JPH0289046A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve reproducibility and to obtain the color photographic sensitive material which decreases after-colors after processing by incorporating dyes the absorption max. wavelength of which in a gelatin film is in a specific range and dyes the absorption max. wavelength of which in the gelatin film is in another specific range into the photographic sensitive material. CONSTITUTION:The photographic sensitive material having at least one layer of silver halide emulsion on a base contains respectively at least >=1 kinds of the dyes the absorption max. wavelength in the gelatin film is from 480nm to 530nm and the dyes the absorption max. wavelength in the gelatin film is from 680nm to 630nm. The half-amplitude level of the absorption of the dyes the absorption max. wavelength in the gelatin film is from 480nm to 530nm is preferably >=90nm and the dyes the absorption max. wavelength in the gelatin film is from 680nm to 630nm is preferably <=100nm. The silver halide color photographic sensitive material which is greatly improved in the color reproducibility is obtd. in this way and the after-colors after processing are decreased.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a silver halide color photographic light-sensitive material, and more particularly to a silver halide color photographic light-sensitive material with improved photographic performance.

(Prior Art) In silver halide photographic materials, photographic emulsion layers or other layers are often colored for the purpose of absorbing light in a specific wavelength range.

When it is necessary to control the spectral composition of light incident on the photographic emulsion layer, a colored layer is provided on the photographic light-sensitive material on the side farther from the support than the photographic emulsion layer.

Such a colored layer is called a filter layer. When there are a plurality of photographic emulsion layers, such as in a zero-layer color light-sensitive material, the filter layer may be located between them.

It is based on the fact that light scattered during or after passing through the photographic emulsion layer is reflected at the interface between the emulsion layer and the support, or at the surface of the light-sensitive material opposite to the emulsion layer, and enters the photographic emulsion layer again. Between the photographic emulsion layer and the support, for the purpose of preventing image blurring, that is, halation,
Alternatively, a colored layer may be provided on the opposite side of the support from the photographic emulsion layer. In the case of a zero-layer color photosensitive material, such a colored layer is called an antihalation layer.
An antihalation layer may be placed between each layer.

Deterioration of image sharpness due to light scattering in the photographic emulsion layer (this phenomenon is generally called irradiation)
In order to prevent this, the photographic emulsion layer is also colored.

These layers to be colored are often composed of hydrophilic colloids, and therefore, for coloring them, a water-soluble dye is usually incorporated into the layer. This dye must satisfy the following conditions.

111 Must have appropriate spectral absorption according to the purpose of use.

(2) being photochemically inert, that is, having an adverse chemical effect on the performance of the silver halide photographic emulsion layer;
For example, reduced sensitivity, latent image regression, or no capri.

(3) Although it is decolored during the photographic processing process, it is dissolved and removed and does not leave any harmful coloring on the photographic material after processing.

Many efforts have been made by those skilled in the art to find dyes that meet these conditions, and the following dyes are known: eg British Patent No. 506,385;
．． No. 429, No. 1.311.884, No. 1,338,
No. 799, No. 1゜385.371, No. 1,467.2
No. 14, No. 1.433, 102, No. 1,553,51
6, JP-A No. 48-85.130, JP-A No. 49-114゜420, JP-A No. 52-20.830, JP-A No. 55-161.
No. 233, No. 59-111,640, U.S. Patent No. 3.
No. 247,127, No. 3,469゜985, No. 3,7
Oxonol dyes having a pyrazolone nucleus or barbyl nucleation described in U.S. Patent Nos. 46,539 and 4,078.933, etc., U.S. Pat.
Other oxonol dyes described in British Patent No. 9,533, British Patent No. 1,278,621, West German Patent No. 2,928,184, British Patent No. 575,691, West German Patent No. 68
No. 0,631, No. 599.623, No. 786.907
No. 907.125, No. 1゜045.609, U.S. Patent No. 4,255.326, JP-A-59-211,
Ab dye described in No. 043 etc., JP-A-50-100
, No. 116, No. 54-118,247, British Patent No. 2
．． Azomethine dyes described in US Pat. No. 014.598 and US Pat. No. 750.031, anthraquinone dyes described in US Pat. No. 2,865.752, and US Pat. No. 2,538.
, No. 009, No. 2,688,541, No. 2,538,
No. 008, British Patent No. 584゜609, British Patent No. 1,210
, No. 252, JP-A No. 50-40.625, No. 51=3
, No. 623, No. 51-10,927, No. 54-118
, No. 247, Special Publication No. 48-3.286, No. 59-37
, No. 303, etc., azomethine dye, Special Publication Sho 2B
-3,082, 44-16,594, 59-2
Styryl dyes described in 8.898, etc., British Patent No. 446,583, British Patent No. 1,335°422, JP-A-5
9-228,250 etc., British Patent No. 1゜075.653, British Patent No. 1,15
3.341, 1.284.730, 1,475
Examples include merocyanine dyes described in US Pat. No. 2,843,486 and US Pat. No. 3,294,539, etc.

Among these, oxonol dyes, which have two pyrazolone nuclei, have the property of being decolorized in developing solutions containing sulfites, and are used as dyes for photosensitive materials as useful dyes that have little negative effect on photographic emulsions. It's here.

(Problem to be Solved by the Invention) However, some dyes belonging to this family may have little effect on the photographic emulsion itself, but may cause spectral sensitization in unnecessary areas of the spectral sensitized emulsion. It has the disadvantage of causing a decrease in sensitivity, which is thought to be due to the desorption of the sensitizing dye.

Furthermore, due to the speeding up of development processing that has been carried out in recent years, some residual particles may remain after processing. In order to solve this problem, it has been proposed to use dyes that are highly reactive with sulfite ions, but in this case, the stability in the photographic film is insufficient, and the concentration may decrease over time. It has the disadvantage that the desired photographic effect cannot be obtained.

In addition, in order to improve color reproducibility and safelight safety in color photosensitive materials, Japanese Patent Laid-Open No. 52-20
No. 830, US Pat. No. 3,746.539, and German Pat. No. 2,928,184 propose the use of certain oxonol dyes. However, in addition to the above-mentioned drawbacks, these methods also have the drawback that, because the spectral absorption of the dye is not appropriate, if a large amount is added to obtain a sufficient effect, the photographic sensitivity may be reduced.

Therefore, an object of the present invention is to provide a color photographic material with improved color reproducibility and with less residual color after processing.

(Means for Solving the Problems) The object of the present invention is to provide a photographic light-sensitive material having at least one silver halide emulsion layer on a support, wherein the maximum absorption wavelength in the gelatin film is 48.
This was achieved by a silver halide color photographic light-sensitive material containing at least one dye having a wavelength of 0 nm to 530 nm and a dye having a maximum absorption wavelength of 58 onm to 63 on- in the gelatin film.

In the silver halide color photographic light-sensitive material achieved by the present invention, the photographic light-sensitive material contains a dye whose maximum absorption wavelength in the gelatin film is from 480 nm to 530 nm and a dye whose maximum absorption wavelength in the gelatin film is 580 nm to 530 nm.
Each of them contains at least one kind of dye having a wavelength of 630 nm to 630 nm.

For such dyes, dyes whose maximum absorption wavelength in the gelatin film is 480 nm to 530 nm have an absorption half-width of 90 nm or more, and dyes whose maximum absorption wavelength in the gelatin film is 58 onm to 530 nm have a half-width of absorption of 90 nm or more. It is desirable that the half width is 1100n or less.

Next, we will discuss dyes related to the present invention whose absorption maximum wavelengths in the gelatin film range from 480 nm to 530 nm and dyes whose absorption maximum wavelengths in the gelatin film range from 5BOnm to 630 nm.
The compound represented by the following general formula [I], or [■], or [■], or [IV], which is particularly preferably used among the dyes in m, will be explained.

General formula [+] R,R.

In the formula, R1 and R3 represent an aliphatic group, an aromatic group, or a heterocyclic group, and R,, R, are -OR.

NR8R, (here, R5 and R represent a hydrogen atom, an aliphatic group, or an aromatic group, and R2 and R6 may be connected to form a 5- or 6-membered ring), and L+ , L
t, L3, L-a, Ls represent a methine group, nl
r n z represents 0 or l, and MS represents hydrogen or other monovalent cation.

General formula [1] In the formula, R1 and R14 are hydrogen atoms, aliphatic groups, aromatic groups,
Heterocyclic group, N R+ t Rl @-N RI? C
ON R+ t Rla, N Rl * COR+ *
, or -NR+*SOz Rts, and RI! ,R
IS is a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group,
Cyano group, sulfonic acid group, NR+tR+aN RIs
CORl 9, N Rt s S Oz R+ *
,N Rl? CON Rl? R+s, G
OOR+t, CON RI? R+s, -COR
,,,5OtR++ or -3o! NR+vR+*
, R13 and R1& are each a hydrogen atom, an aliphatic group,
Aromatic group, heterocyclic group, -OR,, -COOR+y,
COR+*, CON RI? Rr snow, N R
lt Rr *, N R+ m CORI 9 or -N
R+aS Ox R19, -N Rl? COR+
, R+ *, 5OtR+*, -3o, NR, FR1
, -OR? or represents a cyano group (here R1'l, R
1 each represents a hydrogen atom, an aliphatic group or an aromatic group,
R1, represents an aliphatic group or an aromatic group, and R1, and R1
1 or Rts and R19 may be connected to form a 5- or 6-membered ring).

