * 5CHtC
Hzα14CJs Main-3CHCOt CHsC dew Hs *-QCs H, *-3CHgCOO-CJt n)
*-3CHCO,C*HsCH.

*-3CH*C00CJ*(n) *-3CHt
COOIJItCll(CHs)z *-3CHt
CH*O11tts *-3CCOOCHs *-NHCm Hs
Book-NHCm)1? CHs *NHCOCFs *-NHCOCs F
t*-NH3OtCFs*-5CHtCO
OCHtCHtOCHs * -5CHxC
In the general formula [I] of OOCH*CONHCHs, Z represents a sulfur atom or an oxygen atom, with a sulfur atom being more preferred.

In general formula [I], n represents an integer of 1 or 2, but 1 is more preferable.

When A represents a coupler residue in general formula [I], A
Preferred examples are the following general formulas (Cp-1) and (Cp-2)
, (Cp-3), (Cp-4), (Cp-5), (Cp
-6), (Cp-7), (Cp-8) or (Cp-9
) is the coupler residue represented by These couplers are preferred because of their high coupling speed.

General formula (Cp-1) General formula (Cp-2) General formula (Cp-3) General formula (cp-4) M '0
)＜S? General formula (Cp-5) General formula (Cp-6) General formula (C
p-7) General formula (Cp-8) General formula (Cp-
9) General formula (Cp-10) In the above formula, the free bond derived from the coupling position represents the bonding position of the coupling-off group.

In the above formula, R5l+ Rsx, R531Rsa
+Rss+Rs-+Rs? +Rs@+R
3el R&@l R1+ Rhz or R63
If it contains a diffusion-resistant group, it is selected so that the total number of carbon atoms is 8 to 40, preferably 10 to 30; otherwise, the total number of carbon atoms is preferably 15 or less, bis type, telomer type. Alternatively, in the case of a polymer type coupler, any of the above substituents represents a divalent group and connects repeating units. In this case, the range of carbon numbers may be outside the specified range.

RSl"RSl d and e will be explained in detail below. In the following, R41 represents an aliphatic group, an aromatic group or a heterocyclic group, R4! represents an aromatic group or a heterocyclic group, R43+ R44 and R4S are hydrogen Represents an atom, aliphatic group, aromatic group or heterocyclic group.

Rs+ has the same meaning as R41 @R%! and R5
3 each represents the same meaning as R41, RSd is R□R4
3R4 co-RarSOzN- group, R413- group, Ra5O- group 1R
43R44R43 eR5S representing a - group or NmiC- group represents a group having the same meaning as R41 sR8 & and R5? are each Raff
A group having the same meaning as the group, R41S- group, Ra*O- group, R,
, C0N- group, R41N W, R,, NC0N- group,
1 1 1 l R43Ra3Raa Ras or I? ,,5ON- group *R51 represents a group with the same meaning as Ro, R3, represents a group with the same meaning as R41,
R4U R43 Ra+5OxN- group, R42NCON- group, R42R4
4R45 R44R4! d represents a halogen atom or a Ra IN- group; d represents 4x O to 3; when d is a plurality of R59s, a plurality of R59s represent the same substituent or different substituents;

Further, each Rsq may become a divalent group and connect to form a cyclic structure. Examples of divalent groups for forming a cyclic structure include R43R4s 4m an integer from 4 to 4, g an integer from 0 to 20, s representing each
R&. represents a group with the same meaning as R41 eR&1 is R4
eR&t, which represents a group with the same meaning as 1, is a group with the same meaning as R41, R4I CON H- group, R,,0CONHR,
, R,5 Rap R4S represents a halogen atom or R41N- group. Ruff is a group with the same meaning as R41, R43CON- group, R44R4
4 RnzNSOt- group, R4+5Ot- group, Rn*OCO
One R4! O-S Represents an os- group, a halogen atom, a nitro group, a cyano group or an R55CO- group. e represents an integer from 0 to 4, and when there are multiple Rhz or Ru3, each represents the same or different.

In the above, the aliphatic group is a saturated or unsaturated, chain or cyclic, straight chain or branched, substituted or unsubstituted aliphatic hydrocarbon group having 1 to 32 carbon atoms, preferably 1 to 22 carbon atoms. Examples include methyl, ethyl, propyl, isopropyl, butyl, (1)-butyl, (
i)-Butyl group, ([)-amyl group, hexyl group, cyclohexyl group, 2-ethylhexyl group, octyl group, 1
．． 1.3°3-Tetramethylbutyl group, decyl group, dodecyl group, hexadecyl group, or octadecyl group.

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

A heterocyclic group is a substituted or unsubstituted heterocyclic group having 1 to 20 carbon atoms, preferably 1 to 7 carbon atoms, preferably a 3- to 8-membered ring selected from a nitrogen atom, an oxygen atom, or a sulfur atom. It is.

Representative examples of the heterocyclic group include 2-pyridyl group, 4-pyridyl group, 2-chenyl group, 2-furyl group, 2-imidazolyl group, pyrazinyl group, 2-pyrimidinyl group, 1-imidazolyl group, l- Indolyl group, phthalimide group, 1
, 3.4-thiadiazol-2-yl group, benzoxazol-2-yl group, 2-quinolyl group, 2.4-dioxo-1,3-imidazolidin-5-yl group, 2.4-dioxo-1 , 3-imidazolidin-3-yl group, succinimide group, phthalimide group, 1.2.4-triazol-2-yl group or l-pyrazolyl group.

When the aliphatic hydrocarbon group, aromatic group and heterocyclic group have a substituent, typical substituents include halogen atom, R4,〇- group, R,6S- group, R4@R4
1R4? Rat R4 R41R4t R,, COO- group, R,, oso, - group, cyano group, or nitro group. R4& represents an aliphatic group, an aromatic group, or a heterocyclic group;

R4 and Raq each represent an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom, and the meanings of aliphatic group, aromatic group or heterocyclic group are the same as defined above.

Next, preferred ranges of R51-R1, d and e will be explained.

R51 is preferably an aliphatic group or an aromatic group.

R5! +Rss and I'2ss are preferably aromatic groups.

R54 is Ra + CON H- group, or R41N-
groups are preferred mR8 & and R8? is an aliphatic group, R,
O- group or R41S- group is preferred *R5I is preferably an aliphatic group or aromatic group. In general formula (Cp-6), R3 is a chloro atom, an aliphatic group or R,, C
0NH- group is preferred, d is preferably 1 or 2, R
4, is preferably an aromatic group. In general formula (Cp-7), Ra9 is preferably R,, CONH- group, general formula (C
In p-7), d is preferably 1, R1 is preferably an aliphatic group or aromatic group, e in general formula (Cp-8) is preferably 0 or 1, R12 is R,,0C
ONH- group, R,, C0NH- group, or R4+5Oz
NH- group is preferable, and the substitution position thereof is preferably the 5-position of the naphthol ring. In general formula (Cp-9), R1 is Ra + CON H- group, Ra IS Ot N
H- group, Ra + N S Oz- group, Ra + S
An O group, a R4IN C0Ra3R43 group, a nitro group or a cyano group are preferred.

In the general formula (Cp-10), R1 is RhxOCO- group, Ra5CO- group or R4CoNC○
One unit is preferred.

Next, a typical example of Rs r "" R62 will be explained.

R8I includes (1) -butyl group, 4-methoxyphenyl group, phenyl group, 3-(2-(2,4-di-t-
Examples include amylphenoxy)butanamido)phenyl group, 4-octadecyloxyphenyl group, or methyl group *R5! and Rsa as 2-chloro-5-dodecyloxycarbonylphenyl group, 2-chloro-5-hexadecylsulfonamidophenyl group, 2-chloro-5
-tetradecanamidophenyl group, 2-chloro-5-(
4-(2,4-di-t-amylphenoxy)butanamido) phenyl group, 2-chloro-5-(2-(2゜4-di-t-amylphenoxy)butanamido) phenyl group,
2-methoxyphenyl group, 2-methoxy-5-tetradecyloxycarbonylphenyl group, 2-chloro-5-(
l-ethoxycarbonylethoxycarbonyl) phenyl group, 2-pyridyl group, 2-chloro-5-octyloxycarbonylphenyl group, 2,4-dichlorophenyl group,
Examples include 2-chloro-5-(1-dodecyloxycarbonylethoxycarbonyl)phenyl group, 2-chlorophenyl group, and 2-ethoxyphenyl group.

