JPH0473748A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the photosensitive material having excellent sharpness of color reproducibility and preservable property ;by incorporating a yellow colored cyan coupler into green photossensitive silver halide emulsion layers. CONSTITUTION:The yellow colored cyan coupler is incorporated into the silver halide color photosensitive material having respectively at least one layer of the blue sensitive silver halide emulsion layers, green sensitive silver halide emulsion layers and red sensitive silver halide emulsion layers on a base. The coupler which has the absorption max. in the visible absorption region of the coupler between 400nm and 500nm and forms the cyan dye having the absorption max. in the visible absorption region of the coupler between 630nm and 750nm by coupling with the oxidant of a primary amine developing agent is used as the yellow colored cyan coupler. The photosnesitive material which has a highly sensitivity and soft gradation, excellent color reproducibility, less fluctuation in photographic performance during preservation and high sharpness is obtd. in this way.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a silver halide color photographic light-sensitive material, and in particular contains a yellow-colored cyan coupler in a green-sensitive layer to improve sharpness of color reproducibility and This invention relates to a photosensitive material with excellent storage stability.

(Prior Art) Silver halide color photographic materials are desired to have excellent color reproducibility and little change in photographic performance during storage. As a means to improve color reproducibility, green-light silver halide Incorporating a cyan coupler in the emulsion layer is disclosed in JP-A-62-34160 and JP-A-62-121453.
However, color reproducibility is not fully satisfied using these methods, and the photographic performance of sensitive materials using these methods changes significantly over time from shooting to development. There was a problem.

Furthermore, it was disclosed in JP-A-50-180 that the green photosensitive layer contains a magenta coupler and a development inhibitor-releasing cyan coupler.
No. 40, however, even if this method is used, the color reproduction is not fully satisfied, and this method also has the problem of low sensitivity and soft tone.

On the other hand, Japanese Patent Application Laid-Open No. 59-214853 proposes that a green-red light-sensitive layer contain a magenta coupler, a cyan coupler, and a yellow-colored cyan coupler. This patent is characterized by a configuration that does not use any color, and is completely different from the present invention.Although the above-mentioned patent achieves high sensitivity, the color reproducibility deteriorates on the contrary.

Further, it has been proposed in U.S. Pat. No. 4,186,011 to contain a magenta coupler in a non-photosensitive layer located outside the highest green-sensitive layer having a magenta coupler, but the present invention uses yellow colored cyan. They have completely different effects and configurations.

In addition, in JP-A-51-135, it was proposed to use a diffusion-resistant colored coupler in the non-photosensitive layer between the green photosensitive layer and the red photosensitive layer.
No. 535, the coupler is specified to be red before coupling, but the coupler of this patent is yellow before coupling, and the effect and content are completely different.

(Problems to be Solved by the Invention) The purpose of the present invention is, first, to provide a photosensitive material with high sensitivity, soft tone, and extremely excellent color reproducibility; The object of the present invention is to provide a light-sensitive material with little variation in photographic properties, and the third object is to provide a light-sensitive material with high sharpness.

(Means for Solving the Problems) The objects of the present invention have been achieved by the following color photographic material.

In a silver halide color light-sensitive material having at least one blue-sensitive silver halide emulsion layer, one green-sensitive silver halide emulsion layer, and one red-sensitive silver halide emulsion layer on a support, yellow is added to the green-sensitive silver halide emulsion layer. A silver halide color photographic material containing a colored cyan coupler.

and/or at least one non-light-sensitive layer adjacent to the blue-sensitive silver halide emulsion layer, green-sensitive silver halide emulsion layer, red-sensitive silver halide emulsion layer and green-sensitive silver halide emulsion layer on the support. 1. A silver halide color photographic material characterized in that the non-photosensitive layer contains a yellow colored cyan coupler.

/ Next, the yellow colored cyan coupler of the present invention will be explained.

In the present invention, a yellow colored cyan coupler is defined as having an absorption maximum of 400 nm in the visible absorption region of the coupler.
m to 500 nm, and is a cyan coupler which forms a cyan dye having an absorption maximum in the visible absorption region between 630 nm and 750 nm by coupling with an oxidized aromatic primary amine developing agent. say.

Among the yellow colored cyan couplers of the present invention, a water-soluble 6-hydroxy-2-pyridon-5-ylazo group and a water-soluble pyrazolone-4- Ylazo group, water-soluble 2-acylaminophenylazo group or water-soluble 2
A cyan coupler capable of releasing a compound residue containing a -sulfonamidophenylazo group is preferably used.

The yellow colored cyan coupler of the present invention is preferably represented by the following general formulas (CI) to (CIV).

General formula ((, In general formula (CII) General formula % Formula % [[) In general formulas (CI) to (CIV), Cp represents the cyan coupler residue i (T is bonded to its coupling position). , T is a timing group, k is an integer of O or 1, X includes N, 0, or S, and thereby represents a divalent linking group that binds to (T) k and connects Q, and Q represents an arylene group or a divalent heterocyclic group.

In the general formula (CI), R1 and Rt are independently a hydrogen atom, a carboxyl group, a sulfo group, a cyano group, an alkyl group, a cycloalkyl group, an aryl group, a heterocyclic group, a carbamoyl group, a sulfamoyl group, a carbonamide group, a sulfone group. amide group or alkylsulfonyl group; R3 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group, provided that TSX, Q, R
,, at least one of R2 or R3 is a water-soluble group (
For example, hydroxyl, carboxyl, sulfo, amino,
ammoniamil, phosphono, phosphino, hydroxysulfonyloxy).

It is well known that can take the following tautomeric structure, and these tautomeric structures also have the general formula (
CI).

(When R3 is a hydrogen atom) (When R is a hydrogen atom) (When R3 is a hydrogen atom) (When Rs is a hydrogen atom) In the general formula (C1l), R4 is an acyl group or a sulfonyl group, and R1 is an acyl group or a sulfonyl group. j represents a substitutable group, and j represents an integer of 0 to 4. When j is an integer of 2 or more, R4 may be the same or different, provided that at least one of T, X, Q, R, or R2 is a water-soluble group (e.g., hydroxyl, carboxyl, sulfo, phosphono , phosphino,
hydroxysulfonyloxy, amino, ammoniamil].

In the general formulas (CI[[) and (CTV), R.

H hydrogen atom, carboxyl group, sulfo group, cyano group, alkyl group, cycloalkyl group, aryl group, alkoxy group, cycloalkyloxy group, aryloxy group, heterocyclic group, carbamoyl group, sulfamoyl group, carbonamide group, sulfone R111 represents an amide group or an alkylsulfonyl group, and R11l represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a heterocyclic group, respectively, provided that T, X;

At least one of Q, R, or R1° shall contain a water-soluble group (eg, hydroxyl, carboxyl, sulfo, phosphono, phosphino, hydroxysulfonyloxy, amino, ammoniamyl).

The coupler residue represented by CP includes known cyan coupler residues (eg, phenol type, naphthol type, etc.).

Preferred examples of cp include the following general formula (Cp-6),
Coupler residues represented by (Cp-7) or (Cp-8) can be mentioned.

General formula (Cp-6) General formula (Cp-7) They are isomers and are the same compound.

The compounds represented by formulas (CI) to (CI) will be explained in more detail below.

General Formula (Cp-8) 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, when R511R51l R5ff+ Rsa or Rss contains a diffusion-resistant group, it is selected such that the total number of carbon atoms is 8 to 40, preferably 10 to 3o; otherwise, the total number of carbon atoms is 15 or less. is preferred. In the case of bis-type, telomer-type or polymer-type couplers, any of the above-mentioned substituents represents a divalent group and connects repeating units and the like. In this case, the range of carbon numbers may be outside the specified range.

In the following, R41 represents an aliphatic group, an aromatic group or a heterocyclic group, Rt2 represents an aromatic group or a heterocyclic group, and R4
31R44 and R4S represent a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group.

Below are R51+ R52+R53, R54+Rss
+d and e will be explained in detail.

R5I has the same meaning as R4g *R52 has the same meaning as RaI, R,, C0N- group, Ra 10CON- group, R4 unit
R43 R,,5o2N- group, R,,NC0N- group, R43R4
4Ras Roo- group, R,, S- group, halogen atom, or R4
, N- group; d represents 0 to 3;

When d is plural, the plural R5ts represent the same two substituents or different rIt substituents, and each RS! may become divalent groups and connect to form a cyclic structure.

Typical examples of divalent groups for forming a cyclic structure include: Here r is an integer from 0 to 4,
g represents an integer from 0 to 2, respectively *R1ff is R4
, 2 represents a group with the same meaning as R4+, Rss represents a group with the same meaning as R□, R,,0CONH-
Group, R,, So, NH- group, R,2N CON 6,
R,, NS○2N- group, Ram Ras
R44R45When there is a plurality of R5S representing R, 20- group, R4, S- group, halogen atom or R,, N-5, each R (ff) 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, (
1) Amino, hexyl, cyclohexyl, 2-ethylhexyl, octyl, 1,1,3.3-tetramethylbutyl, decyl, dodecyl, hexadecyl, or octadecyl.

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 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.

Typical examples of heterocyclic groups include 2-pyridyl, 2-thienyl, 2-furyl, 1,3.4-thiadiazole-2-
yl, 2,4-dioxo-1,3-imidazolidine-5
-yl, 1,2.4-)lyazol-2-yl or 1
-Pyrazolyl.

When the aliphatic hydrocarbon group, aromatic group and heterocyclic group have a substituent, typical substituents include a halogen atom, R,, o- group, R4, s- group, group, R4, SO, N-
Group, R,, NSO2- group, R4? R, @RahS Oz- group, R4? ○CO- group, R41R
49 group, cyano group or nitro group. Here R4
b represents an aliphatic group, an aromatic group, or a heterocyclic group, and R
4□, R4, and R49 are each an aliphatic group, an aromatic group,
Represents a heterocyclic group or a hydrogen atom. Aliphatic, aromatic or heterocyclic have the same meanings as defined above.

In the general formula (Cp-6), R5I is preferably an aliphatic group or an aromatic group. *Lt is preferably a chloro atom, an aliphatic group or R, or a CONH- group, and d is preferably 1 or 2. R5ff is preferably an aromatic group.

In the general formula (Cp-7), Rsz is R,,C0NH
- groups are preferred. d is preferably l.

R54 is preferably an aliphatic group or an aromatic group.

In general formula (Cp-8), e is preferably O or 1 *R5S is R,,0CONH- group, R,,C0
NH- group or R, SO□NH- group is preferable, and the substitution position thereof is preferably the 5-position of the naphthol ring.

The timing group represented by T is a group whose bond with X is cleaved after the bond with Cp is cleaved by a coupling reaction between the coupler and the oxidized product of the aromatic primary amine developer;
It is used for various purposes such as adjusting coupling reactivity, stabilizing couplers, and adjusting release timing below X. Examples of the timing group include the following known groups.