L+, La, Ls, L4% Ls S
n+, n*, and M. have the same meanings as defined in general formula (1).

General formula (III) Rst In the formula, Rx+s Rsts R33 and R34 each represent a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group, and Ll
, Lx, Ll, La, Ls-, n+, nz,
MΦ has the same meaning as the definition in the general expression (general formula).

General formula [JV] In the formula, R3ss R3? , R31 each represent an aliphatic group, an aromatic group, or a heterocyclic residue;
g, Las each represent a methine group, n41 represents l, 2 or 3, provided that either R8, R5, Rst or Rss has a carboxyl group or a sulfo group, and the total number is at least two or more. .

Next, general formula (1) will be explained in more detail.

The aliphatic group represented by R+, Rx, Rs and R6 may be a straight chain, branched or cyclic alkyl group, aralkyl group or alkenyl group, such as methyl, ethyl, n-butyl, benzyl, 2-sulfoethyl, Examples include groups such as 4-sulfobutyl, 2-sulfobenzyl, 2-carboxyethyl, carboxymethyl, trifluoromethyl, dimethylaminoethyl, and 2-hydroxyethyl.

Examples of the aromatic group represented by R+, Rs, Rs, Ra include phenyl, naphthyl, 4-sulfophenyl, 3-sulfophenyl, 2,5-disulfophenyl,
Examples include groups such as 4-carboxyphenyl and 5,7-disulfo-3-naphthyl.

The heterocyclic group represented by R+ or Rs represents a 5- or 6-membered nitrogen-containing heterocyclic group (including fused rings), such as 5-sulfopyridin-2-yl, 5-sulfobenzothiazole-
2-yl and the like.

R, and Rh1 5 or 6 formed by connecting Rh and R1
Examples of the i4 ring include a pyrrolidine ring, a piperidine ring, and a morpholine ring.

Examples of dyes represented by the general formula (2) are shown below.

■ ! -5 Summer-9 ! -10 ■ CH3 CH! ■-8 ! ■ ! -18 ■-19 H (CHi)i So, K (CI-1ri3 So, to ■-20 Examples of methods for synthesizing these compounds are shown below.

Synthesis Example 1-1 (Dye Example 1-1) 3-hydroxy-1-(4'-sulfophenyl)-5
-Pyrazolone 5.1g, N-(2,4-dinitrophenyl)pyridinium hydrochloride 2.8g, ethanol 5Q
When the mixture of mJ is saturated with ammonia gas at 10 to 20°C while stirring, it becomes a homogeneous solution. When this was stirred for 24 hours, dark green-blue crystals were precipitated. The crystals were filtered, thoroughly washed with ethanol and then acetone, and dried to obtain 5.8 g of the desired dye. The maximum absorption wavelength of the aqueous solution of this dye was 584 nm.

Synthesis example! -2 (Dye example!-2) 3-ethoxy-1-(4'-sulfophenyl)-5-
153 g of pyrazolone sodium salt was added to 1. ! M
! was dissolved in 100 g of triethylamine, 71 g of glutacondialdehyde cyanyl hydrochloride was added, and the mixture was stirred at room temperature for 5 hours. - Ethyl acetate 3j after standing overnight! was added, and the precipitated crystals were filtered, thoroughly washed with ethanol and then acetone, and dried. 47 g of the desired dye was obtained. The absorption maximum wavelength of the aqueous solution of this dye was 598 nm.

Synthesis Example I-3 (Dye Example ■-4) 36 g of 3-amino-1-(4'-sulfophenyl)-5-pyrazolone in 250 mm of methanol! was dissolved in 30 g of triethylamine, and 14 g of malonaldehyde dianyl hydrochloride was added while cooling with water, followed by vigorous stirring. The mixture was stirred for 3 hours, and the precipitated crystals were filtered and washed with methanol. After drying, 46 g of the desired dye was obtained. The maximum absorption wavelength of the aqueous solution of this dye was 505 nm.

Synthesis Example ■-4 (Dye Example I-9) 3-hydroxy-1-(4'-sulfophenyl)-5-
Pyrazolone 5.1 g, N-(2,4-dinitrophenyl>-r-picolinium hydrochloride 2.9 g, ethanol 50
When the mixture of m1 is saturated with ammonia gas at 10 to 20°C while stirring, it becomes a homogeneous solution. After stirring for 24 hours, the precipitated crystals were filtered, thoroughly washed with ethanol and then acetone, and dried to obtain 5.0 g of the desired dye. The absorption maximum wavelength of an aqueous solution of this dye was 607 nm.

Synthesis example! -5 (Synthesis of dye example 1-16) 3-ethoxy-
A mixture consisting of 5 g of 1-(3'-sulfopropyl)5-pyrazolone, 2.8 g of glutacondialdehyde cyanyl hydrochloride, 100 mff1 of methanol and 4 g of triethylamine was stirred at 30-40°C for 3 hours. A solution of 2 g of anhydrous potassium acetate in 20 ml of methanol was added to the stirring, resulting in a blue precipitate. After stirring for 1 hour, the precipitate was filtered, thoroughly washed with acetone, and dried to obtain 4.3 g of the desired dye. The aqueous solution of this dye exhibits a blue color, and its absorption pilot flame is 59
It was 6 mμ.

Next, the dye represented by the general formula (n) will be explained in detail.

Ro, Rlt, R+sSR, R, s, R, Rat,
The aliphatic group represented by R11 or R19 is, for example, methyl, ethyl, isopropyl, 2-chloroethyl, trifluoromethyl, benzyl, 2-sulfohensyl, 4-sulfophenethyl, carboxymethyl, 2-carboxyethyl, 2-sulfoethyl, 2 Examples include groups such as hydroxyethyl, dimethylaminoethyl, and cyclopentyl.

R1 Rus-R, R3 R1ff, R11 or Rl
The aromatic group represented by t is, for example, phenyl, naphthyl, 3-sulfophenyl, 4-sulfophenyl, 2.5-
Disulfophenyl, 4-(3-sulfopropyloxy)
Examples include groups such as phenyl, 3-carboxyphenyl, and 2-carboxyphenyl.

Examples of the heterocyclic group represented by R11, R13, RI4 or RI& include groups such as 2-pyridyl, morpholino, and 5-sulfohencyimidazol-2-yl.

Examples of the 5- or 6-membered ring formed by linking R1 and R1, or Rus and R1, include a piperidine ring, a pyrrolidine ring, a morpholine ring, a pyrrolidine ring, and the like.

Specific examples of the dye represented by general formula (II) are shown below.

(N -1) (N -2) (II -3) CHLCHL SO3NA CH, CH1SO2NA (II -4) (II-5) CHG CHG CHTSOSHNETS CHICH4 Island 11nel3 CHS CHG SOA NA Chg! NA (II -6) ) CHs CHx 0H CHx CHt 0H (II-10) (II-7) 1e C yo H3 C*Hs (II-11) The dye represented by the monocatalytic formula (II) is the British patent tube 1゜27
No. 8.621, No. 1,512,863, No. 1.579
, No. 899 or the synthesis examples shown below.

Synthesis Example 11-1 Synthesis of dye ■-1O l-ethyl-6
-Hydroxy-4-methyl-3sulfomethylpyrido-2
-On! 4.0 g of sodium salt, malonaldehyde cyanyl salt M salt 1.981 1.6 mj of acetic anhydride was added dropwise into a mixture of 5.0 ml of triethylamine and 120 ml of isopropyl alcohol, and the mixture was stirred at room temperature for one day. The generated precipitate was collected by filtration, and a mixed solvent of water/methanol = 1/3 was added.
An ethanol solution containing 1.4 g of potassium acetate was added dropwise to this solution, and the resulting precipitate was collected by filtration and dried under reduced pressure. Yield 1゜1g Maximum absorption in water 592n
m, melting point 300°C or higher Synthesis Example n-2 Synthesis of dye 11-1 l-carboxymethyl-3-cyano-6-hydroxy-
3.0 g of 4-methylpyrid-2-one.

1.3.3-Trimethoxypropene (1.3 g), ethylamine (2.8 ml) in ethanol solution is heated under reflux for 2 days. The mixture was cooled to room temperature, and the precipitate was filtered and dried, yielding 1.5 g of dye n-4. Absorption maximum in water 610 nm Synthesis example 11-3 Dye 11-7
Synthesis of 3-cyano-6-hydroxy-4-methyl-1-
(2-Sulfoethyl)-pyrid-2-one 5.6 g 1 malonaldehyde cyanyl hydrochloride 4.5 g.

Dissolve 5.9 ml of triethylamine in 50 ml of methanol and lower the internal temperature to 5°C or lower. Add 3.1 ml of acetic anhydride to this solution.
mj! was added dropwise and stirred at room temperature for 13 hours. The formed precipitate was collected by filtration and treated with 5QmJ of acetonitrile, 1.) ethylamine, and 1. After heating and washing with Oml and drying the precipitate, 1.9 g of dye U-7 was obtained. Absorption maximum in N,N-dimethylformamide 625 nm Next, general formula (III) will be explained in detail.

The aliphatic group represented by R1, R12, R33, and R34 represents the same group as the aliphatic group defined in the general formula (R,, Ri, R3, R,).

The aromatic groups represented by R1, R15, R3ff, and R34 are the same as the aromatic groups defined by R,, R□, R3, and R4 in the general formula (+).