As Ra4, 3-(2-(2,4-di-t-amylphenoxy)butanamido)benzamide group, 3-
(4-(2,4-di-t-amylphenoxy)butanamido-)benzamide group, 2-chloro-5-tetradecanamidoanilino group, 5-(2,4-di-t-amylphenoxyacetamide)benzamide group , 2-chloro-
5-dodecenylsuccinimide anilino group, 2-chloro-5-(2-(3-t-butyl-4-hydroxyphenoxy)tetradecanamido)anilino group, 2,2-dimethylpropanimide group, 2-( 3-pentadecylphenoxy)butanamide group, pyrrolidino group or N, N
-dibutylamino group. As R55, 2
, 4.6-) dichlorophenyl group, 2-chlorophenyl group, 2.5-dichlorophenyl group, 2.3-dichlorophenyl i, 2.6-dichloro-4-methoxyphenyl group, 4- (2-(2,4- di-t-amylphenoxy)
butanamido) phenyl group or 2,6-dichloro-4
-methanesulfonylphenyl group is a preferred example.

R5& is a methyl group, an ethyl group, an isopropyl group,
Examples include methoxy group, ethoxy group, methylthio group, ethylthio group, 3-phenylureido group, 3-butylureido group, or 3-(2,4-di-t-amylphenoxy)propyl group *R1? The end is 3-(2,4-di-t-amylphenoxy)propyl group, 3-C4-
(2-(4-(4-hydroxyphenylsulfonyl)phenoxycotetradecanamido)phenyl]propyl group, methoxy group, ethoxy group, methylthio group, ethylthio group, methyl group, 1-methyl-2-(2-octyloxy- 5-[2-octyloxy-5-(1゜1.3.3-
Tetramethylbutyl)phenylsulfonamido]phenylsulfonamido)ethyl group, 3-[4-(4-dodecyloxyphenylsulfonamido)phenyl)propyl group, 1,1-dimethyl-2-(2-octyloxy-
Examples thereof include 5-(1,1°3.3-tetramethylbutyl)phenylsulfonamido)ethyl group and dodecylthio group. R51l is a 2-chlorophenyl group, a pentafluorophenyl group, a heptafluoropropyl group,
Examples include 1-(2,4-di-t-amylphenoxy)propyl group, 3-(2,4-di(-amylphenoxy)propyl group, 2,4-di-t-amylmethyl group, or furyl group) .R5 is a chloro atom, a methyl group,
Ethyl group, propyl group, butyl group, isopropyl group, 2
- (2,4-di-t-amylphenoxy)butanamide group, 2-(2,4-di-t-amylphenoxy)hexanamide group, 2-(2,4-di-t-octylphenoxy)octanamide group group, 2-(2-chlorophenoxy)tetradecanamide group, 2,2-dimethylpropanamide group, 2-[4-(4-hydroxyphenylsulfonyl)phenoxy)tetradecanamide group, or 2
- (2-(2,4-di-t-amylphenoxyacetamido)phenoxy)butanamide group. R
1° is 4-cyanophenyl group, 2-cyanophenyl group.

4-butylsulfonylphenyl group, 4-propylsulfonylphenyl group, 4-ethoxycarbonylphenyl group,
4-N,N-diethylsulfamoylphenyl group, 3,
Examples include 4-dichlorophenyl group or 3-methoxycarbonylphenyl group. R1 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-
Dodecyloxyprobyl group, 2-tetradecyloxyphenyl group, t-butyl group, 2-(2-hexyldecyloxy)phenyl group, 2-methoxy-5-dodecyloxycarbonylphenyl group, 2-butoxyphenyl group, or A 1-naphthyl group is mentioned. R1 is an isobutyloxycarbonylamino group, an ethoxycarbonylamino group, a phenylsulfonylamino group, a methanesulfonamide group, a butanesulfonamide group, a 4-methylbenzenesulfonamide group, a benzamide group, a trifluoroacetamide group, and a 3-phenylureido group. , a butoxycarbonylamino group, or an acetamido group.
&2 is a 2.4-di[-amylphenoxyacetamide group, 2-(2゜4-di-t-amylphenoxy)butanamide group, hexadecylsulfonamide group, N
-methyl-N-octadecylsulfamoyl group, N,
N-dioctylsulfamoyl group, dodecyloxycarbonyl group, chloro atom, fluorine atom, nitro group, cyano group, N-3-(2,4-di-t-amylphenoxy)
Propylsulfamoyl M, N-(4-(2,4-di-
Examples thereof include t-amylphenoxy)butyl)carbamoyl group, methanesulfonyl group, and hexadecylsulfonyl group.

Specific examples of compounds represented by the general formula [IF used in the present invention are shown below, but the present invention is not limited thereto.

(Compound example) ■ CH.

Koshi4 r1 drop (1) (5)
0H3Lnt and I'll tyuishi r15 (9)
OH
SshiaFlq (15) 0H(
16) OH5CH
m CH 寞 CO*CHs し g H SL;H! (,,H(shiNs)! 5CHx Cot CHs Ntll,,suNIIL,t!s goshisl'1v(n) The compound represented by the general formula [I] of the present invention is described in, for example, JP-A-60-185950. It can be synthesized by the synthesis method described in No. 61-233741 and No. 61-238047. Synthesis examples of the compounds of the present invention are shown below.

(Synthesis example) Synthesis of exemplified compound (3) Exemplary compound (3) was synthesized according to the following scheme.

Takumi J'' Yoshiharu Ushishi (Synthesis of Compounds) Dissolve 12.7g of the compound and 26.9g of the potassium salt in 100ml of dimethylformamide, 1
The 0 reaction solution reacted at 30° C. for 2 hours was neutralized with diluted hydrochloric acid water, and 200 ml of methylol was added dropwise. By filtering the precipitated crystals, 22.3 g of the compound was obtained.

(Synthesis of compound sample) 22.3g of compound sample, 200ml of ethanol, 10ml of water
Add 12.4 mjl of potassium hydroxide to this.
The reaction mixture was refluxed for 2 hours to make it acidic, and the product was extracted with ethyl acetate.

After washing with water, it was dried with anhydrous sodium sulfate. After concentrating the extract under reduced pressure, anhydrous butafluorobutanoic acid and 1
8.5 g was added dropwise at room temperature. After stirring for 1 hour, the organic layer was washed with water and further washed with diluted sodium chloride water. The solvent was distilled off under reduced pressure, and the obtained crude crystals of the compound were suspended in 100 ml of acetonitrile and filtered. After drying, 19.6 g of white crystals were obtained.

(Synthesis of Compound E) 19.6 g of Compound I, 15 g of iron powder, 1 g of ammonium chloride, 10 mj of water! , and isopropyl alcohol8
After adding 1 mJ of acetic acid and refluxing for 20 minutes, the reaction solution was filtered to remove iron powder.
The filtrate was concentrated under reduced pressure.

Furthermore, 100 ml of acetonitrile was added to this, and compound Jj, 9. og was added dropwise at 40°C. After stirring for 1 hour,
By filtering the precipitated crystals, compounds 1, 21.
2g was obtained.

(Synthesis based on the compound) 21.2 g of the compound, l, was mixed with 100 g of dimethylacetamide.
mff1 and added 5.4 thionyl chloride to it at 0°C.
g was added dropwise. After stirring for 30 minutes, the reaction solution was cooled to -10°C, and 50ml of a solution of 8.1g of propylamine in dimethylacetamide was added dropwise so as not to exceed 0°C.

After stirring for 2 hours, the reaction product was extracted with ethyl acetate, washed with water, and then the solvent was distilled off.

60 mj of acetic acid and 2 ml of hydrochloric acid were added to the obtained crude crystals, and the mixture was refluxed for 1 hour. After cooling, 120 ml of water was slowly added dropwise to the reaction solution to precipitate crystals.

After filtering the crystals, they were washed with acetonitrile,
12.9 g of white crystals of the compound were obtained.

(Synthesis of Exemplary Compound (3)) Compound: 12.9 g, 2-(2-methoxycarbonyl)ethylthio-5-chlorothio-1,3°4-thiadiazole, 17.4 g, and triphenylphosphine 4.2 g.
g was dissolved in 130 ml of tetrahydrofuran and refluxed for 2 hours.