In the following, *marks are bonded to CP, **marks are bonded to X, or *marks are bonded to CP, and **marks are bonded to Q, respectively.

(T-1) (T-2) CH, -** (T~3) (T-4) (T-5) (T-6) *-OCH -* In the formula, RIa is substituted with a benzene ring represents a possible group, R
1 has the same meaning as described for R41, and RI!
represents a hydrogen atom or a substituent, t represents an integer from 0 to 4 * RIG and a substituent for R12 include R4
1, halogen atom, R, ff0-R,, S-1R8 (R
4-) NCO-1R, 300C-R4zSOz-1R4
3(R,4)NSCh −R=sCON (R4a)−
1R-+ S Oz N (R4s) -R,,C0
-1R,1COO-1R,,50-, nitro, R43(
R44) NC0N (R4S)-, Cyano, R, 0
CON (R,j) -1Ra y OS Oz-R,
2(R4,)N-R4! (R-4)NSO□N(Ras)-1 or (
T-7) *-QC-** is an integer of 0 or 1, but it is generally preferable that k is 0, that is, that Cp and X are directly bonded.

X is a divalent linking group bonded to one or more (T) by N, O or S, -0- to S-II II
II II-〇C--
〇CO--〇C3--0CNH--O20,--○5O
zNH- or N (T).

A heterocyclic group bonded to the above (e.g. pyrrolidine, piperidine, morpholine, piperazine, pyrrole, pyrazole,
Derived from imidazole, 1,2,4-triazole, benzotriazole, succinimide, phthalimide, oxazolidine-2,4-dione, imidazolidine-2,4-dione, 1,2,4-triacylidine-3,5-dione, etc. ) or these groups and alkylene groups (
(e.g. methylene, ethylene, propylene), cycloalkylene groups (e.g. 1,4-cyclohexylene), arylene groups (e.g. 0-phenylene, p-phenylene), 2
valent heterocyclic groups (e.g. groups derived from pyridine, thiophene, etc.), -CO-SO, -CO0--CONH -SotNH--3o, O--NHCO--NH3O,
-1=NHCONH- -NH3O, NH--NHCOO-, etc., are preferred as a composite linking group. More preferably, X is represented by the general formula (It).

General formula ([[)%Formula% In the general formula (II), * is the position where it is bonded to (T)k or more, ** is the position where it is bonded to Q or less, X is 10- or -S-, L is an alkylene group, x2 is a single bond, -o
--s--c.

CNHSCh NHNH30t --so, o --
oso, --○C○-NH302NH--0C5-
-5CO-o 0 -osot NH- or -NH3O! 〇-, m is 0~
The total number of carbon atoms of X (hereinafter referred to as the number of C), which represents an integer of 3, is preferably 0 to 12, more preferably 0 to 8. The most preferred X is -0CR, CH, O-.

Q represents an arylene group or a divalent heterocyclic group. When Q is an arylene group, the arylene group may be a substituent (for example, a halogen atom, hydroxyl, carboxyl, sulfo, nitro, cyano, amine, ammonium,
phosphono, phosphino, alkyl, cycloalkyl, aryl, carbonamide, sulfonamide, alkoxy, aryloxy, acyl, sulfonyl, carboxyl, carbamoyl, sulfamoyl), and the number of C is preferably 6 to 15, and more Preferably 6-10
It is. When Q is a divalent heterocyclic group, the heterocyclic group is a 3- to 8-membered, preferably 5- to 7-membered heterocyclic group containing at least one petro atom selected from N, O, S, P, Se, or Te in the ring.
jii monocyclic or condensed heterocyclic groups (e.g. lysine, thiophene, furan, pyrrole, pyrazole, imidazole, thiazole, oxazole, benzothiazole, benzoxazole, benzofuran, benzothiophene, l, 3,4-thiadiazole, indole) , a group derived from quinoline, etc.), which may have a substituent (same as the substituent when Q is an arylene group), and the number of C is preferably 2 to 15, more preferably 2 to 15. 10
It is. It is the most preferable as Q, and therefore the most preferable in the present invention.

When R+, Rz or R1 is an alkyl group, the alkyl group may be linear or branched, may contain an unsaturated bond, and may contain a substituent (for example, a halogen atom,
and toxyl, carboxyl, sulfo, phosphono, phosphino, cyano, alkoxy, aryl, alkoxycarbonyl, amino, ammoniamyl, acyl, carbonamide, sulfonamide, carbamoylsulfonyl).

When R,, Rz or R3 is a cycloalkyl group,
A cycloalkyl group is a 3- to 8-membered cycloalkyl group, even if it has a bridging group or an unsaturated bond, and if the substituent (R, R. or R, is an alkyl group) may have the same substituent.).

R, ,R. Or, when R is an aryl group, even if the aryl group is a condensed ring, there are substituents (in addition to substituents when R, R2 or R is an alkyl group, there are alkyl, cycloalkyl, etc.) It may have.

When R+, Rz or R, is a heterocyclic group, the heterocyclic group is a 3 to 8 membered (preferably 5 ~7 noble) monocyclic or fused ring heterocyclic group (
For example, imidazolyl, thienyl, pyrazolyl, thiazolyl, pyridyl, quinolinyl), and the substituent (R+
, Rz or R, is the same as the substituent when it is an aryl group)
It may have.

Here, the carboxyl group may contain a carboquinrad group, the sulfo group may contain a sulfonate group, the phosphino group may contain a phosphinate group, and the phosphono group may contain a phosphonate group, and in this case, counterions include Li'Na'', K'', ammonium etc.

R1 is preferably a hydrogen atom, a carboxyl group, or a C number of 1 to
10 alkyl groups (e.g. methyl, t-butyl, carbomethyl, 2-sulfomethyl, carboxymethyl, 2-carboxymethyl, 2-hydroxymethyl, benzyl, ethyl, isopropyl) or C6 to C2 aryl groups (e.g. phenyl , 4-methoxyphenyl, 4-sulfophenyl), and particularly preferably a hydrogen atom, a methyl group or a carboxyl group.

R2 is preferably a cyano group, a carboxyl group, or a C number of 1 to
10 carbamoyl groups, sulfamoyl groups having 0 to 10 carbon atoms, sulfo groups, alkyl groups having 1 to 10 carbon atoms (e.g. methyl, sulfomethyl), sulfonyl groups having 1 to 10 carbon atoms (e.g. methylsulfonyl, phenylsulfonyl), C @1
~10 carbon amide groups (e.g. acetamide', benzamide) or sulfonamide groups with 1 to 10 carbon atoms (
Examples include evamethanesulfonamide, toluenesulfonamide), and particularly preferably a cyano group, a carbamoyl group, or a carboxyl group.

R is preferably a hydrogen atom, an alkyl group having 1 to 12 carbon atoms (e.g. methyl, sulfomethyl, carboxymethyl, 2
-sulfomethyl, 2-carboxymethyl, ethyl, n-
butyl, benzyl, 4-sulfobenzyl) or C number 6
~15 aryl groups (e.g. phenyl, 4-carboxyphenyl, 3-carboxyphenyl, 4-methoxyphenyl, 2,4-dicarboxyphenyl, 2-sulfophenyl, 3-sulfophenyl, 4-sulfophenyl, 2,
4-disulfophenyl, 2.5-disulfophenyl), more preferably a C1-7 alkyl group or C
It is an aryol group having numbers 6 to 1o.

Specifically, R4 is an acyl group represented by the general formula (I[I) or a sulfonyl group represented by the general formula (rV).

General formula (Il[) C General formula (IV) R. , So. ~ When R1+ is an alkyl group, the alkyl group may be linear or branched, may contain an unsaturated bond, and may contain a substituent (for example, a halogen atom, hydroxyl, carboxyl, sulfo, phosphono, phosphino, cyano,
alkoxy, aryl, alkoxycarbonyl, amino, ammoniamyl, acyl, carbonamide, sulfonamide, carbamoyl, sulfamoyl, sulfonyl)
It may have.

When R11 is a cycloalkyl group, the cycloalkyl group is a 3- to 8-membered cycloalkyl group, and even if it has a bridging group or an unsaturated bond, the substituent (R
When 11 is an alkyl group, it may have the same substituent).

When RI+ is an aryl group, the aryl group may be a fused ring or may have a substitution, M (in addition to substituents when R, is an alkyl group, there are alkyl, cycloalkyl, etc.). good.

When R1+ is a heterocyclic group, the heterocyclic group has at least one
A 3- to 8-membered (preferably 5- to 7-membered) monocyclic or fused-ring heterocyclic group containing a heteroatom selected from N, S, O, P, Se, or Te in the ring (e.g., imidazolyl,
thienyl, pyrazolyl, thiazolyl, pyridyl, quinolinyl), and may have a substituent (same as the substituent when R31 is an aryl group).

Here, the carboxyl group may contain a carboxylade group, the sulfo group may contain a sulfonate group, the phosphino group may contain a phosphinate group, and the phosphono group may contain phosphonate x, and the counterion is Li.

These include Na'', ni°, ammonium, etc.

RI+ is preferably an alkyl group having 1 to 10 carbon atoms (e.g. methyl, carboxymethyl, sulfoethyl, cyanethyl), a cycloalkyl group having 5 to 8 carbon atoms (e.g. cyclohexinope 2-carboxycyclohexyl), or a cycloalkyl group having 6 to 6 carbon atoms. -10 aryl groups (phenyl, 1-naphthyl, 4-sulfophenyl), particularly preferably C1-3 alkyl groups and C6 aryl groups.

R3 is a substitutable group, preferably an electron-donating group, particularly preferably -NR+zR+3 or -OR
,, is. The preferred substitution position is the 4-position, R1
1, R1ff and R14 are a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group. Further, a ring may be formed between RIz and RI2, and the nitrogen heterocycle formed is preferably an alicyclic ring.

j represents an integer from O to 4, preferably 1 or 2, particularly preferably 1.

When R9 or RIG is an alkyl group, the alkyl group may be straight or branched, may contain an unsaturated bond, and may contain a substituent (for example, a halogen atom, hydroxyl, carboxyl, sulfo, phosphono). , phosphino, cyan, alkoxy, aryl, alkoxycarbonyl, amino, ammonillamyl, acyl, carbonamide, sulfonamide, carbamoyl, sulfamoyl, sulfonyl).

When R7 or Rto is a cycloalkyl group, the cycloalkyl group is a 3- to 8-membered cycloalkyl group, even if it has a bridging group or an unsaturated bond,
It may have a substituent (same as one substituent when R or R1° is an alkyl group).

When R9 or R10 is an aryl group, even if the aryl group is a condensed ring, it may include alkyl, cycloalkyl, etc. in addition to the substituent R, or R, . may have.

When R9 or R1゜ is a heterocyclic group, the heterocyclic group is a 3 to 8R (preferably 5
~7-membered) monocyclic or fused ring heterocyclic group (e.g. imidazolyl, thienyl, pyrazolyl, thiazolyl, pyridyl, quinolinyl), which has a substituent (R, or R +
When o is an aryl group, it may have the same substituent).