R3 Rxis The heterocyclic group represented by Rs3 and R34 represents a group having the same meaning as the heterocyclic group defined by R+, Rz, R2, and Ra in the general formula (r).

Specific examples of the dye represented by the general formula (rV) are shown below.

! [-2 CH,C00K cHt C00K CHzCHzSOJa cHgcHzsOJa 1l-12 (C1lz)zsO3Na (C)IJ 5sOJa CIItCHxOH CHzCHtOH CH,CH,α唖K CH寞C H,COO to C1lxCHtSOsNa CHxCToSOxNa These dyes are , No. 127, No. 3,469,985, No. 3,653゜905, No. 4
．． It can be synthesized by the method described in No. 078.933 and the like.

Synthesis examples of these compounds are shown below.

Synthesis Example +11-1 (Dye ■-3) A suspension of 5.7 g of N-ethyl-N'-(2-sulfoethyl)barbyl, 1.7 g of tetramethoxypropane, and 10 ml of pyridine was stirred under reflux. Dissolved. Triethylamine 2゜5mt+ was added dropwise to this, and 1
The reaction mixture stirred for 0 minutes was cooled to room temperature, 500 mff1 of acetone was added, and the mixture was thoroughly stirred, and the precipitated oil was separated by decantation. After dissolving this oil in 15ml of methanol, 2.5g of sodium iodide
A methanol solution of IQmf was added thereto, heated for 5 minutes, and then cooled with water. The precipitated crystals were filtered, thoroughly washed with acetone, and dried to obtain 4.3 g of reddish brown crystals.

An aqueous solution of this dye exhibits a red color, and its maximum absorption wavelength is 4.
It was 90 nm.

Synthesis example m-2 (dye m-6) N-(n-butyl)-N'-(2nisulfoethyl)barbylic acid 5.7 g, glutaconaldehyde cyanyl hydrochloride 2.4 g, pyridine 50 mA, triethylamine 1 Qml The mixture was heated and stirred on a water bath for 30 minutes.

The reaction mixture was filtered while hot, and at night a solution of 2.6 g of sodium iodide in methanol (ml) was added and cooled with water.

The precipitated crystals were filtered, thoroughly washed with acetone, and dried to obtain 4.1 g of blue crystals. The aqueous solution of this dye exhibited a blue-violet color, and its maximum absorption wavelength was 589 nm.

Synthesis example ■-4 (dye lll-10) 6.2 g of N-phenyl-N'-(2-sulfoethyl)barbylic acid, 2.5 g of malonaldehyde cyanyl hydrochloride
g,) ethylamine l Qml and methanol 50
A methanol solution of 2.0 g of anhydrous potassium acetate was stirred under reflux for 30 minutes.
! was added, stirred for 5 minutes, and then cooled with water. The precipitated crystals were filtered, thoroughly washed with acetone, and dried to obtain 4.8 g of reddish brown crystals.

The aqueous solution of this dye exhibited a reddish-brown color, and its maximum absorption wavelength was 49 Q nrn.

Synthesis example m-5 (dye l1l-11) N-phenyl-N'-(2-sulfoethyl)barbylic acid 6.2 g, glutaconaldehyde cyanyl hydrochloride 2
, 8 g, triethylamine 15 ml and methanol 5
0 ml of the mixture was stirred under reflux for 20 minutes. Next, 20 mg of a methanol solution of 2.0 g of anhydrous potassium acetate was added, stirred for 5 minutes, and then cooled with water. The precipitated crystals were collected by filtration, thoroughly washed with acetone, and dried to obtain 5.3 g of blue crystals.

The aqueous solution of this dye exhibited a blue-violet color, and its maximum absorption wavelength was 590 nm.

Synthesis Example ■-6 (Dye lll-14) 7.2 g of N,N'-bis(2,3-disulfophenyl)barbylic acid sodium salt, 2.8 g of glutaconaldehyde cyanyl hydrochloride, 5 mf of triethylamine and methanol The mixture of g Q ml was stirred under reflux for 30 min. The reaction mixture was then reduced to a volume of 1 at room temperature under reduced pressure.
After concentrating to /3, add isopropatool 200
ml was added. The precipitated crystals were filtered, thoroughly washed with acetone, and dried to obtain 6.1 g of blue crystals.

The aqueous solution of this dye exhibited a blue-violet color, and its maximum absorption wavelength was 590 nm.

Next, general formula (rV) will be explained in detail.

Substituent R1, R3, R3 of dye represented by general formula (IV)? , R2, is an alkyl group (e.g., methyl, ethyl, carboxymethyl, 2-carboxyethyl, 2-hydroxyethyl, methoxyethyl, 2-chloroethyl, benzyl, 2-sulfohensyl, 4-sulfophenethyl)
, aryl groups (phenyl, 4-sulfophenyl, 3-sulfophenyl, 2-sulfophenyl, 4-carboxyphenyl, 3-carboxyphenyl, 4-hydroxyphenyl) or heterocyclic residues (e.g. 2-pyridyl, 2-hydroxyphenyl) imidazole).

L4□ and I-as represent a methine group, and these methine groups may be independently substituted with methyl, ethyl, phenyl, sulfoethyl, carboxyethyl, or the like.

``4+ represents 1.2.3.

However, any one of R1, R3, R2'l, and Rss has at least one carboxyl group or sulfo group, and the total number is at least two or more. In addition, these carboxyl groups and sulfo groups can be used not only as free acids but also as salts (for example, N
a salt, K salt, ammonium salt).

Next, specific examples of the dye general formula (IV) used in the present invention will be shown.

(rV-4) (IV-6) Synthesis examples of compounds according to the present invention will be described below, but the invention is not limited thereto.

Synthesis Example IV-1 (Synthesis of the Invention ■-2) 16.7 g of 1,2-diphenyl-3,5-pyrazolidinedione? 1
4 sulfuric acid f11413 ml and 20% oleum 35 ml
j! Heat in a steam bath for 4 hours.

After cooling, it is added to water and further neutralized with potassium hydroxide solution. When the precipitated crystals are filtered and washed with methanol, 1
．． 27 g of sulfonated 2-diphenyl-3,5-pyrazolidinedione is obtained.

9.7 g of sulfonated product of 1,2-diphenyl-3,5-pyrazolidinedione, 1.3 g of tetramethoxypropane
, 25 ml of methanol were mixed, and further 2 g of triethylamine and 1 mg of acetic acid were added, and the mixture was heated under reflux for 6 hours. The precipitated crystals were collected by filtration, washed with hot methanol, and then dried to obtain 6.9 g of compound TV-2. Melting point 300℃ or higher,
:blJ3 K Synthesis example ■-2 (Compound of the present invention ■-9) Synthesis example rV-1
Dissolve 10.7 g of the sulfonated 1,2-diphenyl-3゜5-bilapridinedione obtained in step 1, 2.8 g of t-anilino-5-phenylimino-1,3-pentadiene hydrochloride, and 4 ml of triethylamine in 25 ml of methanol. , 4.5 mj' of acetic anhydride is added dropwise under PA Pt' at room temperature. After further reaction for 2 hours, the precipitated crystals were collected by filtration.

The crude crystals were added to 50 ml of methanol, heated and washed, and the crystals collected by filtration were dried to obtain 7.1 g of compound rv-tt. Melting point 300°C or higher, a x Synthesis example ■-3 (Compound of the present invention ■-5) l-phenyl-
2-(2-Sulfohensyl)3.5-pyrazolinedione sodium salt (Intermediate C) 104 g of phenylhydrazine was dissolved in 80 Qmf of methanol, and this solution was prepared by dissolving 56 g of sodium O-formylbenzenesulfonate in 20 Qmn of methanol. dropwise at room temperature. While stirring this mixture,
The mixture was heated under reflux for an hour, and the cooled crystals were collected by filtration and washed with methanol to obtain 69 g of sodium 2-phenylhydrazonobenzenesulfonate (intermediate A). Intermediate A30
Dissolve g in 250 ml of water, add rosemium carbonate catalyst, and hydrogenate in an autoclave. After filtering off the catalyst, add isopropanol 25 Qmj! When added, colorless crystals precipitate. The residue is collected by filtration, washed with impropatol, and dried to obtain 43 g of sodium 2-phenylhydrazinobenzenesulfonate (intermediate B). Next, intermediate body 840
g, diethyl malonate 19g, sodium methylate
(28% methanol solution) 25g Sn-butanol 10
0ml were mixed and heated under reflux for 10 hours. Concentrate the n-butanol and add 200 ml of water to the residual aroma. Next, the aqueous layer is acidified with concentrated hydrochloric acid to precipitate crystals. After washing with a small amount of methanol, 39 g of Intermediate C is obtained.

l-phenyl-2-(2-sulfobenzyl) = 3.5-
Add 7.4 g of pyrazolidinedione sodium salt to 5 QmJ of methanol, then add 4.2 ml of triethylamine and 2.5 g of malonaldehyde cyanyl hydrochloride and heat to form a homogeneous solution. After cooling to room temperature, add 4.5 mj of acetic anhydride.
drip.

After reacting for 2 hours, 25 mA of isopropanol is added to precipitate orange crystals. The crystals were collected by filtration, washed with isopropanol, and dried to yield 5 g of compound rV-4. Melting point: 300°C or higher, a-x When the dye used in the present invention is used as a filter dye, anti-irradiation dye, or antihalation dye, any effective amount can be used, but the optical density is 0.05. It is preferable to use it so that the amount is in the range of 3.0 to 3.0 degrees, and it may be added at any step before coating.