The reaction product was extracted with ethyl acetate, washed with water, and then the solvent was distilled off. Further, crystallization was performed using chloroform and hexane to obtain exemplified compound +3), 10. 0 g was obtained. (
m, p, 218.0-219.0°C) Exemplary compound (25
) Synthesis of Exemplary Compound (25) was synthesized in substantially the same manner as the synthesis of Exemplary Compound (3). That is, in the above-mentioned method for synthesizing exemplified compound (3), 2-methoxycarbonylmethylthio-5-chlorothio-1 was used instead of 2-(2-methoxycarbonyl)ethylthio-5-chlorothio-1°3.4-thiadiazole. Exemplary compound (25) could be synthesized in exactly the same manner except that 3.4-thiadiazole was used. (mp, 208.0-209.0
°C) Synthesis of Exemplified Compound (6) Exemplified Compound (6) was synthesized in exactly the same manner as the method for synthesizing Exemplified Compound (3), except that the compound foot shown below was used instead of the compound base. We were able to. (
mp, 207.0-212.0°C) (Comparative Experimental Example) In order to demonstrate that the coupler of the present invention has excellent solubility in organic solvents, the solubility of the coupler in ethyl acetate was measured. That is, 2 ml of ethyl acetate was placed in a test tube that could be sealed tightly, kept at 25° C. in a thermostatic water bath, and 10 Qmg of coupler was added until it no longer dissolved. After the bottle was sealed tightly and allowed to stand for 2 weeks, the supernatant liquid was taken into a weighing bottle and weighed, and then the ethyl acetate was removed by evaporation on a hot plate at 80°C, and the solubility of the coupler was determined by weighing again. The solubility expressed in 1 weight fraction is summarized in Table 1.

Table 1 Exemplary compounds (2) described in JP-A-60-185950
Here, (32) and A and +11 in Table 1. +61
．． (33).

(34) and B each have a common structure other than the Rt group in the general formula [I1].

From Table 1, it can be seen that the solubility of the couplers of the present invention is clearly higher than that of the comparative examples, indicating that they are excellent in solubility.

The 2-equivalent magenta polymer coupler of the present invention has a repeating unit represented by the following general formula [■].

General formula [■] (CH*C) - "Qa (wherein R1 represents a hydrogen atom, a chlorine atom, or an alkyl group having 1 to 4 carbon atoms, and Qa represents an oxidized aromatic group 1
2 which can be coupled with grade amine developers to form dyes.
The repeating unit of the two-equivalent magenta coupler represented by the general formula [I1], which represents a group containing an equivalent magenta coupler residue, is more specifically represented by the general formula [I[I].

In the formula, R1 has the same meaning as defined in the general formula [I11]. D represents -000-5-CONR'-1 or a substituted or unsubstituted phenyl group, E represents a substituted or unsubstituted alkylene group, phenylene group or aralkylene group, and F represents -CONR'-1-NR' C0
NR'-1-NR' C00j, -NR' C0-2
-0CONR'-1-NR'-1-COO-1-OCO
-1-CO-1-0-1-SO, -1-NR'so.

- or -SO□NR'- Rl represents a hydrogen atom or a substituted or unsubstituted aliphatic group or aryl group. When two or more R's exist in the same molecule, they may be the same or different. , 1, m, and n represent O or 1, provided that 1. m and n are never 0 at the same time.

Q is the following general formula (IV), (V), (Vl), [■]
, [■], (EX) and (X) coupler residues of the two-equivalent magenta coupler (Ar, X-, R4-R
It is preferably a 5-pyrazolone represented by the general formula (TV), in which any part of Ith is bonded to the Ith group in the general formula (III).

General formula (IV) General formula (V) R.

General formula (Vl) H General formula [■] General formula (IX) General formula (X) λ i In the formula, Ar is a well-known type of substituent at the 1-position of the 2-pyrazolin-5-one coupler, such as an alkyl group, a substituent Alkyl group (e.g. haloalkyl such as fluoroalkyl, cyanoalkyl, benzylalkyl, etc.), aryl group or substituted aryl group [Substituents include alkyl group (e.g. methyl group, ethyl group, etc.), alkoxy group (e.g. methoxy group, ethoxy group) ), ryoroxy groups (e.g. phenyloxy groups, etc.), alkoxycarbonyl groups (
For example, methoxycarbonyl group), acylamino group (
acetylamino group), carbamoyl group, alkylcarbamoyl group (e.g. methylcarbamoyl group, ethylcarbonyl group, etc.), dialkylcarbamoyl group (e.g. dimethylcarbamoyl group), arylcarbamoyl group (e.g. phenylcarbamoyl group), alkylsulfonyl group (e.g. methyl sulfonyl group), arylsulfonyl group (e.g. phenylsulfonyl group), alkylsulfonamide group (e.g. methanesulfonamide group),
sulfonamide group (e.g. phenylsulfonamide group), sulfamoyl group, alkylsulfamoyl group (e.g. ethylsulfamoyl group), dialkylsulfamoyl group (e.g. dimethylsulfamoyl group), alkylthio group (e.g. methylthio group) , an arylthio group (for example, a phenylthio group), a cyano group, a nitro group, and a halogen atom (for example, fluorine, chlorine, bromine, etc.), and when there are two or more of these substituents, they may be the same or different.

Particularly preferred substituents include a halogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group, and a cyano group. ] represents.

R4 is an unsubstituted or substituted anilino group, an acylamino group (
For example, it represents an alkylcarbonamide group, a phenylcarbonamide group, an alkoxycarbonamide group, a phenyloxycarbonamide group), a ureido group (for example, an alkylureido group, a phenylureido group), and these substituents include a halogen atom (for example, a fluorine atom). , chlorine atom, bromine atom, etc.), linear or branched alkyl groups (e.g., methyl group, t-butyl group, octyl group, tetradecyl group, etc.), alkoxy groups (e.g., methoxy group, ethoxy group, 2-ethyl group, etc.) xyloxy group, tetradecyloxy group), acylamino group (e.g. acetamido group,
Benzamide group, butanamide group, octaneamide group,
Tetradecanamide group, α-(2,4-di-tart-
amylphenoxy)acetamide group, α-(2,4-di-te“t-amylphenoxy)butyramide group, α-
(3-pentadecylphenoxy)hexaneamide group, α
-(4-hydroxy-3-tert-butylphenoxy)tetradecanamide group, 2-oxo-pyrrolidine-1
-yl group, 2-oxo-5-tetradecylpyrrolidine-
1-yl group, N-methyl-tetradecanamide group, etc.)
, sulfonamide group (e.g. methanesulfonamide group, benzenesulfonamide group, ethylsulfonamide group, p-toluenesulfonamide group, octane sulfonamide group, p-dodecylbenzenesulfonamide group, N-
methyl-tetradecanesulfonamide group], sulfamoyl group (e.g., sulfamoyl L N-methylsulfamoyl L N-ethylsulfamoyl group, N,N
-dimethylsulfamoyl group, N, N-dihexylsulfamoyl group, N-hexadecylsulfamoyl group, N
-[3-(dodecyloxy)-propyl]sulfamoyl group, N-(4-(2,4-di-tert-7-milphenoxy)butylcarbamoyl group, N-methyl-N-tetradecylsulfamoyl group, etc.), carbamoyl groups (for example, N-methylcarbamoyl group, N-butylcarbamoyl group, N-octadecylcarbamoyl group, N-(4-
(2,4-di-tert-amylphenoxy)butylcarbamoyl group, N-methyl-N-tetradecylcarbamoyl group, etc.), diacylamino group (N-succinimide group, N-phthalimide group, 2.5-dioxo-1- Oxazolidinyl group, 3-dodecyl-2,5-dioxo-1
-hydantoinyl group, 3-(N-acetyl-N-dodecylamino)succinimide group, etc.), alkoxycarbonyl group (e.g., methoxycarbonyl group, tetradecyloxycarbonyl group, benzyloxycarbonyl group, etc.), alkoxysulfonyl group (e.g. , methoxysulfonyl group, butoxysulfonyl group, octyloxysulfonyl group, tetradecyloxysulfonyl group, etc.);
di-tert-amylphenoxysulfonyl group, etc.),
Alkanesulfonyl group (e.g. methanesulfonyl group,
ethanesulfonyl group, octanesulfonyl group, 2-ethylhexylsulfonyl group, hexadecanesulfonyl group, etc.), irisulfonyl group (e.g. benzenesulfonyl group, 4-nonylbenzenesulfonyl group, etc.), alkylthio group (e.g. methylthio group, ethylthio group, hexylthio group, benzylthio group, tetradecylthio group,
2-(2゜4-di-tart-amylphenoxy)ethylthio group, etc.), arylthio group (e.g., phenylthio group, p-tolylthio group, etc.), alkyloxycarbonylamino group (e.g., methoxycarbonylamino group, ethyloxycarbonylamino group) group, benzyloxycarbonylamino group, hexadecyloxycarbonylamino group, etc.), alkylureido group (e.g., N-methylureido group, N-methylureido group, etc.).

N-dimethylureido group, N-methyl-N-dodecylureido group, N-hexadecylureido group, N,N-diotadecylureido group, etc.), acyl group (for example, acetyl group, benzoyl group, octadecanoyl group, (p-dodecaneamide benzoyl group, etc.), nitro group, carboxyl group, sulfo group, hydroxy group, or trichloromethyl group. However, among the above substituents, the number of carbon atoms of those defined as alkyl groups is 1 to 36, and the number of carbon atoms in the aryl group is 6 to 3 days.