Here, the carboxyl group may contain a carboxylade group, the sulfo group may contain a sulfonate group, the phosphino group may contain a phosphinate group, and the phosphono group may contain a phosphonate group, and the counterion is Li.

These include Na', K'', ammonium, etc.

R7 is preferably a cyano group, a carboxyl group, or a C number of 1 to
10 carbamoyl group, C2-10 alkoxycarbonyl group, C7-11 aryloxycarbonyl group, C0-10 sulfamoyl group, sulfo group, C1
~1o alkyl group (e.g. methyl, carboxymethyl, sulfomethyl), C1-10 sulfonyl group (e.g. methylsulfonyl, phenylsulfonyl), C1-1
10 carbonamide groups (e.g. acetamide, benzamide), C1-10 sulfonamide groups (e.g. methanesulfonamide, toluenesulfonamide), alkyloxy groups (e.g. methoxy, ethoxy) or aryloxy groups (e.g. phenoxy). Particularly preferred are a cyano group, a carbamoyl group, an alkoxycarbonyl group, and a carboxyl group.

R1 is preferably a hydrogen atom, an alkyl group having I to 12 carbon atoms (e.g. methyl, sulfomethyl, carboxymethyl, ethyl, 2-sulfoethyl, 2-carboxyethyl,
3-sulfopropyl, 3-carboxypropyl, 5-sulfopentyl, 5-carboxypentyl, 4-sulfobenzyl) or a C6-15 aryl group (e.g. phenyl, 4-carboxyphenyl, 3-carboxyphenyl, 2. 4-dicarboxyphenyl, 4-sulfophenyl, 3-sulfophenyl, 25-disulfophenyl, 2
．． (4-disulfophenyl), and more preferably an alkyl group having 1 to 7 carbon atoms or an aryl group having 6 to IO carbon atoms.

Specific examples of CP in general formulas (CI) to (CrV) are shown below.

(Example of Cp) H Cs H+, (n) (i) C, H, OCN +1H (i) C4H90CN 1H (i) C, H, 0CN 11H -3CH,Coo-,-○CHCONH-CH.

0CH1C1h O3O□-5-○C0-OCH,CH
-, -OCH, CHCHl -CO, HCo□H OCH, CHO-.

0CRCH,0 Co,H CO□H (Example of Q) (Example of X) 0-, -'S-, -OCH,-, -OCH,CH,--
OCH, CH, O-, -OCH, CH, CH, 0--0
(CH,CH,O), -, -OCH,CH,5--
OCH, CH, NHC○-, -OCH, CH, NH30
,--OCH,CHz so□-,0CHz CHz
QC○-1OCHICHZCo, 5CHZCON
H.

I.G. H CH.

CH2CH.

Oz　Na Co,H 3O3Na R7゜ ShiUzn Oz　Na O3Na Yellow color of the present invention Tonen coupler ingredients Shows the side of the body, It is not limited to these.

(YC-1) (YC-2) (VC (YC (YC (YC-9) (YC-4) (YC-5) (YC-6) (YC-10) (YC (YC-12) (YC -13) (YC (YC-15) (YC-20) H CH2CHz SOi Na (YC (YC (YC H (YC-22) (YC-23) H 3○=Na (YC-24) (YC (YC -28) (YC-29) Ch H+1(n) C= HIz(n) 0OH (YC-27) (YC-30) (YC-31) (YC-32) H C○0H CtH2 C,H,, (n) zHs C○0H Ni'1UU1., nko (YC-33) 0H (VC H ShikuYC H (YC Cs Ho, (n) NHCOCHz H NMCQCHs (YC (YC (VC-38) H (YC ( YC (YC (YC-44) (YC-47) (YC-48) (YC (VC (YC-49) (YC-50) CH2CH3 (YC-51) CH2Co, H (YC-54) CHI cHz so, The yellow colored coupler represented by the general formula (CI) of the present invention can generally be synthesized by a diazo coupling reaction between a 6-hydroxy-2 pyridone and an aromatic diazonium salt or a heterocyclic diazonium salt containing a coupler structure. .

The former, 6-hydroxy-2-pyridones, are described in "Heterocyclic Compounds - Pyridine and Its Derivatives - Part 3" edited by Klinsberg (Interscience Publishing, 1962).
), Journal of the American Chemical Society (J.

Am, Chem, Soc, ) 1943, 65 volumes,
449 pages, Journal of the Chemical Technology and Biotechnology (J, Chem, T.
ech.

BioLechnol, ) 1986, Volume 36, 41
Page 0, Tetrahedron 1
966, Vol. 22, p. 445, Japanese Patent Publication No. 61-52827, West German Patent No. 2,162.612, No. 2.349.7
No. 09, No. 2,902,486, U.S. Patent No. 3,763
．． It can be synthesized by the method described in No. 170 and the like.

The latter diazonium salt is disclosed in U.S. Patent No. 4.004°929.
No. 4,138,258, JP-A-61-72244
No. 61-273543 and the like. The diazo coupling reaction between 6-hydroxy-2-pyridones and diazonium salts can be carried out using methanol, ethanol, methyl cellosolve, acetic acid, N,N-dimethylformamide, N,N-dimethylacetamide,
The reaction can be carried out in a solvent such as tetrahydrofuran, dioxane, water, or a mixed solvent thereof. At this time, sodium acetate, potassium acetate, sodium carbonate, potassium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide, pyridine, triethylamine, tetramethylurea, tetramethylguanidine, etc. can be used as the base.

The reaction temperature is usually -78°C to 60°C, preferably 20°C.
°C to 30°C.

Examples of synthesis of the yellow colored coupler of the present invention are shown below.

○ Compound supervision aO) Synthetic taurine 125.2g and potassium hydroxide 66g methanol 500rr+j! was added, heated and stirred, and 110 g of methyl cyanoacetate was added dropwise over about 1 hour.

After heating under reflux for 5 hours, it was left to stand overnight, and the precipitated crystals were filtered.
By washing with ethanol and drying, 202.6 g of crystals of compound a were obtained.

± 11.5 g of Kikushinjounikizo compound a and 3.5 g of potassium carbonate and 11 g of water
．． 5 mf was added thereto, 7.8 g of ethyl acetoacetate was added dropwise while heating and stirring on a steam bath, and the mixture was further stirred for 7 hours. 9.2 m of hydrochloric acid after cooling! ! .

By adding and stirring, crystals were precipitated. The mixture was filtered, washed with methanol, and dried to obtain 10.4 g of crystals of the compound.

1 g of the compound clo synthesized by the synthesis method described in U.S. Patent No. 4,138,258 of Kaboo YC-1 was dissolved in 60 mf of N,N dimethylformamide and 60 mf of methyl cellosolve, and the solution was poured into 4.3 ml of hydrochloric acid under water cooling. was added, and then a 5 ml solution of 1.84 g of sodium sulfite was added dropwise to prepare a diazonium solution.Next, to 7.8 g of compound b and 2 g of sodium acetate was added 60 mj2 of methyl cellosolve and 20 m2 of water.
The diazonium solution was added dropwise while stirring under water cooling, and the mixture was further stirred for 1 hour and at room temperature for 2 hours, and the precipitated crystals were filtered. After washing with water and drying, the crystals were dispersed in 500 mj2 of methanol, heated under reflux for 1 hour, and then allowed to cool. By filtering the crystals, washing them with methanol, and drying them,
Red crystals of the desired exemplary coupler (YC-1) 13.
6g was obtained.

The melting point of this compound was 269-272°C (decomposed) and the structure was confirmed by 'HNMR spectrum, mass spectrum and elemental analysis. The maximum absorption wavelength of this compound in methanol is 457.7 nm, and the molecular extinction coefficient is 41.
300, and showed good spectral absorption characteristics as a yellow colored coupler.

(Synthesis Example 2) Synthesis of Exemplary Coupler (YC-3) JP-A No. 6
75r of N,N-dimethylformamide was added to 19.2g of the compound d synthesized by the synthesis method described in No. 2-85242.
Add r+42 and 75mf of methyl cellosolve and melt.
While stirring under water cooling, 5.6 ml of monohydrochloric acid was added, and then a solution of 2.5 g of sodium nitrite in 5 ml of water was added dropwise.

After dropping for 1 hour, the mixture was stirred at room temperature for another 1 hour to prepare 8 diazonium solutions.

Compound blo, 1 g and sodium acetate 10.7 g to 75 m of methyl cellosolve! and 26 mf of water were added, and while stirring under water cooling, the diazonium solution was added dropwise. After 0 dropwise addition, the mixture was further stirred for 2 hours at room temperature, and the precipitated crystals were filtered. Next, 200 mj of crystal! A solution of 2.2 g of sthorium hydroxide in 10 mIV of water was added dropwise, and the mixture was stirred for 3 hours. After neutralization with concentrated hydrochloric acid, the precipitated crystals were washed with water and methanol, and then dried. By purifying the obtained crude crystals with hot methanol in the same manner as in Synthesis Example 1, the desired exemplary coupler (YC3) was obtained in 14.
I got 8g. The melting point of this compound was 246-251°C (decomposed), and the structure was confirmed by 'HNMR spectrum, mass spectrum and elemental analysis. The maximum absorption wavelength of this compound in methanol was 457.6 nm, the molecular absorption coefficient was 42,700, and it exhibited good spectral absorption characteristics as a yellow colored coupler.

= O 137.1 g of anthranilic acid was added to 600 m of acetonitrile.
The mixture was heated and stirred, and 92.5 g of diketene was added dropwise over about 1 hour. After heating under reflux for 1 hour, the mixture was cooled to room temperature, and the precipitated crystals were filtered, washed with acetonitrile, and dried to obtain 200.5 g of compound e crystals.

■1 compound gold layer compound e199.1g, ethyl cyanacetate 89°2g,
Add 344 g of 28% sodium methoxide to 0.0 g of methanol.
91 and reacted for 8 hours at 120°C in an autoclave. - After standing overnight, the reaction mixture was concentrated under reduced pressure, and water
mf was added, and the mixture was acidified with hydrochloric acid with 230 ml of concentrated hydrochloric acid. The precipitated crystals were collected by filtration, and the obtained crude crystals were heated and washed with a mixed solvent of ethyl acetate and acetonitrile to obtain compound f, 152.
I got g.

Synthesis of Exemplary Coupler (YC-28) 13.0 g of compound g, synthesized according to the synthesis method described in US Pat. No. 4,138,258, was dissolved in 40 mf of NN-dimethylformamide, cooled with water, and 4.0 mf of concentrated hydrochloric acid. 5mj
! and then add 1.48 g of sodium nitrite in 5 m of water.
j! The solution was added dropwise to prepare a diazonium solution. Next, compound f6. Add 20mf of N,N-dimethylformamide and 15mj2 of water to 8g of Og and sodium acetate,
The diazonium solution was added dropwise while stirring under water cooling.