The dyes according to the invention can be dispersed in emulsion layers and other hydrophilic colloid layers (interlayers, protective layers, antihalation layers, filter layers, etc.) by various known methods.

■ A method in which the dye of the present invention is directly dissolved or dispersed in a fine solid state in an emulsion layer or a hydrophilic colloid layer, or a method in which the dye of the present invention is dissolved or dispersed in a fine solid state in an aqueous solution or solvent, and then the dye is dissolved in an emulsion layer or a hydrophilic colloid layer. Methods used for the layer, suitable solvents such as methyl alcohol, ethyl alcohol, propyl alcohol, methyl cellosolve, JP-A-4
No. 8-9715, U.S. Pat. No. 3,756,830, halogenated alcohol, acetone, water, lysine, etc. or a mixed solvent thereof may be dissolved and added to the emulsion in the form of a solution. can.

■ A method in which a wood-philic polymer with an opposite charge to the dye ion is made to coexist in the layer as a mordant, and this interacts with the dye molecules to localize the dye in a specific layer.

A polymer mordant is a polymer having a nitrogen-containing heterocyclic moiety containing secondary and tertiary amino groups, or a polymer containing these quaternary cation groups, and has a molecular weight of 500.
Preferably 0 or more, particularly preferably 10,000
That's all.

For example, vinylpyridine polymers and vinylpyridinium cationic polymers disclosed in U.S. Pat. No. 2,548,564, etc.; vinylimidazolium cationic polymers disclosed in U.S. Pat. Polymer mordants capable of crosslinking to gelatin, etc., disclosed in No. 3,625.694; aqueous sol type mordants, disclosed in U.S. Pat. No. 3,958.995, JP-A-54-115228, etc.; U.S. patent 3
, 898,088; reactive mordants capable of covalently bonding with dyes as disclosed in U.S. Pat. No. 4,168.976; British Patent No. 685,475; Polymers derived from ethylenically unsaturated compounds having dialkylaminoalkyl ester residues as described; products obtained by reaction of polyvinyl alkyl ketones with aminoguanidine as described in British Patent No. 850,281; Examples include polymers derived from those described in US Pat. No. 3,445,231.

■ A method of dissolving a compound using a surfactant.

Useful surfactants may be oligomers or polymers.

For details of this polymer, please refer to JP-A-60-15843.
No. 7, pages 19 to 27 of the specification.

Further, in the hydrophilic colloid dispersion obtained above, for example, hydrosyl, a lipophilic polymer described in Japanese Patent Publication No. 51-39835, may be added.

Gelatin is a typical hydrophilic colloid, but any other conventionally known hydrophilic colloids that can be used for photography can be used.

The photographic emulsion layer of the photographic material used in the present invention contains silver bromide, 2-methyl-1-vinylimidazole,
Any silver halide such as silver iodobromide, silver iodochlorobromide, silver chlorobromide, and silver chloride may be used.

The silver halide grains in the photographic emulsion may be so-called regular grains having a regular crystal structure such as a cube, octahedron, or dodecahedron, or may have an irregular crystal shape such as a spherical shape. Particles having crystal defects such as twin planes or a composite form thereof may be used, or a mixture of particles of various crystal forms may be used.

The silver halide grains may be fine grains with a grain size of about 10 microns or less, or large grains with a projected area diameter of about 10 microns, and may be monodisperse emulsions with a narrow distribution or polydisperse with a wide distribution. An emulsion may also be used.

The silver halide photographic emulsion that can be used in the present invention can be produced by a known method, such as Research Disclosure,
Volume 176, Nα17643 (December 1978), 2
pp. 2-23, “I. Emulsion P.
187, Nα18716 (November 1979)
May), p. 648 can be followed.

The photographic emulsion used in the present invention is described in "Physics and Chemistry of Photography" by Grafkide, published by Beaumontel (P.

Glafkides, Chisie et Phys
ique Photographique Paul
Montel, l 967), “Photographic Emulsion Chemistry” by Duffin, published by Focal Press (G, F, D
uffin.

Photographic Emulsion Ch
emistry (Focal Press.

1966), “Manufacture and Coating of Photographic Emulsions” by Zelikman et al.
, Published by Focal Press (V, L, Zelikman'
etal, Making and Coating
Photographic EmulsionFoca
1 Press+ 1964). That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt with the soluble halogen salt may be any one-sided mixing method, simultaneous mixing method, or a combination thereof. good. It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method). PAg in the liquid phase where silver halide is produced as a type of simultaneous mixing method
The method of keeping constant is the so-called chondral
A double jet method can also be used. According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained.

In addition, known silver halide solvents (for example, ammonia, rhodankali, or Showa 54-100'71
Physical ripening can also be carried out in the presence of 1,000-onythyls and thione compounds described in No. 7 or JP-A-54155828. This method also yields a silver halide emulsion with a regular crystal shape and a nearly uniform grain size distribution.

The silver halide emulsion consisting of the regular grains described above can be obtained by controlling PAg and pH during grain formation. For more information, see Photographic Science and Engineering (Photographic Science and Engineering).
5science and I! engineering)
Vol. 6, pp. 159-165 (1962); Journal
Op Photography Inc. Science (Journa)
l or Photographic 5science
), Vol. 12, pp. 242-251 (1964), U.S. Patent No. 3,655.394 and British Patent No. 1,413
, No. 748.

Monodispersed emulsions that can be used in the present invention include silver halide grains having an average grain size of more than about 0.05 μm;
Emulsions of which at least 95% by weight are within 140% of the average grain size are typical. Furthermore, the average particle size is 0.1
An emulsion can be used in which the average grain size is 5 to 2 μm and at least 95% by weight or at least 95% (by number of grains) of halogenated root particles are within the range of ±20% of the average grain size. A method for producing such an emulsion is described in U.S. Pat. No. 3,574°628.
No. 3,655,394 and British Patent Nos. 1 and 4
No. 13,748.

Also, JP-A-48-8600, JP-A-51-39027,
No. 51-83097, No. 53-137133, No. 5
No. 4-48521, No. 54-99419, No. 5B-3
Chemical dispersion emulsions such as those described in No. 7635 and No. 5B-49938 can also be preferably used.

Further, tabular grains having an aspect ratio of 5 or more can also be used in the present invention. Tabular grains are described in Cutoff, Photographic Science and Engineering.
ence and Engineering) + 14th
Vol. 248A+257 (1970): U.S. Patent No. 4
, 434°226, 4,414,310, 4,
433.048, 4,439,520, and British Patent No. 2,112,157. When using tabular grains,
Advantages include improved covering power and improved color sensitization efficiency with sensitizing dyes, which are detailed in the above-cited US Pat. No. 4,434,226.

It is also possible to use particles whose crystal shape is controlled by using aggravating dyes or certain additives during the particle formation process.

The crystal structure of these emulsion grains may be --like, the inside and outside may have different halogen compositions, or they may have a layered structure.
No. 46, U.S. Patent No. 3.505.068, U.S. Patent No. 4,44
No. 4,877 and Japanese Patent Application No. 58-248469.

Further, silver halides having different compositions may be joined by epitaxial joining, and for example, silver halides, rhodan silver,
These emulsion grains, which may be grafted with compounds other than silver halides, such as lead oxide, are described in U.S. Pat.
, No. 684, No. 4.142.900, No. 4,459,
No. 353, British Patent No. 2.038,792, U.S. Patent No. 4,349.622, U.S. Patent No. 4,395,478, U.S. Pat.
．． It is disclosed in No. 656,962, No. 3,852,067, Japanese Unexamined Patent Publication No. 162540/1983, and the like.

Furthermore, photosensitive nuclei (AgzS, Ag
It is also possible to use a grain structure having a so-called internal latent image type grain structure in which silver halide is further grown on the periphery after the formation of silver halide (n, Au, etc.).

In the process of silver halide grain formation or physical ripening,
A cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a tIF salt thereof, an iron salt or an iron complex salt, etc. may be present.

These various emulsions may be either a surface latent image type in which a latent image is formed mainly on the grain surface or an internal latent image type in which a latent image is formed inside the grain.

Furthermore, a direct reversal emulsion may be used. The direct reversal emulsion may be of the solarization type, internal latent image type, photofog type, nucleating agent type, etc., or a combination of these may be used.

Among these, an internal latent image type emulsion that has not been fogged in advance is used, and is fogged by light before or during processing.
Alternatively, it is preferable to directly obtain a positive image by fogging using a nucleating agent.

The unfogged internal latent image type silver halide emulsion used in the present invention is an emulsion containing silver halide in which the surface of the silver halide grains is not fogged in advance and forms a latent image mainly inside the grains. However, more specifically, a silver halide emulsion is coated on a transparent support at a constant rate, and then a 0. A sample exposed for a fixed time of 10 to 10 seconds was placed in the following developer A (internal developer) for 2
The maximum density measured by the usual photographic density measurement method when developed at 0°C for 6 minutes is the same as the maximum density when a similarly exposed sample is developed at 18"C for 5 minutes in the following developer B (surface type developer). 1 at least 5 times greater than the maximum concentration obtained.
Preferably, the concentration is at least 10 times greater.