Rs, R1, Rq, Rs, R9, R+. ,Ro,
Rtss Rtss R14, R1, and R1& are each a hydrogen atom, a hydroxyl group, or an unsubstituted or substituted alkyl group (preferably one with 1 to 20 carbon atoms, for example, a methyl group, a propyl group, a t-butyl group) , trifluoromethyl group, tridecyl group, etc.), aryl group (preferably one having 6 to 20 carbon atoms).

For example, phenyl group, 4-t-butylphenyl group, 2.
4-di-t-amylphenyl group, 4-methoxyphenyl group, etc.), heterocyclic group (e.g., 2-furyl group, 2-chenyl group, 2-pyrimidinyl group, 2-benzothiazolyl group, etc.), alkylamino group (preferably has 1 to 20 carbon atoms. For example, methylamino group, diethylamino group, t-
butylamino group, etc.), acylamino group (preferably one with 2 to 20 carbon atoms, e.g., acetylamino group, propylamide group, benzamide group, etc.), anilino group (e.g., phenylamino group, 2-chloroanilino group, etc.), alkoxy Carbonyl group (preferably one with 2 to 20 carbon atoms)
For example, methoxycarbonyl group, butoxycarbonyl group, 2-ethylhexyloxycarbonyl group, etc.), alkylcarbonyl group (preferably one with 2 to 20 carbon atoms; for example, acetyl group, butylcarbonyl group, cyclohexylcarbonyl group, etc.), Arylcarbonyl groups (e.g.
Preferably one having 7 to 2 carbon atoms. Benzoyl group, 4-
t-butylbenzoyl group, etc.), alkylthio group (preferably one having 1 to 20 carbon atoms).

For example, methylthio group, octylthio group, 2-phenoxyethylthio group), arylthio group (preferably one with 6 to 20 carbon atoms, such as phenylthio group, 2-butoxy-5-t-octylphenylthio group, etc.), carbamoyl Groups (preferably those having 1 to 20 carbon atoms, e.g., N-
ethylcarbamoyl group, N,N-dibutylcarbamoyl group, N-methyl-N-butylcarbamoyl group, etc.), sulfamoyl group (preferably one having up to 20 carbon atoms), for example, N-ethylsulfamoyl group, N,N- diethylsulfamoyl group, N,N-dipropylsulfamoyl group, etc.) or sulfonamide group (preferably 1 to 2 carbon atoms)
0 represents a methanesulfonamide group, benzenesulfonamide group, p-toluenesulfonamide group, etc.).

X is a halogen atom (e.g., chlorine atom, bromine atom, etc.),
Coupling-off groups linked via an oxygen atom (e.g. acetoxy group, propanoyloxy group, benzoyloxy group,
Ethoxyoxaloyloxy group, bilbinyloxy group,
Cinnamoyloxy group, phenoxy group, 4-cyanophenoxyl group, 4-titanesulfonamidophenoxy group,
α-naphthoxy group, 4-cyanoxyl group, 4-methanesulfonamide-phenoxy group, α-naphthoxy group, 3-
Pentadecylphenoxy group, benzyloxycarbonyloxy group, ethoxy group, 2-cyanoethoxy group, benzyloxy group, 2-phenethyloxy group, 2-phenoxy-ethoxy group, 5-phenyltetrazolyloxy group, 2
-benzothiazolyloxy group, etc.), coupling-off groups connected via a nitrogen atom (e.g., Japanese Patent Application No. 189-189-53)
8, specifically benzenesulfonamide group, N-ethyltoluenesulfonamide group, heptafluorobutanamide group, 2,3゜4.5.6-pentafluorobenzamide group, octane sulfonamide group. Amido group, p-cyanophenylureido group SN, N-diethylsulfamoylamino group, 1-piperidyl group, 5.5-
Dimethyl-2゜4-dioxo-3-oxazolidinyl group, i-<Fuji-5-ethoxy-3-hydantoynyl group, 2-oxo-1,2-dihydro-1-pyridinyl group,
imidazolyl group, pyrazolyl group, 3.5-diethyl-1
, 2,4-triazol-1-yl group, 5- or 6-
(promobenzotriazol-1-yl group, 5-methyl-1,2,3,4-triazoJL/-1-yl group, benzimidazolyl group, etc.), coupling-off groups linked via a sulfur atom (e.g. phenylthio group, 2-carboxyphenylthio group, 2-methoxy-5-octylphenylthio group, 4-methanesulfonylphenylthio group, 4-octanesulfonamidophenylthio group, benzylthio group, 2-cyanoethylthio group, 5-phenyl-2, 3,4
, 5-tetrazolylthio group, 2-hendithiazolyl group, etc.).

Preferably, it is a coupling-off group connected via a nitrogen atom, and particularly preferably a pyrazolyl group, an imidazolyl group, or a triazolyl group.

E represents an unsubstituted or substituted alkylene group, aralkylene group, or phenylene group having 1 to 10 carbon atoms;
The alkylene group may be linear or branched; examples of the alkylene group include methylene, methylmethylene, dimethylmethylene, dimethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, decylmethylene; examples of the aralkylene group include benzylidene; and the phenylene group. Examples include p-phenylene, m-phenylene, and methylphenylene.

Substituents for the alkylene group, aralkylene group, or phenylene group represented by E include aryl groups (e.g., phenyl groups, etc.), nitro groups, hydroxyl groups, cyano groups, sulfo groups, alkoxy groups (e.g., methoxy groups, etc.), oxy groups (e.g., phenoxy groups, etc.), acyloxy groups (e.g., acetoxy groups, etc.), acylamino groups (e.g., acetylamino groups, etc.), sulfonamide groups (e.g., methanesulfonamide groups, etc.), sulfamoyl groups (e.g., methylsulfamoyl groups, etc.) ), halogen atoms (e.g. fluorine atoms,
This substituent includes If there are two or more, they may be the same or different.

The polymer coupler latex of the present invention has the general formula (II3
It may be a homopolymer of monomeric couplers of general formula (II), or a copolymer of monomeric couplers of general formula (n) and aromatic-class amine development. It may also be a copolymer of a non-chromogenic ethylene-like monomer that does not couple with the oxidation product of the main drug.

In this case as well, two or more types of monomeric couplers included in general formula (II) may be used as the monomeric coupler of general formula (n).

Examples of non-color-forming ethylene-like monomers that do not couple with the oxidized aromatic amine developer include acrylic esters, methacrylic esters, crotonic esters, vinyl esters, maleic diesters, and fumaric acid esters. Examples include acid diesters, itaconic acid diesters, acrylamides, methacrylamides, vinyl ethers, and styrenes.

More specific examples of these monomers include acrylic esters such as methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, t, n-butyl acrylate, isobutyl acrylate, tart-butyl acrylate, and hexyl acrylate. Acrylate, 2-ethylhexyl acrylate, acetoxyethyl acrylate, phenyl acrylate, 2-
Methoxy acrylate, 2-ethoxy acrylate, 2
-(2-methoxyethoxy)ethyl acrylate and the like. Methacrylic acid esters include methyl methacrylate, ethyl methacrylate, low propyl methacrylate, n-butyl methacrylate, lart-butyl methacrylate, cyclohexyl methacrylate, 2
-hydroxyethyl methacrylate, 2-ethoxyethyl methacrylate, and the like. Examples include crotonate ester, butyl crotonate, hexyl crotonate, and the like. Examples of the vinyl ester include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methoxy acetate, benzo M vinyl, and the like. Examples of maleic acid diesters include diethyl maleate, dimethyl maleate, dibutyl maleate, and the like.

Examples of fumaric acid diesters include diethyl fumarate, dimethyl fumarate, and dibutyl fumarate. Examples of itaconic acid diesters include diethyl itaconate, dimethyl itaconate, dibutyl itaconate, and the like. Acrylamides include acrylamide, methylacrylamide, ethylacrylamide, propylacrylamide, n-butylacrylamide, tert-butylacrylamide, cyclohexylacrylamide, 2-methoxyethylacrylamide, dimethylacrylamide,
Examples include diethylacrylamide and phenylacrylamide. Methacrylamides include methyl methacrylamide, ethyl methacrylamide, n-butyl methacrylamide, tart-butyl methacrylamide, 2
-Methoxymethacrylamide, dimethylmethacrylamide, diethylmethacrylamide and the like. Examples of vinyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, methoxyethyl vinyl ether, dimethylaminoethyl vinyl ether, and the like. Styrenes include styrene, methylstyrene, dimethylstyrene, trimethylstyrene,
Examples include ethylstyrene, isopropylstyrene, butylstyrene, chloromethylstyrene, methoxystyrene, butoxystyrene, acetoxystyrene, chlorstyrene, dichlorostyrene, bromustyrene, vinylbenzoic acid methyl ester, 2-methylstyrene, and the like.