After the dropwise addition, the mixture was further stirred at room temperature for 30 minutes. acidify with hydrochloric acid,
After extraction with ethyl acetate and washing with water, the mixture was concentrated under reduced pressure, and the concentrate was recrystallized from a mixed solvent of ethyl acetate and methanol to obtain 13 g of yellow crystals of the exemplary coupler (YC-28).

The melting point of this coupler (VC-28) was 154-6°C, and the structure was confirmed by HNMR spectrum, mass spectrum, and elemental analysis. The maximum absorption wavelength of this compound in methanol is 458.2 nm, and the molecular extinction coefficient is 42.
800, showing good spectral absorption characteristics as a yellow colored coupler.

V ○=Q ○ (1) Synthetic phenyl ester compound, L 445.5g and isopropanolamine! 90.1g of acetonitrile 600mI
The mixture was heated under reflux for 2 hours. After cooling with water, the precipitated crystals were collected by filtration and dried to obtain 37,342 g of a compound. mp, 162
-5°C (2) Synthesis of Compound Σ 341 g of hydroxyl compound and 231 g of 2-hexyldecanoyl chloride were heated under reflux in 880 ml of acetonitrile for 2 hours, and after cooling with water, the precipitated crystals were collected by filtration and dried to form the compound, 437 g of L was obtained.

mp, 97-100°C (3) Synthesis of compound 370 g of nitro substance Σ, 6 g of 10% Pd-C catalyst, and ethyl acetate In were charged into an autoclave and hydrogenated at 50°C for 3 hours. After completion of the reduction, the catalyst was filtered off, and the filtrate was concentrated under reduced pressure. The resulting residue was crystallized with n-hexane, and the precipitated crystals were collected by filtration and dried to obtain amine compound 2. 327g was obtained.

mp, 95-7°C (4) Synthesis of Exemplary Coupler YC-42 720.8 g of amine compound was dissolved in dimethylformamide 60A, and 7.5 g of concentrated hydrochloric acid was added under water cooling. 6rM! was added. Furthermore, add 2.7 g of sodium nitrite and 10 ml of water to 20
The mixture was added dropwise over several minutes, and stirring was continued for 30 minutes to prepare a diazo solution.

Meanwhile, add 79.7 g of pyridone and 13 g of sodium acetate to 30 g of water.
ml! , dimethylformamide (301 nl), and after heating and dissolving, cooling with water, the above diazo solution was slowly added while stirring at 10° C. or lower.

After continuing stirring for an additional 15 minutes, extraction was carried out with ethyl acetate.
Washing with water was performed three times. The organic layer was concentrated under reduced pressure, and the residue was crystallized from methanol-ethyl acetate. The precipitated crystals were collected by filtration and dried to obtain 21.2 g of exemplary coupler YC-42.

mp, 117-96C The yellow colored cyan couplers represented by the general formulas (CI) to (CIV) are described in Japanese Patent Publication No. 58-6939, Japanese Patent Application Laid-open No. 197563/1993, and the method for synthesizing the couplers represented by the general formula (CI). It can be synthesized by methods described in patents and the like.

In the present invention, general formula (CI) and general formula (Cn
) Yellow-colored cyan couplers represented by the formula (CI) are more preferably used, and those represented by the general formula (CI) are particularly preferably used.

The yellow-colored cyan coupler of the present invention is added to the green-sensitive silver halide emulsion layer and/or its adjacent layer in the light-sensitive material. When the green-sensitive emulsion layer is composed of two or more layers having different sensitivities, it may be added to any of the layers (the highest sensitivity layer, the intermediate sensitivity layer and/or the lowest sensitivity layer). In addition, the non-photosensitive layer adjacent to the green-sensitive emulsion layer includes a non-photosensitive layer located between the green-sensitive emulsion layers, a non-photosensitive layer between the green-sensitive emulsion layer and a different color-sensitive emulsion layer (e.g. yellow filter, etc.), and it is particularly preferable to add it to the yellow filter layer.

The total amount added to the photosensitive material is 0.003 to 0°20g/
rn', preferably 0. O1~0.15g/rT
? , more preferably 0. 03~0. It is 10g/M.

The yellow-colored cyan coupler of the present invention can be added to a photosensitive material in the same manner as a conventional coupler, as described below.

The light-sensitive material of the present invention has at least 11 silver halide emulsion layers of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer on a support.
There is no particular restriction on the number and order of the silver halide emulsion layer and the non-photosensitive layer. A typical example is a silver halide photographic window light having on a support at least one light-sensitive layer consisting of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different light sensitivities. The photosensitive layer is a unit photosensitive layer sensitive to blue light, green light, or red light, and in a multilayer silver halide color photographic light-sensitive material, the unit photosensitive layer is sensitive to -g The color layers are arranged in this order from the support side: a red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer. However, depending on the purpose, the above-mentioned order of installation may be reversed, or the order of installation may be such that different photosensitive layers are sandwiched between the same color-chromic layer.

Non-photosensitive layers such as various intermediate layers may be provided between the above-mentioned silver halide photosensitive layers and between the uppermost layer and the lowermost layer.

The intermediate layer includes JP-A Nos. 61-43748 and 59-1.
No. 13438, No. 59-113440, No. 61-20
Coupler, DIR compound, etc. as described in No. 037 and No. 61-20038 may be included,
It may also contain a commonly used color mixing inhibitor.

A plurality of silver halide emulsion layers constituting each unit photosensitive layer are composed of a high-speed emulsion layer and a low-speed emulsion layer, as described in German Patent No. 1,121,470 or British Patent No. 923.045. A two-layer configuration can be preferably used.

Usually, it is preferable to arrange the layers so that the photosensitivity decreases toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer.
No. 112751, No. 62200350, No. 62-20
As described in No. 6541, No. 62-206543, etc., a low-sensitivity emulsion layer may be provided on the side far from the support, and a high-sensitivity emulsion layer may be provided on the side close to the support.

As a specific example, from the side farthest from the support, low sensitivity blue sensitive layer (BL) / high intensity blue sensitive layer (Bl() / high sensitivity green sensitive layer (Gll) / low sensitivity green sensitive layer N ( GL
) / high-sensitivity red-sensitive layer (R) I) / low-sensitivity blue-sensitive layer (RL), or BH / BL / GL / Gll / RH
/RL order, or 8B/BL/GH/GL/RL/R
They can be installed in the order of H, etc.

Further, as described in Japanese Patent Publication No. 55-34932, from the side farthest from the support, the blue-sensitive layer/Gll/
They can also be arranged in the order of R1(/GL/IIL.Also, as described in JP-A-56-25738 and JP-A-62-63936, the blue-sensitive layer/ They can also be arranged in the order of GL/RL/Gll/RH.

In addition, as described in Japanese Patent Publication No. 49-15495, the upper layer is a silver halide emulsion layer with the highest sensitivity, the middle layer is a silver halide emulsion layer with lower sensitivity, and the lower layer is more sensitive than the middle layer. An example is an arrangement consisting of three layers with different photosensitivity, in which a silver halide emulsion layer with a low density is disposed and the photosensitivity gradually decreases toward the support. Even when it is composed of three layers with different photosensitivity, as described in JP-A No. 59-202464,
In the same color-sensitive layer, a medium-temperature emulsion layer/high-temperature emulsion layer/low-temperature emulsion layer may be arranged in this order from the side remote from the support.

In addition, high-sensitivity emulsion layer / low-sensitivity emulsion layer / medium-sensitivity emulsion layer,
Alternatively, they may be arranged in the order of low-speed emulsion layer/medium-speed emulsion layer/high-speed emulsion layer, etc.

Furthermore, even in the case of four or more layers, the arrangement may be changed as described above.

As mentioned above, various layer structures and arrangements can be selected depending on the purpose of each photosensitive material.

The preferred silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention is silver iodobromide, silver iodochloride, or silver iodochlorobromide, containing about 30 mol% or less of silver iodide. . Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mole percent to about 10 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 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) Nα17643
(December 1978), pp. 22-23, ``1. Emulsion preparation
d types)”, and Nα18716 (
November 1979), 648 pages, Nα30710
5 (November 1989), pp. 863-865, and "Physics and Chemistry of Photography" by Glafkides, published by Beaumontel (P, Glafkides, Chemie et P.
h1sique Photographique, P
aul Montel, 1967), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (G, F, Du
ffinPhotographic Emulsion
Chemistry (Focal Press19
66)), “Manufacture and Coating of Photographic Emulsions” by Zelikman et al.
Published by Focal Press (V, L, Zelikmane
tal、Making and Coating
Photographic E+wul-sion,
Focal Press, 1964).

U.S. Patent No. 3,574.628, U.S. Patent No. 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 3 or greater can also be used in the present invention. Tabular grains are described by Gutoff, Photographic Science and Engineering.
ence and Engineering), Vol. 14, pp. 248-257 (1970); U.S. Patent No. 4
, 434.226, 4,414.310, 4,
433,048, British Patent No. 4,439.520, and British Patent No. 2.112.157.

The crystal structure may be --like, the inside and outside may have different halogen compositions, it may be a layered structure, or silver halides with different compositions may be joined by epitaxial bonding. They may also be bonded with compounds other than silver halide, such as silver rhodan or lead oxide, and mixtures of particles of various crystal forms may be used.

The above-mentioned emulsions may be of the surface latent image type that forms latent images primarily on the surface, of the internal latent image type that forms inside the grains, or of the type that has latent images both on the surface and inside the grains, but negative-tone emulsions It is necessary that Among the internal latent image type emulsions, a core/shell type internal latent image type emulsion described in JP-A-63-264740 may be used. A method for preparing this core/shell type internal latent image type emulsion is described in JP-A-59-133542.

The thickness of the shell of this emulsion varies depending on development processing and the like, but is preferably 3 to 40 nm, particularly preferably 5 to 20 nm.

The silver halide emulsion used is usually one that has been subjected to physical ripening, chemical ripening, and spectral sensitization. Additives used in such processes are subject to Research Disclosure Nα1
7643, Nα18716, and Kaikai 307105, and the relevant parts are summarized in the table below.

The photosensitive material of the present invention includes grain size, grain size distribution, halogen composition, grain shape,
Two or more types of emulsions differing in at least one characteristic of sensitivity can be mixed and used in the same layer.

Silver halide grains coated with grain surfaces as described in U.S. Pat. No. 4,082,553, U.S. Pat. No. 4,626,4
Silver halide grains and colloidal silver with covered grain interiors described in No. 98 and JP-A No. 59-214852 are preferably used in a photosensitive silver halide emulsion layer and/or a substantially non-photosensitive hydrophilic colloid layer. Can be used.

Silver halide grains that have their interiors or surfaces covered are defined as - (
refers to silver halide grains that can be developed (non-imagewise). A method for preparing silver halide grains with a fogging inside or on the grain surface is described in U.S. Pat.