Internal developer A Metol 2g Sodium sulfite (anhydrous) 90g Hydroquinone
8g Soda carbonate (-water salt)
52.5gKBr
5gKI
O, add 5g water 11
Surface developer B Metol 2.5g! -Ascorbic acid logNaBOt'
4Hz 0 35gKBr
Add 1g water
11 Specific examples of the internal latent image type emulsion include British Patent No. 1011062 and U.S. Patent No. 2,59.
Conversion type silver halide emulsions and core /
Examples include shell-type silver halide emulsions, in which the core/
As a shell type silver halide emulsion, JP-A-47-32
No. 813, No. 47-32814, No. 52-13472
No. 1, No. 52-156614, No. 53-60222, No. 53-66218, No. 53-66727, No. 5
No. 5-127549, No. 57-136641, No. 58
-70221, 59-208540, 59-2
No. 16136, No. 60-107641, No. 60-24
No. 7237, No. 61-2148, No. 61-3137, Japanese Patent Publication No. 56-18939, No. 5B-1412, No. 58-1415, No. 5B-6935, No. 5B-10
No. 8528, Japanese Patent Application No. 61-36424, U.S. Patent No. 32
No. 06313, No. 3317322, No. 3761266
No. 3761276, No. 3850637, No. 39
No. 23513, No. 4035185, No. 4395478
No. 4504570, European Patent 001714
No. 8, Research Disclosure Magazine Na16345
(November 1977) and the like.

In order to remove soluble root salts from the emulsion before and after physical ripening, Tardel water washing, flochieration sedimentation method, ultrafiltration method, etc. can be used.

The emulsion used in the present invention is usually one that has been subjected to physical ripening, chemical ripening and spectral sensitization. Additives used in such processes are described in the aforementioned Research Disclosure Nα17643 (December 1978) and Research Disclosure Nα18716 (November 1979), and the relevant parts are summarized in the table below. .

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

11 Plasticizers, lubricants Page 27 Page 650 Right column 12 Coating aids, surfaces Pages 26-27 Same as above Active agent 13 Statink prevention Page 27 Same as above Agent l Chemical sensitizer 2 Sensitivity increasing agent 3 Spectral sensitizer, superchromic enhancement Sensitizer 4 Brightener 5 Anti-fog agent and stabilizer 6 Light absorber, filter dye UV absorber 7 Anti-stin agent 8 Dye image stabilizer 9 Hardener lO binder 23 pages 23-24 page 648 right column Same as above Page 648 right column ~ Page 649 Right column 24 pages 24-25 Page 649 Right column Pages 25-26 Page 649 Right column ~ Page 650 Left column 25 Page Right column 25 Page 26 Page 26 Page 650 Left to right column Page 651 Left column Same as above In the color photographic light-sensitive material of the present invention, various color couplers can be used in addition to the yellow coupler.
) 17643, ■-C to G.

As the magenta coupler, 5-pyrazolone and pyrazoloazole compounds are preferred, and U.S. Pat.
No. 0,619, No. 4,351°897, European Patent No. 73,636, U.S. Patent No. 3,061,432, No. 3. 725. No. 067, Research Disclosure 24220 (June 1984), Japanese Patent Publication No. 1983
-33552, Research Disclosure Nα2
4230 (June 1984), JP-A-60-43659
No. 4,500,630, U.S. Pat. No. 4,540
Particularly preferred are those described in No. 654 and the like.

Cyan couplers include phenolic and naphthol couplers, and are described in U.S. Pat. No. 4,052,212.
No. 4,146,396, No. 4,228,23
No. 3, No. 4,296,200, No. 2,369,92
No. 9, No. 2,801゜171, No. 2,772,16
No. 2, No. 2゜895.826, No. 3,772.0
No. 02, No. 3.758,308, No. 4,334,
No. 011, No. 4,327,173, West German Patent Application No. 3,329,729, European Patent No. 121°365A, U.S. Patent No. 3,446,622, No. 4,333,
No. 999, No. 4,451.559, No. 4.427
, 767, European Patent No. 161.626A, etc. are preferred.

Colored couplers for correcting unnecessary absorption of coloring dyes are available from Research Disclosure Toru 17643.
- Section G, U.S. Patent No. 4,163゜670, Japanese Patent Publication No. 1983
-39413, U.S. Patent No. 4,004,929, U.S. Patent No. 4,138,258, British Patent No. 1,146,36
The one described in No. 8 is preferred.

Couplers whose coloring dyes have appropriate diffusivity include U.S. Patent No. 4,366.237 and British Patent No. 2.125.
, 570, European Patent No. 96.570, and German Patent Publication No. 3.234,533 are preferred.

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

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

As a coupler that releases a nucleating agent or a development accelerator imagewise during development, British Patent No. 2.097.140;
No. 2,131.188, JP 59-157638
No. 59-170840 is preferred.

Other couplers that can be used in the light-sensitive material of the present invention include competitive couplers described in U.S. Pat. No. 4,130,427, U.S. Pat. , a multi-equivalent coupler described in JP-A No. 4.310.618, a DIR redonx compound releasing coupler described in JP-A-60-185950, etc., and a dye that recolors after separation as described in European Patent No. 173.302A. Examples include couplers that emit light.

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 process, effects, and specific examples of latices for impregnation of the Latin lath dispersion process are described in U.S. Pat. Are listed.

The light-sensitive material of the present invention includes dyes other than the above-mentioned dyes that prevent irradiation and halation, ultraviolet absorbers, plasticizers, optical brighteners, matting agents, air capping inhibitors, coating aids, and hardening agents. , antistatic agents, slipperiness improvers, various development accelerators, etc. can be added. Representative examples of these additives are listed in Research Disclosure magazine Nα17643.
■~■ pages 225-27 (published December 1978), and 1B716 (published November 1979) p647~
651.

The invention is also applicable to multilayer, multicolor photographic materials having at least two different spectral features on the support.

Multilayer natural color photographic materials usually have a red-sensitive emulsion layer on a support,
It has at least one green-sensitive emulsion layer and at least one blue-sensitive emulsion layer. The order of these layers can be arbitrarily selected as necessary. The preferred order of layer arrangement is red sensitivity, green sensitivity, and blue sensitivity from the support side, or green sensitivity, red sensitivity, and blue sensitivity from the support side. Further, each of the above emulsion layers may be made up of two or more emulsion layers having different sensitivities, and a non-photosensitive layer may exist between two or more emulsion layers having the same color sensitivity. Usually, the red-sensitive emulsion layer contains a cyan-forming coupler, the green-sensitive emulsion layer contains a magenta-forming coupler, and the pre-malignant emulsion layer contains a yellow-forming coupler.

In addition to the silver halide emulsion layer, the light-sensitive material according to the present invention is preferably provided with auxiliary layers such as a protective layer, an intermediate layer, a filter layer, an antihalation agent, a back layer, and a white reflective layer.

In the photographic light-sensitive material of the present invention, the photographic emulsion layer and other layers are those described in Research Disclosure Magazine Nα17643 Section 228 (published December 1978), European 'tH4' No. 0.102,253, and JP-A-61 -9
No. 7655. Also, Research Disclosure Magazine N [117643 Section XV p28
~29: The coating method described can be utilized.

The present invention can be applied to various color photosensitive materials.

For example, color negative film, color print film, color reversal film for slides or television,
A typical example is color reversal paper. The present invention can also be applied to full-color copying machines and color hard copies for storing CRT images.
It can also be applied to black and white photosensitive materials using a mixture of three color couplers, as described in Magazine K17123 (published in July 1978).

The present invention is preferably applied directly to positive photosensitive materials.

When the photosensitive material of the present invention is a direct positive, fogging treatment is carried out by the following "photofogging method" and/or "chemical fogging method J." The entire surface exposure, that is, fogging exposure in the "photofogging method" of the present invention is as follows: After imagewise exposure, development processing and/or
Or done during the development process. The imagewise exposed light-sensitive material is immersed in a developer solution or a pre-bath of the developer solution, or is taken out from the solution and exposed before drying, but it is most preferable to expose the material in the developer solution.

As a light source for fogging exposure, a light source within the wavelength range to which the photosensitive material is sensitive may be used, and generally any of fluorescent lamps, tungsten lamps, xenon lamps, sunlight, etc. may be used.

These specific methods are described, for example, in British Patent No. 1,151,
No. 363, Special Publication No. 45-12'710, No. 45-12
No. 709, No. 58-6936, JP-A-48-9727
No. 56-137350, No. 57-129438, No. 58-62652, No. 58-60739, No. 5
B-70223 (corresponding U.S. Patent No. 4,440°851), No. 5B-120248 (corresponding European Patent No. 89101)
A2) etc.

For photosensitive materials sensitive to all wavelength ranges, such as color photosensitive materials, Japanese Patent Application Laid-open Nos. 56-137350 and 5B-702
A light source with high color rendering properties (as close to white as possible) as described in No. 23 is preferable. The illuminance of the light is 0.01-200
0 lux, preferably 0.05 to 30 lux, more preferably 0.05 to 5 lux is suitable. For light-sensitive materials that use emulsions with higher sensitivity, exposure at lower illuminance is preferable. The illuminance may be adjusted by changing the luminous intensity of the light source, by reducing the light using various filters, by changing the distance between the photosensitive material and the light source, or by changing the angle between the photosensitive material and the light source. Further, the illuminance of the fogging light can be increased continuously or stepwise from low illuminance to high illuminance.