Examples of other monomers include allyl compounds (such as allyl acetate), vinyl ketones (such as methyl vinyl ketone), and vinyl heterocyclic compounds (such as vinyl pyridine).
, glycidyl esters (e.g. glycidyl acrylate, etc.), unsaturated nitriles R (e.g. acrylonitrile, etc.), acrylic acid, methacrylic acid, itaconic acid, maleic acid, monoalkyl itaconate (e.g. monomethyl itaconate, etc.), monoalkyl maleate ( (e.g., monomethyl maleate, etc.), citraconic acid, vinylsulfonic acid, acryloyloxyalkylsulfonic acid (e.g., acryloyloxymethylsulfonic acid, etc.), acrylamide alkylsulfonic acid (e.g., 2-acrylamide-2-
methylethanesulfonic acid, etc.). These acids may be salts of alkali metals (eg, Na, etc.) or ammonium ions.

Among these monomers, comonomers that are preferably used are selected based on the hydrophilicity and lipophilicity of the monomer, the copolymerizability of the monomer, the color forming property of the produced polymer coupler, the oil pKa', the color tone of the produced dye, etc. These include acrylic esters, methacrylic esters, styrenes, maleic esters, acrylamides, and methacrylamides.

Two or more of these monomers may be used in combination.

Examples of combinations when using two or more types include n-
Butyl acrylate and styrene, n-butyl acrylate and butylstyrene, t-butyl methylacrylamide and n
-butyl acrylate and the like.

The proportion of the color-forming portion corresponding to general formula (n) in the polymer coupler of the present invention is normally desirably 5 to 80% by weight, but from the viewpoint of color reproduction, color-forming property, and stability, it is preferably 30 to 70% by weight.
Weight percent is preferred, where the molecule 1t (grams of polymer containing 1 mole of monomeric coupler) is from about 250 to
4000, but is not limited to this.

The polymeric coupler latex of the present invention is based on coupler monomer and is applied to the silver halide emulsion layer at 0.00.
005 mol to 0.5 mol, preferably 0.01 mol to 0
．． It is best to add 1 mole.

The magenta polymer coupler used in the present invention is a lipophilic polymer coupler obtained by polymerizing the above-mentioned monomer couplers in an organic solvent. Showa 58
-120252, JP-A-58-145944, JP-A-5
8-211756, JP 58-224352, JP 59-42543, JP 59-171956, JP 59-228252, JP 60-35732 and JP 60-46555. This is done using a compound.

The polymerization temperature must be set in relation to the molecular weight of the polymer to be produced, the type of initiator, etc.
It is possible to polymerize at a temperature of 30°C to 100°C, but polymerization is usually carried out at a temperature of 30°C to 100°C.

Typical 2-equivalent magenta polymer couplers used in the present invention are shown below, but are not limited thereto.

C-2 CH.

2 x/y=50150 (wt%) CH.

CH.

■ 2 x/y/z-50/25/25 (wt) CH3 ■ CH.

x/y-50150 (wt) x/y=70/30 (wt) C-9 CH, CI.

Hs ■ Shi! x/y-70/30 (wt) Shil x/y-40/60 (wt) Shil x/y/z 55/4015 (w t) Hs Shi2 X/1-50150 (wt) Shi2 x/y=5015G (wt) C-17 C-18 1 x/y/z=70/2515 (wL)x/F/
z −50/30/20 (w t )x/y=60
/40 (wt) CH.

x/y direction 40/60 (wt) C-25 C-26 Hs Hs ■ x/y direction 5015G (wt) A typical synthesis example of the polymer coupler of the present invention is shown below.

Production method example 1 - (2,4,6-)lichlorophenyl)-3-methacryloylamino-4-pyrazolyl-2-pyrazoline-
A copolymerized lipophilic polymer coupler of 5-one, styrene, and n-butyl acrylate (a mixture of 50 g of C monomer coupler, 25 g of styrene, 25 g of n-butyl acrylate, and 300 ml of ethyl acetate was stirred at 75°C in a nitrogen stream, After adding 20 ml of an ethyl acetate solution in which 4 g of dimethyl azobisisoacetate was dissolved, the mixture was reacted for 6 hours. After cooling, the ethyl acetate solution was distilled off under reduced pressure, taken out and dried to obtain 98.6 g of polymer coupler (C-5).

Elemental analysis (nitrogen analysis, chlorine analysis) revealed that the copolymer composition of polymer coupler (C-5) had a coupler monomer content of 49.8%.

The 2-equivalent magenta polymer coupler of the present invention is contained in the green-sensitive silver halide emulsion layer, and the coating amount is 0.0
05 to 1.0 g/+yf, preferably 0.01 to
0.1g1rd, more preferably 0.05-0.5g/
It is rd.

The compound represented by the general formula [I1 of the present invention is contained in the blue-sensitive silver halide emulsion layer and/or the red-sensitive silver halide emulsion layer, and the coating amount is determined in the blue-sensitive silver halide emulsion layer, the red-sensitive silver halide emulsion layer, and the red-sensitive silver halide emulsion layer. In each case of silver emulsion layer, 1.0X10-' to 1, Ox 10-'g/cd
and preferably 1.0XIO-' to 5. Ox
10-"g/rd, more preferably 5.0X10-'~
3.0 x 10-'', preferably contained in the both-sensitive silver halide emulsion layer.

The preferred silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention is silver iodobromide, silver iodochloride, or silver iodochlorobromide, containing about 30 mol% or less of silver iodide. . Particularly preferred is silver iodobromide containing from about 2 mole percent to about 25 mole percent silver iodide.

Silver halide grains in photographic emulsions include those with regular crystals such as cubes, octahedrons, and tetradecahedrons, those with irregular crystal shapes such as spherical and plate shapes, and those with twin planes. may have crystal defects, or may be a composite form thereof.

The grain size of the silver halide may be fine grains of about 0.2 microns or less or large grains with a projected area diameter of up to about 10 microns, and may be a polydisperse emulsion or a monodisperse emulsion.

Silver halide photographic emulsions that can be used in the present invention include, for example, Research Disclosure (RD), 1IkL176
43 (December 1978), pp. 22-23, '■, Emulsion preparation
andtypes)'', and N118716 (1
November 979), 648 pages, Graphic "Physics and Chemistry of Photography", published by Paul Montell (P, GIafk+
des.

Chemic et Ph1sique Photog
raphique paul montel.

1967), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (G, F, Photogra
phicEmulsion Chemistry (F
ocal Press, 1966'), "Manufacture and coating of photographic emulsions" by Zeliks+an et al., published by Focal Press (V, L, Zeliks+an et al.
.

Making and coating photo
graphic emulsion.

Focal Press+ 1964).

U.S. Patent Nos. 3,574,628 and 3,655.39
Monodisperse emulsions such as those described in No. 4 and British Patent No. 1,413.748 are also preferred.

Tabular grains having aspect ratios of about 5 or more can also be used in the present invention. Tabular grains are described in Cutoff, Photographic Science and Engineering.
nce and Engineering), 1st
4, pp. 248-257 (1970); U.S. Patent No. 4
．． No. 434.226, No. 4,414,310, No. 433.048, No. 4,439,520, and British Patent No. 2,112,157. can.

The crystal structure may be uniform, the inside and outside may have different halogen compositions, it may have a layered structure, or silver halides with different compositions may be bonded by epitaxial bonding. , or may be bonded with a compound other than silver halide, such as silver rhodan or lead oxide.

Also, mixtures of particles of various crystal forms may be used.

The silver halide emulsion used is usually one that has been subjected to physical ripening, chemical ripening, and 1-minute photosensitization. Additives used in such processes are subject to Research Disclosure No. 1.
7643 and patient 18716, and 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 descriptions are shown in the table below.

',, RD17643 DR187
161 Chemical sensitizers Page 23 Page 648 Right column 2
Sensitivity enhancer Same as above 3 Spectral enhancer, pages 23-24 Page 648 right column - Super sensitizer
Page 649 Right column 4 Brightener 2
Page 4 5 Antifogging agent Pages 24-25 Page 649 Right column ~
and stabilizer 6 light absorber, fu pages 25-26 page 649 right column ~
Ilter dye page 650 left column UV absorber 7 stain inhibitor page 25 right column page 650 left to right column 8 dye image stabilizer page 25 9 hardener page 26 page 651 left column 10
Binder Page 26 Same as above 11 Plasticizer, lubricant Page 27 650 Right column 12 Coating aid, surface Pages 26-27 Same as above Activator 13 Static prevention Page 27 Same as above Various color couplers can be used in the present invention. A specific example of this can be found in the aforementioned Research Disclosure (
RD) No. 17643, ■-〇-G.