The silver halides forming the inner core of the core/shell type silver halide grains whose interiors are fogged may have the same halogen composition or may have different halogen compositions. As the silver halide coated inside or on the surface of the grain, any of silver chloride, silver chlorobromide, silver iodobromide, and silver chloroiodobromide can be used. Although there is no particular limitation on the grain size of these fogged silver halide grains,
The average particle size is preferably 0.01 to 0.75 μm, particularly 0.05 to 0.6 μm. In addition, there are no particular limitations on the particle shape, and regular particles may be used.
It may be a polydisperse emulsion, but it may be a monodisperse emulsion (at least 95% of the weight or number of silver halide grains is ±4 of the average grain size).
0% or less) is preferable.

In the present invention, it is preferred to use non-photosensitive fine grain silver halide. Non-photosensitive fine grain silver halide is a silver halide fine grain that is not exposed to light during imagewise exposure to obtain a dye image and is not substantially developed during the development process. preferable.

The fine grain silver halide has a silver bromide content of 0 to 100 mol %, and may contain silver chloride and/or silver iodide as necessary. Preferably, it contains 0.5 to IO mol% of silver iodide.

The fine grain silver halide preferably has an average grain size (average diameter equivalent to a circle of projected area) of 0.01 to 0.5 μm, and preferably 0.01 to 0.5 μm.
02 to 0.2 μm is more preferable.

Fine-grain silver halide can be prepared in the same manner as ordinary photosensitive silver halide. In this case, the surface of the silver halide grains does not need to be optically sensitized, nor is spectral sensitization necessary. However, before adding these to the coating solution, it is preferable to add a known stabilizer such as a triazole group, azaindene type, benzothiazolium type, or mercapto type compound or zinc compound in advance. Colloidal silver can preferably be contained in the silver halide grain-containing layer.

The coating silver amount of the light-sensitive material of the present invention is preferably 6.0 g/bo or less, most preferably 4.5 g/bo or less.

Known photographic additives that can be used in the present invention are also described in the three Research Disclosures mentioned above, and the relevant descriptions are shown in the table below.

In addition, in order to prevent deterioration of photographic performance due to formaldehyde gas, US Pat.
It is preferable to add to the light-sensitive material a compound that can be immobilized by reacting with formaldehyde as described in No. 435.503.

The photosensitive material of the present invention includes U.S. Patent No. 4,740,454, U.S. Pat.
It is preferable to contain a mercapto compound described in JP-A No. 1283551.

A compound that releases a fogging agent, a development accelerator, a silver halide solvent, or a precursor thereof irrespective of the amount of developed silver produced during the development process, which is described in JP-A-1-106052, is added to the light-sensitive material of the present invention. It is preferable to contain.

International Publication 1v088104794
It is possible to contain dyes dispersed by the method described in Japanese Patent Application Publication No. 11-502912 or dyes described in BP 317,308A, U.S. Pat. preferable.

Various color couplers can be used in the present invention, specific examples of which are listed in Research Disclosure N.
α17643, ■-C-G, and Nα307105
, ■-〇-G.

As a yellow coupler, for example, U.S. Patent Tube 3.93
No. 3,501, No. 4,022,620, No. 4.3
No. 26,024, No. 4,401,752, No. 4,
No. 248,961, Japanese Patent Publication No. 58-10739, British Patent No. 1,425,020, British Patent No. 1,476.760, U.S. Patent No. 3,973,968, Japanese Patent No. 4.314.
No. 023, No. 4,511,649, European Patent No. 24
9.473A, etc. are preferred.

As magenta couplers, 5-pyrazolone and pyrazoloazole compounds are preferred, and US Pat.
No. 0,619, No. 4,351,897, European Patent No. 73,636, U.S. Patent No. 3,061,432,
No. 3725.067, Research Disclosure No. 24220 (June 1984), JP-A No. 6
No. 0-33552, Research Disclosure Nα
24230 (June 1984), JP-A-60-436
No. 59, No. 61-72238, No. 60-35730, No. 55-118034, No. 60-185951,
U.S. Patent No. 4°500.630, U.S. Patent No. 4,540,6
No. 54, No. 4.556,630, International Publication WO38
Particularly preferred are those described in No. 104795 and the like.

Cyan couplers include phenolic and naphthol couplers, and are described in U.S. Patent No. 4.052.212.
No. 4.146.396, No. 4,228.23
No. 3, No. 4.296.200, No. 2.369.9
No. 29, No. 2,801.171, No. 2.772.
No. 162, No. 2.895.826, No. 3,772
．． No. 002, No. 3.758.308, No. 4,33
No. 4.011, No. 4,327,173, West German Patent Publication No. 3329.729, European Patent No. 121.365A
No. 249453A, U.S. Patent No. 3,446,6
No. 22, No. 4.333,999, No. 4,775,
No. 616, No. 4,451,559, No. 4,427
．． No. 767, No. 4,690,889, No. 4, 2
No. 54212, No. 4,296,199, JP-A-61
-42658 etc. are preferred. Furthermore, JP-A No. 64.553, No. 64-554, No. 64-55
5, No. 64-556 and the imidazole couplers described in U.S. Pat. No. 4,818,672 can also be used.

Typical examples of polymerized dye-forming couplers are U.S. Pat.
No. 4.576910, British Patent No. 2.102.1
No. 37, European Patent No. 341188A, etc.

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.

In addition to the colored couplers of the present invention, colored couplers for correcting unnecessary absorption of coloring dyes include Research Disclosure No. 17643 ■-G item and Nα307105
Section ■-G, U.S. Patent No. 4,163,670, Japanese Patent Publication No. 57-39413, U.S. Patent No. 4,004,929, Japanese Patent No. 4.138.258, British Patent No. 1.146.
No. 368 is preferred, and also U.S. Pat.
, 774,181, which uses a fluorescent dye released during coupling to correct the unnecessary 9 yield of a coloring dye; and U.S. Pat. No. 4,777,120, which reacts with a developing agent to form a dye. It is also preferred to use couplers which have a dye precursor group as a leaving group.

Compounds that release photographically useful residues upon coupling can also be preferably used in the present invention.

DIR couplers that release development inhibitors are the aforementioned RD
17643, ■-F section and Doso 307105, ■-F
The patent described in JP-A-57451944, JP-A-57451944,
No. 7-154234, No. 60-184248, No. 63
-37346, 6337350, U.S. Patent 4,2
Preferred are those described in No. 48.962 and No. 4.7B2.012.

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.

Also, JP-A-60-107029, JP-A No. 60-2523
40, JP-A No. 1-44940, and JP-A No. 1-45687, compounds that release a glaring agent, a development accelerator, a silver halide solvent, etc. through a redox reaction with an oxidized form of a developing agent are also preferred. .

Other compounds 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. , DIR redox compound releasing couplers, DIR coupler releasing couplers, DIR described in JP-A-60485950, JP-A-6224252, etc.
Coupler-releasing redox compound or DIR redonx-releasing redox compound, European Patent No. 173°302A
No. 313.308A, a coupler that releases a dye that recovers color after separation, R, D, No. 11449,
No. 24241, bleach accelerator releasing coupler described in JP-A-61-201247, etc., U.S. Patent No. 4,555.47
Ligand releasing coupler described in No. 7 etc., JP-A-63-7
Couplers that release leuco dyes described in US Pat. No. 5,747, couplers that release fluorescent dyes described in US Pat. No. 4,774,181, and the like.

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 US Pat. No. 2,322,027 and the like.

The boiling point at normal pressure used in the oil-in-water dispersion method is 175°C.
Specific examples of the above-mentioned high boiling point organic solvents include phthalic acid esters (dibutyl phthalate, dichlorohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis(2,4-di-t-amylphenyl) phthalate, bis( esters of phosphoric acid or phosphonic acid (triphenyl phosphate, tricresyl phosphate, 2-
Ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, l-lichloropropyl phosphate,
di-2-ethylhexylphenylphosphonate, etc.),
Benzoic acid esters (2-ethylhexyl benzoate, dodecyl benzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), amides (N, N-diethyl dodecanamide, N, +1 diethyl lauryl amide, N-tetradecyl pyrrolidone, etc.), alcohols or phenols (isostearyl alcohol, 2.4
-di-tert-amylphenol, etc.), aliphatic carboxylic acid esters (bis(2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc.), aniline derivatives (N, N -dibutyl 2
-butoxy-5-tert-octylaniline, etc.),
Examples include hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.).

Further, as the auxiliary solvent, an organic solvent having a boiling point of about 30°C or higher, preferably 50°C or higher and about 160°C or lower, can be used, and typical examples include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, and cyclohexanone. , 2-ethoxyethyl acetate, dimethylformamide, and the like.

Specific examples of latex dispersion process steps, effects, and latex for impregnation include U.S. Pat. It is described in.

The color photosensitive material of the present invention contains phenethyl alcohol and JP-A-63-257747, JP-A-62-272248
1,2-benzisothiazolin-3-one, n-butyl p-hydroxybenzoate, phenol, 4-chloro-3,5 described in JP-A-1-80941
-dimethylphenol, 2-phenoxyethanol, 2
It is preferable to add various preservatives or antifungal agents such as -(4thiazolyl)benzimidazole.

The present invention can be applied to various color photosensitive materials. Typical examples include color negative film for general use or movies, color reversal film for slides or television, color paper, color positive film, and color reversal paper.

Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D, page 28 of floor 17643, page 647 right column to page 648 left column of circular 18716, and page 87 of 307105.
It is described on page 9.

In the photosensitive material of the present invention, the total thickness of all the hydrophilic colloid layers on the side having the emulsion layer is preferably 28 μm or less, more preferably 23 μm or less, even more preferably 18 μm or less, and 16 μm or less. Particularly preferred, the membrane swelling rate TI/□ is preferably 30 seconds or less, more preferably 20 seconds or less. The film thickness was measured at 25°C and 55% relative humidity (2
It means the film thickness measured in days), and the film swelling rate T I /□
can be measured according to techniques known in the art.
Photographic Science and Engineering (Photogr, Sci, Eng)
), Vol. 19, No. 2, pp. 124-129, T I/□ can be measured using a swellometer (swelling membrane) of the type described in Vol. 19, No. 2, pp. 124-129. The saturated film thickness is defined as 90% of the maximum swollen film thickness reached at that time, and is defined as the time until the saturated film thickness reaches 172.

The membrane swelling rate Tl/□ can be adjusted by adding a hardening agent to gelatin as a binder or by changing the aging conditions after coating. Further, the swelling rate is preferably 150 to 400%. The swelling rate can be calculated from the maximum swollen film thickness under the above-mentioned conditions according to the formula: (maximum swollen film thickness - film thickness)/film thickness.

The photosensitive material of the present invention is preferably provided with a hydrophilic colloid layer (referred to as a back layer) having a total dry film thickness of 2 μl to 20 μl on the side opposite to the side having the emulsion layer. The swelling rate of this back layer is 150-500% is preferred.