It is preferable to immerse the light-sensitive material in a developer solution or a pre-bath solution, and to irradiate the light-sensitive material after the solution has sufficiently penetrated into the emulsion layer of the light-sensitive material.

In the present invention, the aeAi agent used when applying the so-called "chemical fogging method" can be contained in the light-sensitive material or in the processing solution for the light-sensitive material. Preferably, it can be incorporated into the photosensitive material.

Here, the term "nucleating agent" refers to a substance that acts to directly form a positive image during surface development of an internal latent image type silver halide emulsion that has not been fogged in advance. It is particularly preferable to carry out fogging treatment using a nucleating agent.

When incorporated into a light-sensitive material, it is preferably added to the latent type halide emulsion layer, but as long as the nucleating agent is adsorbed to the silver halide by diffusion during coating or processing, it may be added to other layers. For example, it may be added to an intermediate layer, undercoat layer or bank layer.

When adding a nucleating agent to the processing solution, use a developing solution or a low pH
It may be included in the pre-bath.

Furthermore, two or more types of nucleating agents may be used in combination.

Regarding the nucleating agent used in the present invention, JP-A-63-10
No. 6506, and in the same specification, it is particularly preferable to use compounds represented by general formulas (N-1) and (N-11).

When the nucleating agent is contained in the sensitive material, the amount used is preferably io-'-to-' moles, more preferably 10-' to 10-3 moles, per mole of the halogenated material.

In addition, when adding a nucleating agent to the processing solution, the amount used is:
The amount is preferably 10-'' to 10-3 mol, more preferably 10-7 to 10-' mol per 12.

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 include 3-methyl-4-amino-N, N-diethylaniline, 3- Methyl-4-amino-N-ethyl-N
-β-hydroxyethylaniline, 3-methyl4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N-
Examples include β-methoxyethylaniline and their sulfates, hydrochlorides, and P-1-luenesulfonates. Two or more of these compounds can be used in combination depending on the purpose.

Further, when performing reversal processing, black and white development is usually performed and then color development is performed. In this black and white developer, known black and white developing agents such as dihydroxybenzenes such as hydroquinone, 3-virazolidones such as ■-phenyl-3-virapritone, or aminophenols such as N-methyl-ρ-aminophenol may be used alone or Can be used in combination.

The pH of these color developing solutions and black and white development is generally 9 to 12. In addition, the amount of replenishment during the night of development (development) depends on the color photographic light-sensitive material to be processed, but it is 31 or less per square meter of light-sensitive material for -M, and by reducing the bromide ion concentration in the replenisher, 50 (
It can also be less than ld.

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. Furthermore, in order to speed up the processing, it is possible to use a processing method in which bleaching is followed by bleach-fixing, furthermore, processing in two consecutive bleach-fixing baths, fixing before bleach-fixing, or bleach-fixing. A post-bleaching treatment can also be optionally carried out depending on the purpose. Examples of bleaching agents include iron (■), Kobal) (I
Compounds of polyvalent metals such as I[), chromium (■), and copper (II), peroxide M14, quinones, nitro compounds, and the like are used.

Examples of fixing agents include thiosulfate, thiocyanate, thioether compounds, thioureas, and large amounts of iodide salts, but thiosulfate is commonly used, and ammonium thiosulfate is the most commonly used. Can be used widely. As the preservative for the bleach-fix solution, sulfites, bisulfites, or carbonyl bisulfite adducts are preferred.

The silver halide color photographic light-sensitive material of the present invention is generally subjected to water washing and/or stabilization steps after 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
Urnalof the 5ociety of Mo
tion Picture and Televisi
onEngrneers Volume 64, P, 248-2
53 (May 1955 issue).

(Example) Next, the present invention will be explained in more detail based on examples.

Example 1 Paper support laminated on both sides with polyethylene (thickness 10
A color photographic light-sensitive material was prepared by coating the next four layers from the second layer on the front side of the film (0 microns) and the fifth layer through the sixth layer on the back side. The polyethylene on the coating side of the first layer contains titanium oxide as a white pigment and a trace amount of ultramarine as a bluish dye (the chromaticity of the surface of the support is Lll, a).
The values were 88.0, -0.20, and -0.75 for the ll and be systems. ) (Photosensitive layer composition) Below are the ingredients and coating! (in g/i units), and for silver halide, the coating amount is shown in terms of silver.

The emulsion used in each layer was prepared according to the manufacturing method of emulsion EMI. However, the four-layer emulsion in the cylinder was a Lippmann emulsion that was not surface chemically sensitized.

1st layer (antihalation layer) Black colloidal silver ... 0.10 Gelatin ... 0.70 2nd layer (middle layer) Gelatin ... 0.70 3rd layer
Layer (low sensitivity red sensitive layer) Silver bromide spectrally sensitized with red sensitizing dyes (ExS-1, 2, 3) (average grain size 0.25 μ, size distribution [coefficient of variation] 8%, octahedral) ... 0.04 Silver chlorobromide spectrally sensitized with red sensitizing dye (ExS-1, 2, 3) (chloride 115 mol%, average particle size 0.40
μ, size distribution 10%, octahedral)
・・・ 0.08 gelatin ・・・
・ l, 00 cyan coupler (ExC-1, 2, 3 in 1
=1:0.2> ... 0.30
Antifading agent (CPd-1, 2, 3, 4 equivalents)... 0
．． 18 Anti-stin agent (Cpd-5) ... 0.003
Coupler dispersion medium (Cpd-6)... 0.03 Coupler solvent (Solv-1, 2, 3 equivalent)... 0
．． 12 4th layer (high sensitivity red sensitive layer) 1B bromide spectrally sensitized with red sensitizing dye (F, xS-1,2,3) (average particle size 0.60μ, size distribution 1
5%, octahedron) ... 0.14 gelatin
... 1.00 cyan coupler (ExC
-1,2,3 = 1:0.2)
... 0.30 Anti-fading agent (Cpd-12, 3, 4 equivalent) ... 0.18 Coupler dispersion medium (Cpd-6) ... 0.03 Coupler solvent (Solv-1, 2, 3) Equal amount)... 0.
12 5th layer (intermediate layer) Gelatin... 1.00 Color mixing inhibitor (Cpd-7)... 0.08 Color mixing inhibitor solvent (Solv-4, 5 equivalent)... 0.16 Polymer latex (Cpd-8) 0° 6th layer (low-sensitivity green-sensitive layer) Silver bromide (
Average particle size 0.25μ, size distribution 8%, octahedral)
... 0.04 green sensitizing dye (ExS-4
) spectrally sensitized silver chlorobromide (chloride! 115 mol%, average grain size 0.40 μ, size distribution 10%, octahedral)
... 0.06 Gelatin ... 0.80 Magenta coupler (ExM-1, 2, 3 equivalents) ... 0.
11 Anti-fading agent (Cpd-9, 26 etc. N)...0.1
5 Anti-staining agent (Cpd-10, 11, 12, 13 in 1
0 near:7:l ratio)... 0.025 force puller dispersion medium (Cpd-6)... 0.05 coupler solvent (
Solv-4,6 equivalent)... 0.15 7th layer c high sensitivity green sensitive layer) Bromide 1 spectrally sensitized with green sensitizing dye (ExS-4)!
(Average particle size 0.65μ, size distribution 16%, octahedron) ... 0. lO gelatin
... 0.80 magenta coupler (EXM-
1, 2, 3 equivalents)... 0.11 Anti-fading agent (Cpd-9, 26 equivalents) -0,15 Anti-staining agent (Cpd-IQ, 11.12.13 to 1
0 near:7:1 ratio)... 0.025 force puller dispersion medium (Cpd-6)..., 0.05 coupler solvent (
3o1v 4.6 equivalent)... 0.15 8th layer (intermediate N) 9th layer (yellow filter layer) same as the 5th layer Yellow colloidal silver gelatin color mixture prevention agent (Cpd-7) Color mixture prevention agent solvent ( Solv-4, ... 0.12 ... 0.07 ... 0.03 5 equivalents) ... 0.10 Polymer latex (Cpd-8) ... 0.07 1st O layer (middle Layer) The 11th layer (low sensitivity blue-sensitive layer) same as the 5th layer Silver bromide spectrally sensitized with blue sensitizing dye (ExS-5, 6) (average grain size 0.40μ, size distribution 8%, Octahedron) ... 0.07 blue sensitizing dye (ExS-5
, 6) spectrally sensitized with silver chloride bromide (1!8 mol% chloride)
, average particle size 0.60 μ, size distribution 11%, octahedral) ... 0.14 Gelatin ... 0.80 Yellow coupler (ExY-1,2 equivalent) ... 0.35 ... 0 .10 15 to l:5 ratio... 0.007... 0.05 0.10 Anti-fading agent (Cpd-14) Anti-stinting agent (Cpd-5, with) Coupler dispersion medium (Cpd-6) Kablaan Container (3o1v-2) 12th layer (high-sensitivity blue layer) Silver bromide spectrally sensitized with blue sensitizing dye (ExS-5, 6) (average particle size 0.85μ, size distribution 18%, Octahedron) ... 0.15 gelatin
... 0.60 yellow coupler (ExY-1
, 2 equivalents)... 0.30 Anti-fading agent (Cpd-14)... 0.10 Anti-staining agent (Cpd-5, 15 in a 1:5 ratio)
... O,OO7 power blur dispersion medium (Cpd-6) ... 0.05 coupler solvent (
Solv-2) -0,10 No. 13N (ultraviolet absorbing layer) Gelatin... 1.00 Ultraviolet absorber (Cpd-2, 4, 16, etc.... O, SO Color mixing prevention agent (Cpd-7, 17) Equivalent amount) ... 0.03 Dispersion medium (Cpd-6) ... 0.02 Ultraviolet absorber solvent (Solv-2,7 equivalent) ... 0,
08 Anti-irradiation dye (Cpd-18, 19, 20
, 21, in lO:101115 ratio)
... 0.05 14th layer (protection N) Fine grain silver chlorobromide (chloride 1197 mol%, average size 0.05)
1 μ) ... 0.03 Acrylic modified copolymer of polyvinyl alcohol ... 0.01 Polymethyl methacrylate particles (average particle size 2.4
μ) and silicon oxide (average particle size 5μ) equivalent amount
... 0.05 gelatin
... 1.80 gelatin hardening agent (H-1, H-
2nd class 1) 0, 18 15th layer (back N) Gelatin... 2.50 Ultraviolet absorber (Cp d -2, 4, 16 equivalent)... 0
．． 50 Dye (equal amounts of Cpd-18, 19, 20, 21)...
0.06 16th layer (back protective layer) Polymethyl methacrylate particles (average particle size 2.4
μ) and silicon oxide (average particle size 5μ) equivalent amount
... 0.05 gelatin
... 2.00 gelatin hardening agent (H-1, H-
2 equivalents)... 0.14 How to make emulsion EM-1 An aqueous solution of potassium bromide and silver nitrate was simultaneously added to an aqueous gelatin solution with vigorous stirring at 75°C over 15 minutes.
Octahedral silver bromide grains with an average grain size of 0.40 μm were obtained. To this emulsion was added 0.3 g of 3.4-dimethyl-1 per mole of silver.
, 3-thiazoline 2-thione, 6 parts of sodium thiosulfate and 7 parts of chloroauric acid (tetrahydrate) were added in sequence and heated to 80°C at 75°C.
Chemical sensitization treatment was performed by heating for minutes. Using the thus obtained grains as cores, they were further grown in the same precipitation environment as in the first precipitation to finally obtain an octahedral monodispersed core/shell silver bromide emulsion with an average grain size of 0.7 μm. The coefficient of variation in particle size was approximately 10%.