As a yellow coupler, for example, U.S. Patent No. 3.93
No. 3,501, No. 4,022,620, No. 4,3
No. 26,024, No. 4,401゜752, Special Publication No. 5
No. 8-10739, British Patent No. 1,425,020,
Same 1st. 476, 760, etc. are preferred.

As the magenta coupler, 5-pyrazolone and pyrazoloazole compounds are preferred, and U.S. Pat.
No. 0,619, No. 4,351°897, European Patent No. 73,636, U.S. Patent No. 3,061,432, No. 3. 725. No. 067, Research Disclosure & 24220 (June 1984), JP-A-1983-
No. 33552, Research Disclosure m242
30 (June 1984), JP-A No. 60-43659,
U.S. Patent No. 4,500,630, U.S. Patent No. 4.540.6
Particularly preferred are those described in No. 54 and the like.

Cyan couplers include phenolic and naphthol couplers, and are described in U.S. Pat. No. 4,052,212.
No. 4.146,396, No. 4.228,23
No. 3, No. 4. 296. 200, No. 2,369,
No. 929, No. 2.801°171, No. 2,772.
No. 162, No. 2゜895.826, No. 3,772
．． No. 002, No. 3,758,308, No. 4. 3
34. 011, German Patent Application No. 4.327,173, West German Patent Application No. 3.329,729, European Patent Application No. 121゜3
No. 65A, U.S. Patent No. 3,446,622, U.S. Patent No. 4.
No. 333,999, same No. 4. 451. 559, European Patent No. 4.427.767, European Patent No. 161.626A
Preferably, those described in No.

Colored couplers for correcting unnecessary absorption of coloring dyes are available at Research Disclosure Floor 17643.
- Section G, U.S. Patent No. 4.163゜670, Special Publication No. 1983
-39413, U.S. Patent No. 4,004,929, U.S. Patent No. 4. 138. No. 258, British Patent No. 1,146.
The one described in No. 368 is preferred.

Couplers whose coloring dyes have appropriate diffusivity include U.S. Patent No. 4,366.237 and British Patent No. 2,125.
, 570, European Patent No. 96,570, and German Patent Publication No. 3,234,533 are preferred.

Typical examples of polymerized dye-forming couplers are U.S. Pat. No. 3,451,820, U.S. Pat.
It is described in No. 173, etc.

Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. DIR couplers releasing development inhibitors include the aforementioned RD17643,
Patents listed in Sections ■-F, Japanese Patent Application Laid-Open No. 57-151944
Preferred are those described in No. 57-154234, No. 60-184248, and U.S. Pat.

Couplers that release a nucleating agent or a development accelerator imagewise during development include British Patent No. 2,097.140;
No. 2,131.188, JP 59-157638
No. 59-170840 is preferred.

Other couplers that can be used in the light-sensitive material of the present invention include competitive couplers described in U.S. Pat. No. 4,130,427, U.S. Pat. , European Patent No. 4,310.618, etc., European Patent No. 173,302A
Examples include couplers that release a dye that exhibits aftercoloring after separation, as described in the above issue.

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

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

The process and effects of latex dispersion methods, and specific examples of latexes for immersion are disclosed in U.S. Pat. It is written in the number etc.

Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D, page 28 of 17643, and 6 of 18716
It is described from the right column on page 47 to the left column on page 648.

The color photographic light-sensitive material according to the present invention includes the above-mentioned RDlk
17643, pages 28-29, and the same page 18716, 6
51. Development processing can be carried out by the usual methods described in the left column to right column.

The silver halide color photographic light-sensitive material of the present invention is generally subjected to a water washing and/or stabilization step after desilvering treatment such as fixing or bleach-fixing.

The amount of water used in the washing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the application, the temperature of the washing water, the number of washing tanks (number of stages), the replenishment method such as countercurrent or forward flow, and various other conditions. Can be set over a wide range. Among these, the relationship between the number of flushing tanks and the amount of water in the multistage countercurrent method is described in the Journal on the Society on Motion Picture and Television Engineers (Jo
Urnal of the 5ociety of M
tion Picture and Televisi
on Engineers) No. 64@, P, 248
-253 (May 1955 issue).

According to the multi-stage countercurrent method described in the above-mentioned literature, the amount of water used for washing can be greatly reduced, but the increased residence time of water in the tank causes bacteria to propagate and the generated suspended matter to adhere to the photosensitive material. In the processing of the color photosensitive material of the present invention, the method for reducing calcium and magnesium described in Japanese Patent Application No. 131632/1988 can be used very effectively as a solution to such problems. can. In addition, chlorine-based disinfectants such as isothiazolone compounds, cyabendazole, chlorinated sodium isocyanurate, and other benzotriazoles described in JP-A No. 57-8542, "Chemistry of Antibacterial and Antifungal Agents" by Hiroshi Horiguchi It is also possible to use disinfectants described in ``Microorganism Sterilization, Disinfection, and Anti-Mildew Techniques'', a complete collection of sanitary techniques, and ``Encyclopedia of Antibacterial and Antifungal Agents'' published by Japan Antibacterial and Antifungal Science Wire Net.

The pH of the washing water in the processing of the photosensitive material of the present invention is 4-
9, preferably 5-8. The washing water temperature and washing time can also be set variously depending on the characteristics of the photosensitive material, its use, etc., but generally it is 20 seconds to 10 minutes at 15-45°C, preferably 20 minutes.
A range of 30 seconds to 5 minutes at 5-40°C is selected.

Furthermore, the photosensitive material of the present invention can also be directly processed with a stabilizing solution instead of washing with water. In such stabilization treatment, Japanese Patent Application Laid-open Nos. 57-8543 and 58-1483
No. 4, No. 59-184343, No. 60-220345,
No. 60-238832, No. 60-239784, 60-
No. 239749, No. 61-4054, No. 61-11874
All known methods described in No. 9 etc. can be used. In particular, a stabilizing bath containing 1-hydroxyethylidene-1,1-diphosphonic acid, 5-chloro-2-methyl-4-isothiazolin-3-one, a bismuth compound, an ammonium compound, etc. is preferably used.

Further, following the water washing treatment, a further stabilization treatment may be carried out. An example of this is a stabilizing bath containing formalin and a surfactant, which is used as a final bath for color photographic materials for imaging. can.

(Examples) The present invention will be explained in detail below using Examples, but the present invention is not limited thereto.

Example 1 On a subbed cellulose triacetate film support,
Sample 01, which is a multilayer color light-sensitive material, was prepared by coating layers having the compositions shown below.

(Photosensitive layer composition) The number corresponding to each component indicates the coating amount expressed in g/ITr unit, and for silver halide, it indicates the coating amount in terms of silver. However, for sensitizing dyes, the halogen in the same layer The coating amount per mole of silveride is shown in moles.