The color photographic material according to the present invention includes the above-mentioned RD,
NCL 17643, pages 28-29, same N (L 1B7
16-651 left column to right column and same seed 307105-8
It can be developed by the usual method described on pages 80-881.

The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. Aminophenol compounds are also useful as color developing agents, but p-phenylenediamine compounds are preferably used, representative examples of which are 3-methyl-4-amino-N, N-diethylaniline, 3-methyl- 4-amino-N-ethyl-N-β
- hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-Nβ-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-β-methoxyethylaniline and sulfates thereof, Examples include hydrochloride and p-toluenesulfonate. Among these, especially 3-methyl-4-amino-N-ethyl-N
β-hydroxyethylaniline sulfate is preferred, and two or more of these compounds may be used in combination depending on the purpose.

The color developer may contain pH buffering agents such as alkali metal carbonates, borates or phosphates, chloride salts, bromide salts,
It is common to include development inhibitors or antifoggants such as iodide salts, hengimidazoles, hendithiazoles or mercapto compounds. In addition, if necessary, various preservatives such as hydroxylamine, diethylhydroxylamine, sulfites, hydrazines such as N,N-biscarboxymethylhydrazine, phenyl semicarbazides, triethanolamine, catechol sulfonic acids, ethylene glycol, etc. , organic solvents such as diethylene glycol, development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts, amines, dye-forming couplers, competitive couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity. Imparting agent, aminopolycarboxylic acid, aminopolyphosphonic acid,
Various chelating agents such as alkylphosphonic acids and phosphonocarboxylic acids, such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1, 1-diphosphonic acid, = trilo! 11.11. Representative examples include N-trimethylenephosphonic acid, ethylenediamine-N, N, N, N-tetramethylenephosphonic acid, ethylene glycol (0-hydroxyphenylacetic acid), and salts thereof.

Further, when performing reversal processing, black and white development is usually performed and then color development is performed. This black-and-white developer contains known black-and-white developing agents such as dihydroxydhenzenes such as hydroquinone, 3-pyrazolidones such as -phenyl-3-pyrazolidone, or aminophenols such as N-methyl-p-aminophenol. It can be used alone or in combination.

The pH of these color developing solutions and black and white developing solutions is generally 9 to 12. Although the amount of replenishment of these developing solutions depends on the color photographic light-sensitive material being processed, it is generally less than 3E per square meter of light-sensitive material, and by reducing the bromide ion concentration in the replenisher,
It can also be less than d. When reducing the amount of replenishment, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the area of contact with the air in the processing tank.

The contact area between the photographic processing solution and air in the processing tank can be expressed by the aperture ratio defined below.

That is, the above aperture ratio is preferably 0.1 or less, more preferably 0.001 to 0.05. As a method for reducing the aperture ratio in this way, in addition to providing a shield such as a floating lid on the surface of the photographic processing liquid in the processing tank,
Method using a movable lid described in No. 033, JP-A-63
The slit development processing method described in Japanese Patent No. 216050 can be mentioned. Reducing the aperture ratio is important not only for both color development and black and white development processes, but also for subsequent processes,
For example, it is preferable to apply it to all steps such as bleaching, bleach-fixing, fixing, washing, and stabilization.Also, the amount of replenishment can be reduced by using means to suppress the accumulation of bromide ions in the developer. .

The time for color development processing is usually set between 2 and 5 minutes, but the processing time can be further shortened by using high temperature, high pH, and high concentration of color developing agent.

After color development, the photographic emulsion layer is usually bleached.

The bleaching process may be carried out simultaneously with the fixing process (bleach-fixing process) or separately, or in order to speed up the process, a bleach-fixing process may be performed after the bleaching process. Furthermore, treatment with two consecutive bleach-fixing baths, fixing treatment before bleach-fixing treatment, or bleaching treatment after bleach-fixing treatment can be carried out as desired depending on the purpose. As the bleaching agent, for example, compounds of polyvalent metals such as iron (Cl1l), peracids, quinones, nitro compounds, etc. are used. Typical bleaching agents include organic complex salts of iron (Ill), such as aminopolymer salts such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, and glycol ether diaminetetraacetic acid. Carboxylic acids or complex salts of citric acid, tartaric acid, malic acid, etc. can be used. Among these, aminopolycarboxylic acid iron (Il[) complex salts, including ethylenediaminetetraacetic acid iron (m) complex salt and 1,3-diaminopropanetetraacetic acid iron (I[[) complex salt], are useful for rapid processing and environmental pollution prevention. More preferable from this point of view, iron aminopolycarboxylate (I[)
Complex salts are particularly useful in both bleach and bleach-fix solutions. These aminopolycarboxylic acid iron(ill)
The pH of the bleach or bleach-fix solution using tf salt is usually 4.
0-8, but lower pH for faster processing
It can also be processed with

A bleach accelerator may be used in the bleaching solution, bleach-fixing solution, and their prebaths, if necessary.

Specific examples of useful bleach accelerators are described in U.S. Pat. No. 3,893,858, German Pat.
, No. 290.812, No. 2,059,988, JP-A-53-32736, No. 53-57831, No. 53-
No. 37418, No. 53-72623, No. 53-956
No. 30, No. 53-95631, No. 53-104232
Compounds having a mercapto group or a disulfide group described in JP-A No. 53-124424, No. 53-141623, No. 53-28426, Research Disclosure No. NC117129 (July 1978), etc.; JP-A-50-140129 Thiazolidine derivatives described in Japanese Patent Publication No. 45-8506, Japanese Patent Publication No. 52-20832, Japanese Patent Publication No. 53-32735, U.S. Patent No. 3,706,56
Thiourea derivatives described in No. 1; West German Patent No. 1.127,
No. 715, iodide salts described in JP-A-58-16,235; West German Patent Nos. 966.410 and 2,748.43
Polyoxyethylene compounds described in No. 0; Japanese Patent Publication No. 1973
-Polyamine compound described in No. 8836; Other JP-A No. 4
No. 9-40,943, No. 49-59,644, No. 53
-94.927, 54-35,727, 55-
Compounds described in No. 26,506 and No. 58-163.940; bromide ions, etc. can be used. Among these, compounds having a mercapto group or a disulfide group are preferred from the viewpoint of a large promoting effect, and are particularly preferred as described in U.S. Pat. No. 3,893,85.
No. 8, West German Patent No. 1.290,812, Japanese Unexamined Patent Publication No. 1983-
The compounds described in U.S. Pat. No. 95,630 are preferred, and the compounds described in U.S. Pat. These bleach accelerators are particularly effective when bleach-fixing materials.

In addition to the above-mentioned compounds, bleach and bleach-fix solutions contain I! for the purpose of preventing bleach staining! It is preferable to include an acid, and a particularly preferable organic acid is a compound having an acid dissociation constant (pKa) of 2 to 5, and specifically, acetic acid, propionic acid, hydroxyacetic acid, etc. are preferable.

Examples of fixing agents used in fixing solutions and bleach-fixing solutions include thiosulfates, thiocyanates, 1,000-onythyl compounds, thioureas, and large amounts of iodide salts. Ammonium dithiosulfate is the most common and most widely used. It is also preferable to use a combination of thiosulfate, thiocyanate, thioether compounds, thiourea, etc. As a preservative for fixing solutions and bleach-fixing solutions, sulfites, bisulfites, carbonyl bisulfite adducts, or European patented The sulfinic acid compounds described in No. 294769A are preferred. Furthermore, various aminopolycarboxylic acids and organic phosphonic acids are preferably added to the fixing solution and bleach-fixing solution for the purpose of stabilizing the solution.

In the present invention, the fixing solution or bleach-fixing solution has a pH m
In order to maintain the temperature, a compound having a pKa of 6.0 to 9.0, preferably imidazoles such as imidazole, 1-methylimidazole, 1ethylimidazole, and 2-methylimidazole, is added at 0.1 to 10 mol/i. is preferred.

The total time for the desilvering process is preferably as short as possible without causing desilvering defects.The preferred time is 1 minute to 3 minutes, more preferably 1 minute to 2 minutes. In addition, the processing temperature is 25°C ~
50'C3 is preferably 35°C to 45°C. In a preferred temperature range, the desilvering rate is improved and the occurrence of staining after processing is effectively prevented.

In the desilvering step, it is preferable that stirring be as strong as possible. Specific methods for strengthening agitation include the method of impinging a jet of processing liquid on the emulsion surface of the photosensitive material described in JP-A No. 62-183460, and the method described in JP-A No. 62-183.
No. 461, a method of increasing the stirring effect using a rotating means, and further improving the stirring effect by moving the photosensitive material while bringing the emulsion surface into contact with a wiper blade provided in the liquid to create turbulence on the emulsion surface. Examples include a method of increasing the circulation flow rate of the entire treatment liquid. Such means for improving agitation is effective for all bleaching solutions, bleach-fixing solutions, and fixing solutions. It is believed that improved stirring speeds up the supply of bleach and fixing agent into the emulsion film, and as a result increases the desilvering rate. Further, the agitation improving means described above is more effective when a bleach accelerator is used, and can significantly increase the accelerating effect and eliminate the fixing inhibiting effect caused by the bleach accelerator.

The automatic developing machine used for the photosensitive material of the present invention is
No. 0-191257, No. 60-191258, No. 60
It is preferable to have a photosensitive material conveying means as described in Japanese Patent Laid-open No. 191259-1912. This effect is particularly effective in shortening the processing time in each step and reducing the amount of processing solution replenishment.

It is preferable that the silver halide color photographic light-sensitive material of the present invention undergoes a water washing and/or stabilization step after the desilvering treatment.

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 washing tanks and the amount of water in the multistage countercurrent method is
urn-al of the 5ociety
of Motion Picture and
Te1evision Engineers No. 64
It can be determined by the method described in Vol., P, 2.18-253 (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 significantly reduced, but due to the increase in the residence time of water in the tank, bacteria will breed, and the generated suspended matter will adhere to the photosensitive material. 6. In the processing of the color photosensitive material of the present invention, these problems can be solved by:
The method for reducing calcium ions and magnesium ions described in JP-A No. 62-288.838 can be used very effectively. Also, JP-A-57-8,542
Chlorinated disinfectants such as isothiazolone compounds, cyabendazole, chlorinated sodium isocyanurate, and other benzotriazoles listed in the issue, Hiroshi Horiguchi, "Chemistry of antibacterial and fungicidal agents J (1986), Sankyo Publishing, Hygiene Technology synthesis “Microbial sterilization, sterilization, and anti-mildew technology J (1982)
Society of Industrial Engineers, Japan Antibacterial and Antifungal Society “Encyclopedia of Antibacterial and Antifungal Agents” (
It is also possible to use the fungicides described in (1986).