To this emulsion, 1.5 μ of sodium thiosulfate and 1.5 μ of gold chloride M (tetrahydrate) were added per 1 mole of iN and heated at 60°C for 60 minutes to perform chemical sensitization treatment. A silver oxide emulsion was obtained.

Each photosensitive layer contains ExZK-1 and ExZK- as nucleating agents.
2 to silver halide in an amount of 10-3.10-2% by weight, and cpa-22 as a nucleation accelerator in an amount of 10-z% by weight.
Using. Further, in each layer, Alkanol X C (Dupon Co., Ltd.) and sodium alkylbenzyl sulfonate were used as emulsification dispersion aids, and succinate ester and Magefac F120 (manufactured by Dainippon Ink Co., Ltd.) were used as coating aids. (Cpd-23, 24, 25) was used as a stabilizer in the silver halide and colloidal silver containing layers. This sample was designated as (Sample-1), and the compounds used in the examples are shown below.

xS-1 O3 on H ・N　CCt　Hs)+ xS-2 Oi 03H xS-3 SO, Na O3 xS SO1 O3H xS-5 SOz　H-N　(C!　Hs)s xS SO3H-N (Cz H5)3 pd pd pd C,H.

pd pd pd-4 pd-5 pd pa pd-8 pd pd-17 pd-18 u3 K blJ3 K Cpd-19 cpa cpa saLJsK :! ILJ3 K xC xC Cn)lq xM-1 cpa-22 cpa-24 cpa-26 xC xM-2 xM-3 cpa-23 cpa Hs ExY-2 3o1v-I olv-2 olv-3 olv-4 olv-5 olv -6 olv-7 -I Di(2-ethylhexyl) sebacate trinonyl phosphate di(3-methylhexyl) phthalate tricresyl phosphate dibutyl phthalate trioctyl phosphate di(2-ethylhexyl) phthalate 1.2-bis(vinylsulfonyl) acetamido)ethane 4.6-dichloro-2-hydroxy-1,3,5-) riazine Na salt xZK-1 xZK-2 7-(3-ethoxythiocarbonylaminobenzamide)-9-methyl-10-prohagilu 1. 2゜3.4-
Trahydroacridinium trifluoromethanesulfonate 2-[4-(3-(3-(3-[5-(3-(2-chloro-5-(l-dodecyloxycarbonylethoxycarbonyl)phenylcarbamoyl) ]-4-hydroxy-1-naphthylthio)tetrazol-1-yl)phenyl)ureido]benzenesulfonamido)phenyl]-
1-Formylhydrazine Each sample in this example was prepared by continuously processing Sample 1 using an automatic processor in the processing steps described below until the cumulative replenishment amount of the processing solution was three times the tank capacity, and then each test. The samples were processed.

Color development 135 seconds 38℃ 15 j 300s
f/m”・Bleach fixing 40#・33〃3〃300〃Washing (1140〃33〃3〃Washing +2) 40"33#3' 320
-30# 80# The method of replenishing the washing water is to refill the washing water (washing bath value) and
A so-called countercurrent replenishment system was adopted in which the overflow liquid of ) was led to the washing bath +11. At this time, the amount of bleach-fix solution brought into the washing bath (11) from the bleach-fix bath for photosensitive materials is 35
ml/a'', and the ratio of the amount of washing water replenishment to the amount of bleach-fix solution brought in was 9.1 times.

The composition of each treatment liquid was as follows.

Keiou Matashiri D-Sorbit Sodium naphthalene sulfonate/formalin condensate Ethylene di7mine Tetrakis methylene Phosphonic acid Diethylene glycol Benzyl alcohol Potassium bromide Benzotriazole Sodium sulfite N,N-Bis(carboxymethyl)hydrazine D-Glucose triethanolamine N-Ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-4= Aminoaniline sulfate base 0.15g 0, 15g 0.20g 0.20g 1.5g 1.5g 12.0m A 13 .5s1 0.80g 0.003g 01004g 2.4g 3.2g 6.0g 16.0m1 18.0m1 8.0g 2.0g 6.0 g 6.4g 2.4g 8.0g 8.5g Potassium carbonate 30. 0 g 25.0 g Ammonium nitrate 10°Og Fluorescent brightener (diaminostilbene type) 1.0 g 1.2 pH (25°C) 10.25 Ethylenediaminetetraacetic acid 4.0g disodium
Ethylenediamine tetraacetic acid dihydrate 70. OgFe(In)
・Ammonium dihydrate ammonium thiosulfate 180mj (700g/j
p-) Luenesulfinic acid 20.0 g Sodium Sodium bisulfite 20.0 g 5-Mercapto-1,3,0,58 4-triazole 10.75 Same tap water as mother liquor Both mother liquor and replenisher were tap water in H type Water was passed through a mixed-bed column filled with an acidic cation exchange resin (Amberlite IR-120B, manufactured by Rohm and Haas) and an OH-type anion exchange resin (Amberlite IR-400, manufactured by Rohm and Haas) to adjust the concentration of calcium and magnesium ions. 3.7 g/l of sodium isotheaterate dichloride and 1.5 g/l of sodium sulfate were subsequently added. The pH of this solution is 6.5-7
It was in the range of 5°.

(Sample 2) to (Sample 10) were prepared using the compound of the present invention or a comparative compound in combination with the irradiation-preventing dye in the 13th layer or in place of the irradiation-preventing dye in the 13th layer. did.

The structures of (Sample 2) to (Sample 10) are shown in Table 1.

In order to evaluate the color reproducibility of the obtained sample, the following test was conducted. A manuscript was prepared in which a Macbeth color checker was photographed using a color negative film (SHR-100 manufactured by Fuji Photo Film ■) and printed on color paper (02 ■ manufactured by Fuji Photo Film ■). This manuscript was printed on (sample 2) to (sample 10) using a reflective printer,
A color print was produced by performing development processing in the processing steps shown above. The print density and color are neutral 5 on the Macbeth color checker on the color paper manuscript.
The gray patch was adjusted to have a gray density of 1.0 on the print.

HV according to the modified Munsell symbol for the color batches red, green and blue of the Macbeth color chart on the resulting print
The C value was measured and shown in Table 1. It was also confirmed that the higher the C value, the more saturated the sample is in reproducing that color, and that the magnitude of this value corresponds to the intensity of each color when visually viewing the print. .

According to Table 1, in Samples 4 to 10 according to the present invention, the C value of any or all of red, green, and blue increases compared to Samples 1 to 3 of the comparative example, resulting in prints with high chroma. It is clear that the color reproducibility is improved.

Example 2 Color photographic material sample 11 was prepared by coating the following 1st to 12th layers in multiple layers on a paper support laminated on both sides with polyethylene. The first layer coating side of the polyethylene contains titanium white as a white pigment and a trace amount of ultramarine as a bluish dye.

(Photosensitive layer composition) The components and coating amounts in g/nr are shown below.

Regarding silver halide, the coating amount is shown in terms of silver.