(Sample 101) 1st layer; antihalation layer black colloidal silver ・・・・・・・・・・・・・・・・・・
・・・・Silver 0.18 Gelatin ・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・ 0.40 2nd N: Intermediate layer 2.5-di-t-pentadecylhydroquinone ・・・・・・・・・・・・・・・・・・
・・・・0.18EX-1・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・0.07E
X-3・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・0.02EX-11・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
・・・0.005U-1・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・0.0
8U-2・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・0.08HBS-1・
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・0.10HBS-2・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・0.02 Gelatin ・・・・・・・・・・・・・・・・・・・・・・・・
1.04 Third layer (first red-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide 6 mol%, average grain size 0.70μ)・・・・・・Silver 0.
55 sensitizing dye!・・・・・・・・・・・・・・・・・・
・・・・・・6.9X10-'sensitizing dye■ ・・・・
・・・・・・・・・・・・・・・・・・Bow, 8x10
-s Sensitizing dye■ ・・・・・・・・・・・・・・・・・
・・・・・・3.1X10-'sensitizing dye■ ・・・・
・・・・・・・・・・・・・・・・・・・・・4.0X1
0-'EX-2・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・0.350HBS-1
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・0.005EX-10・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・0.
042 Gelatin ・・・・・・・・・・・・・・・・・・
...Old...1.20 4th layer (second red-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide 8 mol%, average grain size 0.75μ)...・・・・・・・・・・Silver 1.
20 Sensitizing dye l・・・・・・・・・・・・・・・・・・
・・・・・・・・・5. lX10-'sensitizing dye■...
・・・・・・・・・・・・ Old... 1.4X10-
'Sensitizing dye ■... Old... Old... 2.3X10-' Sensitizing dye ■...
......Old...3.0X10-'EX-2
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・0.300EX-3・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
0.050EX-10・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・0.004HB
S-2・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・0.050 Gelatin ・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
・1.30 Fifth layer (third red-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide 14 mol%, average grain size 1.0
0μ)...Old...Silver 1.60 multiplying dye■ ・
・・・・・・・・・・・・・・・・・・・・・・・・5.
4X10-'sensitizing dye■ ・・・・・・・・・・・・・・・
......1.4X10-' sensitizing dye ■
・・・・・・・・・・・・・・・・・・・・・・・・2
．． 4X10-'sensitizing dye■ ・・・・・・・・・・・・
・・・・・・・・・・・・3. lX10-'EX-5・
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・0.150EX-3・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・0
．． 055EX-4・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・0.060HB S
-1・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・0.32 Gelatin ・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
1.63 6th w1 (middle layer) HBS-3・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・0.01 gelatin ・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
・・1.06EX-14・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・0.02 7th
Layer (first green-sensitive emulsion N) Silver iodobromide emulsion (iodide 116 mol%, average grain size 0.6
5μ)・・・・・・・・・・・・5IO140 Sensitizing Dye V・・・・・・・・・・・・・・・・・・・・・・
・3.0X10-'sensitizing dye■ ・・・・・・・・・・・・
・・・・・・・・・・・・・・・1.0X10-' Sensitizing dye■ ・・・・・・・・・・・・・・・・・・・・・
・・3,13xlo-'EX-6・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・0.
260EX-1・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・0.021EX-7・
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・0.030EX-8・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・0
．． 025HBS-1・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・0.100HBS-4・
・・・・・・・・・・・・・・・・・・・・・・・・
・・・0.060 Gelatin ・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・0.7
5 8th layer (second green-sensitive emulsion layer) Silver iodobromide emulsion (iodide! 19 mol%, average grain size 0.7
0μ)・・・・・・・・・・・・Silver 0.80 sensitizing dye V
・・・・・・・・・・・・・・・・・・・・・・・・
2.1X10-'sensitizing dye■ ・・・・・・・・・・・・
・・・・・・・・・・・・7.0X10-' Sensitizing dye■ ・・・・・・・・・・・・・・・・・・・・・・・・
・2.6X10-'EX-6・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・0.15
0EX-8・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・0.010EX-1...
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・0.008EX-7・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・0.0
12HBS-1・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・0.60HBS-4・・・・
・・・Old・・・・・・Old・・・・・・o, o
s.

Gelatin ・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・1.10 9th layer (3rd green-sensitive emulsion N) Silver iodobromide emulsion (silver iodide 12 mol%, average grain size 1.0
μ)・・・・・・・・・・・・・・・Silver 1. 2 Sensitizing dye■ ・・・・・・・・・・・・・・・・・・ Old...
3.5X10-'sensitizing dye■ ・・・・・・・・・・・・
・・・・・・・・・・・・8.0X10-' Sensitizing dye■ ・・・・・・・・・・・・Old・・・・・・・・・3
．． 0X10-'EX-6... Old...
・・・・・・・・・・・・・・・・・・0.065EX-
1・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・0.025HBS-2・・・・・・
・・・・・・・・・・・・Old・・・・・・・・・0.5
5 Gelatin ・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・ 1.74 1st θ layer (yellow filter single layer) Yellow colloidal silver ・・・・・・・・・・・・・・・・・・
...Silver 0. o5EX-14・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・0.0
4HBS-1・・・・・・・・・・・・・・・・・・
Old...0.02 gelatin...
・・・・・・・・・・・・・・・・・・・・・・・・
・0.95 11th layer (first blue-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide 6 mol%, average grain size 0.6μ) Silver 0.24 sensitizing dye■ ・・・・・・・・・・・・・・・
......3.5xlO-'EX-9...
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・0.85EX-8・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・0.12H
BS-1・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・0.28 gelatin ・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
・1.28 12th layer (second blue emulsion layer) Silver iodobromide emulsion (silver iodide 10 mol%, average grain size 0.8
0μ)・・・・・・・・・・・・Silver 0.45 sensitizing dye■
・・・・・・・・・・・・・・・・・・・・・・・・
2. lX10-'EX-9・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・0.20E
X-8・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・0.015HBS-1・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
・0.03 gelatin ・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・0.46 No. 13
Layer (third blue-sensitive emulsion layer) Silver iodobromide emulsion (11116 mol% iodide, average grain size 1
．． 2μ)・・・・・・・・・・・・iIo, 77
Sensitizing dye■ ・・・・・・・・・・・・・・・・・・
...2.2X1 (I'EX-9...
・・・・・・・・・・・・・・・・・・・・・・・・
0.20HBS 1 ・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・0.07 Gelatin ・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・0.69 14th layer (first protective layer) Silver iodobromide emulsion (il iodide 1 mol%, average grain size 0.0
7μ)・・・・・・・・・・・・Silver 0.08U-1・・
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・0.11U-2・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
・・0.17HBS-1・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・0.90 Gelatin
・・・・・・・・・・・・・・・・・・・・・・・・
......1.00 15th layer (second protection N) Polymethyl methacrylate particles (diameter approximately 1.5 μm) ...0.54
S-1・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・0.04S-2・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・0.04 Gelatin ・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・0
．． 72 In addition to the above ingredients, each layer contains a gelatin hardening agent H-
1 and a surfactant were added.

(Samples 102 to 130) Coupler EX-6 in the 7th layer of sample 101, 3rd layer, 4th layer
Samples 102 to 130 were prepared by replacing EX-10 of N and EX-8 of the 12th layer as shown in Table 1.

Samples 101 to 130 obtained in this way were exposed to uniform green light, and then imagewise exposed to red light, and then developed as shown below, resulting in a cyan image as shown in Figure 1. Characteristic curve 1 and magenta color image density 2
was gotten. Here, ΔD and 80 are the effects that the uniformly covered green-sensitive emulsion layer receives when the red-sensitive emulsion layer is developed from the unexposed area (point A) to the exposed area (points B and 0). It shows the degree of restraint. That is, in FIG. 1, curve 1 represents the characteristic curve for the cyan image of the red-sensitive emulsion, and curve 2 represents the magenta image density of the green-sensitive layer upon uniform green exposure. Point A represents the capri portion of the cyan image, and point B and point 0 represent the exposure amount portions that give cyan densities of 0.8 and 2.0.

Density difference between magenta density (a) at point A in the unexposed area and magenta density (b) and (c) at point B and point 0 (
a-b) and (a-c) were expressed as ΔDm+ΔD, and were used as a measure of color reproducibility (interlayer effect).

Additionally, imagewise exposure is performed with blue light to provide uniform green light and yellow density of 1.8 and 2.
．． The value at 5 is 80,'.

It was set as ΔDc'.

Measurement of MTF value is based on The Theory of th
e Photo-raphic Process
The method described in 3rd edd (published by Matsuku Millan, written by Mies) was followed. Relative sensitivity was calculated from cyan density and magenta density values of 25 cycles/mm from a sample processed by imagewise exposure with white light.

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

Color development 3 minutes 15 seconds Bleaching 6 minutes 30 seconds Water
Wash 2 minutes 10 seconds Fix
Wash with water for 4 minutes and 20 seconds
Stable for 3 minutes 15 seconds 1 minute 05
The composition of the treatment liquid used in each step was as follows.

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
1.3w hydroxylamine sulfate 2
．． 4g 4-(N-Ethyl-N-β-hydroxyethylamino)-2-methylaniline sulfate 4.5g Add water 1.01 pH 10.0 Bleach 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. On! pH 6.0 Fixer Ethylenediaminetetraacetic acid disodium salt 1.0g Sodium sulfite 4.0g ThioloRM ammonium aqueous solution (70%) 175.0ml Sodium bisulfite 4.6g Add water
1.0j! pH6.6 Stable liquid formalin (40%) 2.0mj! Add 0.3 g of polyoxyethylene-p-monononylphenyl ether (Heijujo Kokima 10) to water 1.01 From Table 1, it is clear that when only Mazenk polymer coupler is used in the green-sensitive layer, the sharpness of the cyan image is Although the sharpness is good, the effect of improving the sharpness of magenta image is small, and ΔDl+ ΔDC, ΔD,′, Δ
The glabellar effect on the green-sensing layer represented by Dc' is small;
It is clear that by using the compound of the present invention in the blue-sensitive layer and/or the red-sensitive layer, the sharpness of cyan and magenta images is further improved, and the glabellar effect is also large.