The pH of the washing water in the processing of the photosensitive material of the present invention is 4 to 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 to 45°C, preferably 30 seconds to 5 minutes at 25 to 40°C. A range 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 No. 57-854
All known methods described in No. 3, No. 5B-14834, and No. 60-220345 can be used.

Further, following the water washing treatment, a further stabilization treatment may be carried out. For example, a stabilization bath containing a dye stabilizer and a surfactant, which is used as a final bath for a color photosensitive material for photographing, may be further carried out. can be mentioned. Examples of the dye stabilizer include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine, and aldehyde sulfite adducts.

Various chelating agents and antifungal agents can also be added to this stabilizing bath.

The overflow liquid resulting from the water washing and/or replenishment of the stabilizing liquid can also be reused in processes such as the desilvering process.

When each of the above-mentioned processing liquids is concentrated by evaporation in processing using an automatic processor or the like, it is preferable to correct the concentration by adding water.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up processing. In order to incorporate a color developing agent, it is preferable to use various precursors of the color developing agent. U.S. Patent Tube 3.342,59
Indoaniline compound described in No. 7, No. 3,342,
No. 599, Research Disclosure 14, 85
0 and Nα15.159, aldol compounds described in U.S. Patent No. 13.924, metal salt complexes described in U.S. Pat.
Examples include urethane compounds described in No.-135628.

The silver halide color light-sensitive material of the present invention may contain various 1-phenyl-3-
Pyrazolidones may also be incorporated.

Typical compounds are JP-A-56-64339 and JP-A No. 57-
No. 144547 and No. 58-115438.

Various treatment liquids in the present invention are used at 10'C to 50'C. Normally, the standard temperature is 33°C to 38°C, but higher temperatures may be used to accelerate processing and shorten processing time, or conversely, lower temperatures may be used to improve the quality and stability of the processing solution. can be achieved.

Further, the silver halide photosensitive material of the present invention is disclosed in U.S. Pat.
No. 500,626, JP-A-60-133449, No. 5
It can also be applied to the heat-developable photosensitive materials described in No. 9-218443, No. 61-238056, European Patent No. 210.66OA2, and the like.

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

Example 1 On a subbed cellulose triacetate film support,
Sample 101, which is a multilayer color photosensitive material, was prepared by applying layers having the compositions shown below.

(Photosensitivity 1i!i & [!N) The numbers corresponding to each component indicate the coating amount expressed in g/i units, and for silver halide, the coating amount is expressed in terms of silver. However, for sensitizing dyes, halogenated tH in the same layer
The coating amount per mole is shown in mole units.

(Sample 101) 1st layer (Haley silane prevention layer) Black colloidal silver Silver o, 18 gelatin 1.40 2nd layer (intermediate layer) 2.5-di-L-pentadecylhydroquinone 0.1SE
-10,070 EX -30,020 EX-122,0xlO-' 0.060U
-20,080 U-30,1゜HBS-10,10 HBS-2 Third gelatin layer (first red-sensitive emulsion layer) Emulsion A Emulsion B Sensitizing dye I Sensitizing dye ■ Sensitizing dye ■ X-2 X -10 Exemplary coupler (YC-28) J-2 J-3 B5-1 Gelatin 4th layer (second red-glare emulsion layer) Emulsion G Sensitizing dye ■ Sensitizing dye ■ 0.020 1.04 Silver 0.25 Silver 0.25 6.9X10-5 1.8X10-' 3, lX10-' 0.34 0.020 0.015 0.070 0.050 0.070 0.060 0.87 Silver 1.00 5, lX1O -5 1,4X 10-' Sensitizing dye■ Sensitizing dye■ X-2 X-3 .070 1.30 1 barb 1.60 5.4X10-'L4X10-' 2.4 X 10-' 0,097 o, ot.

O,080 0,017 0,22 0,10 gelatin 6th layer (middle layer) X-5 B5-1 gelatin 7th layer (first green emulsion N) Emulsion A Emulsion B Sensitizing dye■ Sensitizing dye■ Sensitizing dye■ X-1 Eχ-6 X-7 X-8 X-10 B5-1 B5-3 gelatin 8th layer (second green emulsion layer) 1.63 0.040 0.020 o, g.

i 艮 0.15 Silver 0.15 3.0X10-' 1.0X10-' 3.8X10-' o,oi.

0.015 0.035 0.00B 0.10 0.010 0.63 Emulsion C Sensitizing dye■ Sensitizing dye V Sensitizing dye■ X-6 X-7 X-8 X-10 B5-1 B5-3 Gelatin 9th layer (third green-sensitive emulsion layer) Emulsion B Emulsion E Enhanced dye■ Sensitizing dye■ Enhanced dye■ X-1 X-10 X-11 Silver 0.45 2, lX10-'7.0X10-' 2 .6 -' 0.025 0.010 0.10 EX-13 HB S - ] HB S -2 Gelatin 10th layer (yellow filter layer) Yellow colloidal silver EX-5 B5-1 Gelatin 11th layer (first blue-sensitive emulsion Layer) Emulsion A Emulsion B Emulsion F Sensitizing dye ■ EX-8 EX-9 B5-1 Gelatin 12th layer (second blue emulsion layer) Emulsion G 0.015 0.25 0.10 1.54 Silver 0. 050 0.080 0.030 0.95 Silver 0.080 Silver 0.070 Silver 0.070 3.5X10-' 0.042 0.72 0.28 1.10 Silver 0.45 Sensitizing dye■ EX-9 EX-1゜B5-1 Gelatin 13th layer (third blue-sensitive emulsion layer) Emulsion H Sensitizing dye ■ EX-9 B5-1 Gelatin 14th layer (first protective layer) Emulsion r B5-1 Gelatin 15th layer (Second protective layer) B-1 (diameter 1.7 μm) 2, lX10-' 0.15 7.0X10-3 0.050 0.78! ! 0.77 2.2X10-' 0.20 0.070 0.69 Silver 0.20 0.11 0.17 5.0XIO-" 1.00 0.40 5.0X10-" B-2 (Diameter 1. 7 μm) 0.10
B-30,1O 5-10,20 Gelatin 1.20 Furthermore, in order to improve preservability, processability, pressure resistance, anti-fungal and anti-bacterial properties, antistatic properties and coating properties, w-1 is added to the entire layer. , W-2, W
-3, B-4, B-5, FL F-2, F-3, F-4
, F-5, F-6, F-7, F-8, F-9, F-10
, F-11, F-12, F-13, and iron salt, lead salt, gold salt, platinum salt, iridium salt, and rhodium salt.

(Sample 102) Sample 102 was prepared by adding 0.015 g/m of coupler RC-1 to the eighth layer and ninth layer of sample 101, respectively.

(Samples 103 to 112) Samples 103 to 112 were prepared by replacing RC-1 in the eighth and ninth layers of Sample 102 with the comparative couplers shown in Table 1 and the yellow colored cyan coupler of the present invention in equimolar amounts.

These samples were imagewise exposed to green light and subjected to the following color development process to determine sensitivity and gamma.

The sensitivity is the relative value of the logarithm of the reciprocal of the exposure amount that gives a magenta density of (fog + 0.2), and Sample 101 was set to 0. Gamma is the slope of the straight line connecting the densities of (fog + 0.2) and (fog + 1.2). In addition, after applying green imagewise exposure, uniform exposure to blue and red was applied, and the following color development was performed, and the values obtained by subtracting the respective fog densities from the yellow and cyan densities at the magenta density (fog + 1.2) were obtained. Table 1 shows the degree of color turbidity for each.

Similar processing is performed for sharpness to obtain the conventional MTF.
(Modulation Transfer Func
tion) method, and the value of 25 cycles/mm for yellow and cyan images was measured.

Further, after performing the same exposure as the green imagewise exposure,
After storage for 7 days under 40% relative humidity conditions (forced deterioration conditions), color development was performed to determine the change in relative sensitivity.

Furthermore, 24 images of 135 cartridge size were taken and processed from samples 101 to 112 using a Minolta (M camera α-7700).
A Macbeth color chart was photographed with a TSO400 setting and subjected to the following color development process.

The processed sample was enlarged to 10 times magnification using Fuji Enlarger 690 Professional, and Fuji Color Super H
It was printed on G paper and subjected to CP-23A standard processing. The color was adjusted so that neutral gray (optical density 0°44) in the Macbeth color chart became gray. Table 1 shows the evaluation of color reproduction on green prints.

These photographed photosensitive materials were subjected to the following color development process.

The processing solution used was one subjected to standard exposure of Super HRI [-100] and processed until the replenishment amount of each solution was three times that of the mother solution tank (Champion 23S automatic processor).

Processing method Processing time Processing temperature Replenishment amount Tank capacity 3 minutes 15 seconds
38°0 45d loAl minute 00 seconds 38
℃ 20J 473 minutes 15 seconds 38℃ 3
0i 8j7 Color development Bleaching Bleach Fixing Washing with water C2) 1 minute 00 seconds 35℃ Stable 40 seconds 38℃ Drying 1 minute 15 seconds 55℃ Replenishment amount is 35W + m width, per 1m length Next, the composition of the processing solution Write down.

(Color developer) Diethylenetriaminepentaacetic acid 1-hydroxyethylidene-3 (7' 41 Mother liquid axis) Replenisher (g) 20m/4j? 1.0 1.1 1, 1-diphosphonic acid Sodium sulfite Potassium carbonate Potassium bromide Potassium iodide Hydroxylamine sulfate 4-[N-ethyl-N-β hydroxyethylamino] 2-Methylaniline sulfate 4.5 Water Add 1.01p H10,0
5 (Bleach solution) Common to mother solution and replenisher solution (Unit g) Ethylenediaminetetraacetic acid ferric ammonium dihydrate Ethylenediaminetetraacetic acid disodium chloride Ammonium bromide Ammonium nitrate Bleach accelerator ■ 0.0 100.0 ] 0. O O,005 mol 120.0 3.0 4.0 30.0 1.4 1.5mg 2.4 2.8 5.5 1.0R 10,10 Ammonia water (27%) Add 15.0ml water te 1,01p)1
6. 3 (Bleach-fix solution) Common to mother solution and replenisher (Unit: g) Ethylenediaminetetraacetic acid ferric ammonia water dihydrate Ethylenediaminetetraacetic acid disodium salt Sodium sulfite Ammonium thiosulfate Ammonia water (27%) Add water to pH (Washing solution ) Common tap water for mother liquor and replenisher was mixed with H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and OH-type anion exchange resin (Amber 5, O 12,0 6, 0rr1 1, Ol 7.2 Water was passed through a mixed bed column packed with 50,0 Lite IR-400) to reduce the concentration of calcium and magnenium ions to below 3 ■/l, followed by 20 mg/A of sodium dichloride isocyanurate. and 0.15 g/ff of sodium sulfate were added.

The pH of this solution is 6. 5-7. It was in the range of 5.

(Stable solution) Common to mother solution and replenisher solution (Unit: g) Formalin (
37%) 2. 0ml'polyoxyethylene-p-7tnonylphenylethyl (average degree of polymerization 10) 0.3 Ethylenediaminetetraacetic acid disodium salt 0.05 Add water 1.01 pH 5,0-8,0 pH 6,3 Table 1 Therefore, Samples 105 to 112, in which the yellow-colored cyan coupler of the present invention was used in the green-sensitive layer, have balanced yellow and cyan color turbidity and are small, which is favorable for green color reproduction, and that yellow and cyan images are MTF
It is clear that the sharpness expressed by the value is excellent, and there is little change in photographic properties over time from exposure and photographing to development.

Example 2 Yellow colloidal silver in the 10th scrap of sample 1.01 of Example 1 was reduced to 0.010 g/m, and EX-5 was reduced to 0.015 g.
/% to prepare sample 201.

(Sample 202) RC-1 was added at 0.035 g/n (
sample 202 was obtained.

(Samples 203 to 21O) Samples 203 to 210 were prepared by replacing RC-1 in sample 202 with other couplers in equimolar amounts as shown in Table 2.

These samples were evaluated for relative sensitivity, gamma, color turbidity, green color reproduction by printing, and MTF value according to Example 1. However, the MTF value was also evaluated for magenta images. In addition, the color development processing method was changed to the following. The results obtained are summarized in Table 2.

Processing process Processing time Processing temperature Replenishment amount Tank capacity Color development 3 minutes 15 seconds 37.8°C 25mf 1
0A bleach 45 seconds 38.0°C 5mA
51 fixation (1) 45 seconds 38.0°C
5n fixing (2) 45 seconds 38.0°C30
mff 541! Stable (1) 20 seconds 3
8.0°C5jl+stable (2) 20 seconds 3
8.0°C51 stable (3) 20 seconds 38,
0°C40m#5. ff drying 1 minute 55°
C The amount of replenishment is per 1 d of 35 mm width, the fixing is by countercurrent method from (2) to (1), the stability is by countercurrent method from (3) to (11), the amount of developer carried into the bleaching process, and the fixing solution. The amount brought into the stabilization process was 2.5rr+1.2.0m1 per 1m length of the 35mm wide photosensitive material.

The composition of the treatment liquid is shown below.

(Color developer) Mother solution (g) Replenisher (
g) Diethylenetriaminepentaacetic acid 5.0 6.0 Thorium sulfite 4.0 5.0 Potassium carbonate
30.0 37,0 Potassium Bromide
l, 30.5 potassium iodide
1.2mg hydroxylamine sulfate 2.0
3.64-[N-ethyl-N-β 4,7 6
．． Add 2-hydroxyethylaminoco-2-methylaniline sulfate solution 1. OA 1. of
pH 10,0010,15 (Bleach solution) Mother liquor (g) Replenisher solution (g)
1,3-diaminopropane 144.0 206.
0 Ferric ammonium tetraacetate hydrate 1.3-diaminopropane 2.8 4.0 Ammonium bromide tetraacetate 84.0 120.0 Ammonium nitrate 17.5 25.0 Aqueous ammonia (27%) 10.0 1 .8 Acetic acid (98%) 51.1 73.0 Add water 1. OIl, 01 pH 4,33,4 (Fixer) Common to mother liquor and replenisher (g) Ethylenediaminetetraacetic acid 1. 7 Disodium salt Sodium sulfite 14.0 Sodium bisulfite 1O10 Ammonium thiosulfate aqueous solution 210.0 mβ (70% fi/volume) Ammonium thiocyanate 163.0 Thiourea
1.8 Add water
1.01 pH 6,5 (Stable solution) Common to mother solution and replenisher (g) Surfactant Surfactant l/Reethanolamine ■, 2-benzisothiazolin 3-one methanol formalin (37%) Add water and turn H 0° 0゜2.0 0.3 ■, 5 1.0f 6, 5 From Table 2, the sample containing the yellow colored cyan coupler of the present invention in the yellow filter layer has excellent color reproducibility and sharpness. It is clear that there are.

Example 3 Colloidal silver and EX-5 in the 10th layer of sample 201 were removed to prepare sample 301.

(Sample 302) 0.045g/0.045g of RC-1 was added to the first O layer of Sample 301.
rr? , 0.010 g/mr was added to the 8th layer to prepare sample 30.
It was set as 3.

(Samples 303 to 310) Samples 303 to 310 were prepared by replacing RC-1 in sample 302 with other couplers in equimolar amounts as shown in Table 3.

These samples were evaluated according to Example 2. However, the color development method was changed to the one below.

From Table 3, it is clear that the samples containing the yellow colored cyan coupler of the present invention in the yellow filter layer and the green photosensitive layer have excellent color reproducibility and excellent sharpness.

Processing process Processing time Processing temperature Color development 3 minutes 15 seconds 37.8°C Bleaching
45 seconds 38.0°C bleach fixing (1145 seconds 3
8.08C bleach fixing (2145 seconds 38.08C water
Washing (1) 20 seconds 38.0°C Water washing [2120 seconds 38.0°C Stable 20 seconds 38.0°C Drying 1 minute 55°C *Replenishment amount is per 1 meter length of 35-pound width Bleach-fixing Each of the steps of washing and water washing is a countercurrent method from (2) to (1), and the overflow of the bleaching solution is all bleach-fixing (
2) was introduced.

In the above process, the amount of bleach-fix solution carried into the washing process was 2 -/m of 35 mm wide photosensitive material.

(Color developer) Diethylenetriamine 0ml Replenisher (g) 0ml 0ml Tank capacity 25rrl 101 5 ml 4f l Mother liquor (g) °Replenishment amount Pentate Sodium sulfite Potassium carbonate Potassium bromide Potassium iodide Hydroxylamine sulfate 4-[N -Ethyl-N-β Add hydroxyethylaminoco-2-methylaniline sulfate and H (bleaching solution) 1,3-diaminopropanetetraacetic acid ferric ammonium hydroxide 1,3-diaminopropanetetraacetic acid bromide Ammonium ammonium nitrate 3.6 6.2 1.01 1.01 10.00 10.15 Mother liquor (g) Replenisher solution (g) 144.0 206.0 2.8 4.0 84.0 120.0 17.5 25.0 Ammonia water (27%) 10.0 1.8
Acetic acid (98%) 51.1 73.0 Add water 1. O401,0j7pH4,33
,4 (bleach-fix solution) Mother liquor (g) Replenisher solution (g
) Ethylenediaminetetraacetic acid 50.0 Ammonium ethylenediaminetetraacetic acid 5.0 25.0 Disodium salt Ammonium sulfite 12.0 20.0 Ammonium thiosulfate 290. (W 320.
(W aqueous solution (700g/l) ammonia water (27%) 6.07n!15.0
J Add water 1. O401,0fp
H6,88,0 (Washing water) Mother liquor and replenisher Common tap water was mixed with H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and OH-type strongly basic anion exchange resin (Amberlite IR-120B manufactured by Rohm and Haas). IRA-4
Water was passed through a mixed bed column packed with 00) to reduce the concentration of calcium and magnesium ions to 3/1 or less, and then 20/l of sodium isonanurate dichloride and 150/l of sodium sulfate were added. .

The pH of this solution was in the range of 6.5-7.5.

(Stabilizing solution) Common to mother solution and replenisher solution (Unit: g) Formalin (37%) 1. 2mn surfactant 0.4 ethylene glycol
Add 1,0 water
1.01pH5,0-7,0 EX~2 I X-3 X X-6 Cs ■]1a(n) CH.

X X-8 X-11 X-12 C2H5O20゜ EX-13 U-1 Sensitizing dye I Sensitizing dye■ Sensitizing dye■ B.S. to licresyl phosphate Di-n-butyl phthalate Sensitizing dye■ Sensitizing dye■ Multiplying dye■ Exacerbating pigment■ S-1 CH.

l( CH2=CH-5O□-CI.

C0NH-CH2 CH2=CH5o2CHz CONH-C8゜ n=2-4 R.C. ■ 〇　− No. 0 green photosensitive layer Cyan coupler (23) used for R.C. ■ No. 0 green photosensitive layer Cyan coupler C-2) used in RC-3 ■ Green sensitivity with No. 3 Procedural amendment Cyan coupler used in the layer ■-4) 1゜ Display of incidents 1990 Patent Application No. 187796 2゜ name of invention Silver halide color photographic material 3゜ person who makes corrections Relationship with the incident

Claims (6)

[Claims] (1) A green-sensitive silver halide emulsion in a silver halide color light-sensitive material having at least one blue-sensitive silver halide emulsion layer, one green-sensitive silver halide emulsion layer, and one red-sensitive silver halide emulsion layer on a support. A silver halide color photographic material characterized by containing a yellow colored cyan coupler in a layer. (2) The yellow colored cyan coupler is the first aromatic
Due to the coupling reaction with the oxidized product of grade amine developing agent,
Water-soluble 6-hydroxy-2-pyridon-5-ylazo group, water-soluble pyrazolone-4-ylazo group, water-soluble 2
Claim (1) characterized in that the cyan coupler is capable of releasing a compound residue containing a -acylaminophenylazo group or a water-soluble 2-sulfonamide phenylazo group.
The silver halide color photographic light-sensitive material described in . (3) At least one non-light-sensitive layer adjacent to the blue-sensitive silver halide emulsion layer, the green-sensitive silver halide emulsion layer, the red-sensitive silver halide emulsion layer, and the green-sensitive silver halide emulsion layer on the support. 1. A silver halide color photographic material comprising a yellow colored cyan coupler in the non-photosensitive layer. (4) The yellow colored cyan coupler is the first aromatic
Due to the coupling reaction with the oxidized product of grade amine developing agent,
Water-soluble 6-hydroxy-2-pyridon-5-ylazo group, water-soluble pyrazolone-4-ylazo group, water-soluble 2
Claim (3) characterized in that the cyan coupler is capable of releasing a compound residue containing a -acylaminophenylazo group or a water-soluble 2-sulfonamidophenylazo group.
The silver halide color photographic light-sensitive material described in . (5) At least one non-light-sensitive layer adjacent to the blue-sensitive silver halide emulsion layer, the green-sensitive silver halide emulsion layer, the red-sensitive silver halide emulsion layer, and the green-sensitive silver halide emulsion layer on the support. 1. A silver halide color photographic light-sensitive material comprising a yellow-colored cyan coupler in the green-sensitive silver halide emulsion layer and the non-light-sensitive layer. (6) The yellow colored cyan coupler is the first aromatic
Due to the coupling reaction with the oxidized product of grade amine developing agent,
Water-soluble 6-hydroxy-2-pyridon-5-ylazo group, water-soluble pyrazolone-4-ylazo group, water-soluble 2
Claim (5) characterized in that the cyan coupler is capable of releasing a compound residue containing a -acylaminophenylazo group or a water-soluble 2-sulfonamide phenylazo group.
The silver halide color photographic light-sensitive material described in .