Example 2 Sample 201 was obtained by removing EX-8 from the 3.4th layer of sample 113, 0.025 g/n in the 11th layer, 0.015 g/rd in the 12th layer, and 0.01 g/n in the 13th layer. 008g/rr
+, comparative compounds R-2, R-3, compound of the present invention (36
), (37) and (14) were added, but samples 202, 203, 204, 205 and 206 were prepared in the same manner.

Uniform green light was applied to these samples, and the samples were further imagewise exposed to blue light to perform color development as described below. The magenta densities at yellow densities of 1.5 and 2.5 were measured, and the values obtained by subtracting 4 degrees of magenta capri were measured in accordance with the method of Example 1 and designated as ΔD, , ΔDc #.

In addition, according to Example 1, 40 cycles of magenta image/
The MTF value in mm was measured.

The processing liquid is Fujicolor Super HR-10036 sheets 3
00 with average exposure (photographed at +30100 setting) and passed through a Champion 23S automatic processor manufactured by Fuji Film Co., Ltd., was used.

Color development process Color development 3 minutes 15 seconds bleaching 1 minute bleaching room @ 3 minutes 15 seconds washing with water ■ 40 seconds washing ■ 1 minute stabilization 40 seconds drying (50℃) 1 minute 15 seconds In the above processing steps, washing with water ■ ■ was a countercurrent water washing method from ■ to ■. Next, the composition of each treatment liquid is calculated as follows.

The replenishment amount of each processing solution was 1200 mf for color development and 800 mj' for all other processes including water washing per 1 d of color photosensitive material. Also, the amount of pre-bath carried into the water washing process is 1r of color photosensitive material.
50mj per rr! Met.

(Color developer) Mother solution Replenisher diethylenetriaminepentaacetic acid 1.0g 1.1g1-hydroxyethylidene-1,1-diphosphonic acid 2.0g 2.2gSodium sulfite 4.0g 4.4g Potassium carbonate
30.0g 32.0g Potassium bromide
1.4g017g potassium iodide
1.3 ■ □Hydroxylamine sulfate 2.4g2.6g4-(N-ethyl-N-β-hydroxyethylamino)-2-methylaniline sulfate 4.5g5.0g Add water
1.0f 1. (1 pH 10,010,
05 (Bleach solution) Common to mother liquor and replenisher Ethylenediaminetetraacetic acid ferric ammonium salt 120.0g Ethylenediaminetetraacetic acid dibasic salt 10.0g Ammonium nitrate 10.0g Ammonium bromide 100.0g Bleach accelerator
Add 5X10-'mol ammonia water p
H6,3 Add water 1.01 (Bleach-fix solution) Common to mother liquor and replenisher Ethylenediaminetetraacetic acid ferric ammonium salt 50.0g Ethylenediaminetetraacetic acid dibasic salt 5.0g Sodium sulfite 12.0g Ammonium thiosulfate aqueous solution (70%) 240mff1 Add ammonia water, pH 7.3 Add water, 11 (washing water) Calcium ion 32■/! , magnesium ion7.
Tap water containing 3w/12 was passed through a column filled with H-swelled acidic cation exchange resin and OH type strong basic anion exchange resin, and calcium ions were 1.2■/1 and magnesium ions were 0.4■/l. 20 parts per 1 part of sodium isocyanurate dichloride was added to the treated water.

(Stabilizing solution) Common formalin (37% W/V) for mother solution and replenisher 2.0 ml Peroxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.3 g Ethylene diamide tetraacetic acid disodium salt 0.05 g Add water 1zp8
5.8 (Drying) The drying temperature was 50°C.

It is clear from Table 2 that the samples of the present invention are excellent in both color reproducibility and sharpness.

Example 3 Comparative compound R-4, compounds (35), (33) and (1) of the present invention were added to the 11th layer of sample 113 at 0°0
37g/n? Samples 301, 302, 303, and 304 were prepared in the same manner as sample 103, except that these substances were added.

The sensitivity and MTF values of these samples were measured by the method of Example 2.

In addition, Table 3 shows the results of processing with the equilibrium processing solution treated with these samples 301 to 304 instead of Fujicolor Super HR-100.

From Table 3, the samples of the present invention have excellent sharpness expressed by the MTF value, and regarding processing liquid contamination, -C〇-
It is clear that sample 304 containing the group-bearing compound (1) is preferred.

Table 3 Relative values of reciprocal of exposure amount Super HR-1 of sample 302
The value for the 00 equilibrium treatment solution was set as 100.

Structure of the compound used in Example 1.2.3 X-2 H -7 CH co CH
.

EX-10 EX-11 EX-12 EX-13 Sui EX-15 EX-16 Shi1 HBS-1) Liclesyl phosphate HBS-2 Dibutyl phthalate HBS-3 Bis(2-ethylhexyl) phthalate B5
-4 CHt -CHSow -CHg C0NHCHzCH
t--CH-3o-CHg-CONHCHg5-
I S-2 sensitizing dye (CHg)s SOs” (CHJs SOs N
a11 [c, Hs ■ C*H* ■ C snow Hsa0m Hs ■ C, H.

Comparative compound R-1 (compound 33 of JP-A No. 60-185950) I R-2 (compound 11 of JP-A-61-251847) R
-4<Compound 18 of JP-A-60-185950)

[Brief explanation of drawings]

1 represents the characteristic curves; 1 represents the characteristic curve of the cyan image of the red-sensitive layer; 2 represents the magenta color image density of the green-sensitive layer with uniform green exposure; and 3 represents the characteristic curve of the blue-sensitive layer with uniform green exposure. represents the theoretical magenta density line. Patent Applicant Fuji Photo Film Co., Ltd. Procedural Amendment 1. Display of incident 1937 patent application No. 1/7tJj
No. 2, Name of the invention Silver halide color photographic light-sensitive material 3, Relationship with the person making the amendment Patent applicant Address 210-46 Nakanuma, Minamiashigara City, Kanagawa Prefecture Subject of amendment The "detailed description of the invention" in the specification Column 5, Contents of Amendment The entire statement in the "Detailed Description of the Invention" section of the description shall be amended as follows. 1) Correct the structural formula of "General formula [■]" on page 61 to [〒°' (-CH2C+]. 2) Correct "R3" in the t-th line from the bottom of page 47 to rR3'J do. 3) Correct "R3" in the Gth line from the bottom of page 62 to rR3'J. 4) Correct the structural formula in “General formula [■]” on page 41. 5) Correct "rR4 to R16" on the third line of page 63 to "R4' to R1e'J." 6) Correct the structural formula of "general formula [■]" on page 1s3 to [ ]. 7) The structural formula of "General formula [V]" on page 63 is amended as follows. 8) Correct the structural formula of "General formula [■]" on page 63 to "". 9) Correct the structural formula of "General formula [■]" on page t. lo) Correct No. 64 to the structural formula of "General formula [■]" on page 1. 11) Correct the structural formula of “General formula [■]” on page t≠ to “ ”. 12) Correct the structural formula of "General formula [X]" on page 71≠. 13) Change the description from rRsJ on the first line from the bottom of page 70 to rRxsJ on the third line from the bottom on page 70 as "R'5, R/ ,, R/ 7, R'8, R/,, R'
l01R'11・R'12, R'13・R'14・
R'l! i and R'16 are corrected as follows. 14) Correct "Sample 01J" on the rth line of page 110 to "Sample 10/". ls) Change the description from "Ratio following the method" on the 1st page l≠ line to "Calculation friend" on the 7th line to "Following the method described, 2 of the magenta and cyan images.
! Next, calculate the value of cycles/W. ” he corrected.

Claims (2)

[Claims] (1) having one or more red-sensitive silver halide emulsion layers, one or more green-sensitive silver halide emulsion layers, and one or more blue-sensitive silver halide emulsion layers on a support, at least one of the green-sensitive silver halide emulsion layers; The layer contains at least one 2-equivalent magenta polymer coupler, and at least one layer of the red-sensitive silver halide emulsion layer and/or at least one layer of the blue-sensitive silver halide emulsion layer has the following general formula [I ] A silver halide color photographic material characterized by containing a compound represented by the following. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the general formula [I], A represents a coupler residue, and R_1 has a hydroxyl group at the 2nd or 4th position counting from the oxygen atom bonding position ( n+1)-valent aromatic residue, Z represents a sulfur atom or an oxygen atom, R_2 represents a substituent having 2 to 7 carbon atoms, and n represents an integer of 1 or 2. (2) In the general formula [I], the substituent represented by R_2 has at least one ester bond ▲A mathematical formula, a chemical formula, a table, etc.▼ ) Silver halide color photographic light-sensitive material described in item 2.