1st layer (gelatin layer) Gelatin...1.30? ,
2JW (antihalation layer) Black colloidal silver ... 0.10 Gelatin ... 0.70 Third layer (low sensitivity red sensitivity layer) Iodine spectrally sensitized with red sensitizing dyes (*l and *2) Silver bromide (silver iodide 5.0 mol%, average grain size 0.4μ)
...0.15 gelatin
...1.00 cyan coupler (*3)
...0.14 cyan coupler (*4)
...0.07 anti-fading agent (*5, *6 and *7)
...0.10 coupler solvent (*8 and *9) ・
...0.06 4th layer (high sensitivity red sensitive layer) Silver iodobromide spectrally sensitized with red sensitizing dyes (*1 and *2) (116.0 mol% iodide, average grain size 0.06) 7μ)
...0.15 gelatin
...1.00 cyan coupler (*3)
...0.20 cyan coupler (*4)
...0.10 anti-fading agent (*5, *6 and *7)
...0.15 coupler solvent (*8 and *9) ・
・・0. IO 5th layer (intermediate layer) Magenta colloid SIm ・0.02 Gelatin ・・1.00 Color mixing prevention agent ($10) ・・0.08 Color mixing prevention agent solvent (*11 and *12) ・・0 .16 Polymer Latex ($13) ...0.10 6th layer (low sensitivity green sensitive layer) Silver iodobromide spectrally sensitized with green sensitizing dye (*14)
Silver iodide 2.5 mol%, grain size 0°4μ)
...0.10 gelatin
...0.80 magenta coupler (*15)
...0.10 anti-fading agent (*16)
...0.10 stain inhibitor ($17)
...0. Ol stain inhibitor ($18)
...0.001 coupler solvent (*11 and *19)
...0.15 7th Ji (high sensitivity green sensitive layer) Silver iodobromide spectrally sensitized with green sensitizing dye (114) (silver iodide 3.5 mol%, grain size 0°9μ)
...0. lO gelatin
...0.80 magenta coupler ($15)
...0.10 anti-fading agent (*16)
...0.10 stain inhibitor (*17)
...0.01 stain inhibitor ($18)
...0.001 coupler solvent ($11 and *1
9) ...0.15 No. 8 [(yellow filter layer) Yellow Colloid L ・0.20 Gelatin ...1.00 Color mixture prevention agent (*10) ...0.06 Color mixture prevention agent solvent (*11 and *12)...0.15 polymer latex ($13)...0. IO No. 9 JIi (Low sensitivity blue sensitive layer) Silver iodobromide spectrally sensitized with blue sensitizing dye ($20) (silver iodide 2.5 mol%, grain size 0°5μ)
...0.15 gelatin
...0.50 yellow coupler ($21)
...0.20 stain prevention agent (*18)
...0.001 coupler solvent (*9)
...0.15 1st O layer (high sensitivity blue-sensitive layer) Silver iodobromide spectrally sensitized with a blue sensitizing dye (*20)
Silver iodide 2.5 mol%, grain size 1°2μ)
...0.25 gelatin
...1.00 yellow coupler (*21
)...0.40 stain inhibitor (*18)
...0.0 O2 coupler solvent (*9)
...0. IO 11th layer (ultraviolet absorbing layer) Gelatin...1.50 Ultraviolet absorbing agent (*22, *6 and *7)...1.00 Color mixing prevention agent ($23)...0.06 Color mixing agent Inhibitor solvent (*9)...0.15 Anti-irradiation dye ($24)...0.02 Anti-irradiation dye (*25)...0.02 12th layer (protective layer) Fine particle salt Silver bromide (silver chloride 97 mol%, average particle size 0
．． 2μ) ...0.07 gelatin
...1.50 gelatin hardener ($
26) ...0.17$15.5'-dichloro-3,3'-di(3sulfobutyl)-9-ethylthiacarbocyanine Na salt *2 *3 *4 *5 *6 *7 Triethylammonium 3- [2-(2-[3-(
3-sulfopropyl)naphtho(1,2-d)thiazoline-2-indenmethyl]-1-butenyl)-3-naphtho(1,2-d)thiazolinoJpropanesulfone-2-[α-(2 ,4-di-t-amylphenoxy)hexanamide]-4,6-dichloro-5-ethylphenol 2-[2-chlorobenzoylamide]-4-chloro-5
-[α-(2-chloro-4t-amylphenoxy)octanamide]-phenol 2-(2-hydroxy-3-sec-5t-butylphenyl)benzotriazole 2-(2-hydroxy-5-
t-Butylphenyl) benzotriazole 2-(2-hydroxy 3.5-di-t-butylphenyl) 6-chlorobenztriazole di(2-ethylhexyl) phthalate trinonyl phosphate 2.5-di-t-octylhydroquinone tri Cresyl phosphate dibutyl phthalate polyethyl acrylate 5.5'-diphenyl-9-ethyl-3゜31-disulfopropyloxacarbocyanine Na salt *157-chloro-6-methyl-2-[1-12 octyloxy-5 -(2-octyloxy-5-t-octylbenzene-sulfonamide) 2-propyl] -1
8-pyrazolo[1,5-b] [1,2,4] )
Riazole*16 3.3.3',3'-tetramethyl-5°6.
5', 6'-tetrapropoxy-1゜1'-bisspiroindane*173-(2-ethylhexyloxycarbonyloxy) -1-(3-hexadecyloxy* 8 * 9 *11 *12 *13 *14 Diphenyl )-2-pyrazoline*182-Methyl-5-t-octylhydroquinone*19 trioctyl phosphate*20 triethylammonium 3-[2-(3-benzylrhodanine-5-indene)-3-benzoxazolinyl]propane Sulfonate *21 α-pivaloyl-α-[(2,4-dioxo-1-benzyl-5-ethoxyhydantoin-3-yl)-2-chloro-5-(α-2,4-di-t-amylphenoxy ) butanamide] acetanilide*225-chloro-2-(2-hydroxy-3-t-7
'Tyl-5-t-octyl)phenylbenztriazole*23 2. 5-di-5ec-octylhydroquinone *24 *25 *261.2-bis(vinylsulfonylacetamide)
Samples 12 to 18 were prepared by adding the compound of the present invention to the 11th sample of ethane sample 11.

Macbeth Color Checker - Inner Reversal Film R
Photographed with DP (manufactured by Fuji Photo Film), CP-56
The color positive film obtained by the P treatment was used as a color positive original, and printed on the color reversal papers of Samples 11 to 18 by a subtractive color method. At this time, printing was carried out by adjusting the gray color of Macbeth Color Checker 221 Toral 5 using a YMC filter so that the density on the print was 1.0 gray. Development processing was carried out using the process shown below.

In order to check the color reproduction of red, green, and blue of the obtained image, the H V C value according to the Munsell symbol was measured, and the C value is shown in Table 2.

On the other hand, in order to check the degree of contamination of the image of each sample due to residual dye after processing, samples 11 to 18 were passed through elementary gas for 50 minutes.
0 CMS with a light sensitive needle at a color temperature of 3200, and the same processing was performed. The cyan concentration of the obtained sample was measured using a Macbeth densitometer.

The measurement was made after processing using an automatic developing machine using the processing solution and processing steps described below until the cumulative replenishment amount of the solution became three times the tank capacity.

Here, the first water washing and the third water washing were each performed using a countercurrent washing method. That is, the washing water is passed through the first washing (2), the overflow is led to the first washing (1), the washing water is allowed to flow through the third washing (3), and the overflow is led to the third washing (2). The overflow of the third water wash (2) was led to the third water wash +11.

The composition of each treatment liquid was as follows.

Xing Erling Nitrilo-N,N,N-trimethylenephosphonic acid pentasodium salt Diethylenetriamine pentaacetic acid pentasodium salt Potassium sulfite Potassium thiocyanate Potassium carbonate Hydroquinone Potassium monosulfonate 1-phenyl-4-hydroxymethyl-4- Methyl-3-pyrazolidone potassium bromide potassium iodide mother liquor replenisher 1.0g 1.0g 3.0g 30.0g 1.2g 35.0g 3.0g 30.0g 1.2g 35.0g 25.0g 25.0g 2.0g 2.0g 0.5g 5, Oa+g Add water 1000cal 10
00ml ltpH 9,609,70 pH was adjusted with hydrochloric acid or potassium hydroxide.

Mother Liquor Replenisher Benzyl Alcohol Diethylene Glycol 3.6-Sythyl 1,8-Octane-Diol Nitrilo-N,N,N-trimethylenephosphonic Acid Pentasodium Salt Diethylenetriamine Pentaacetic Acid Pentasodium Salt Sodium Sulfite Hydroxylamine Sulfate Salt N-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-aminoaniline sulfate 15, Oa+J 12, On+4! 0.20g 0.5g 2.0g 2.0g 3.0g 5.0g 18.0+m1! 14.0m6 0.25g 0.5g 2.0g 2.5g 3.6g 8.0g Fluorescent brightener (diaminostilhene type) 1.0g 1.2
g Potassium bromide 0.5g Potassium iodide 1゜0mg Add water
1000m lt looom j! pH1
0.2510.40 pH was adjusted with hydrochloric acid or potassium hydroxide.

2) 1 jar (mother liquor and replenisher are the same) Ethylenediaminetetraacetic acid, 2-sodium, dihydrate 5.0g Ethylenediaminetetraacetic acid, Fe(III), ammonium, 1-hydrate 80.
0g sodium sulfite 15.
0g ammonium thiosulfate (700g/1)
160m j! 2-mercapto-1,3,4 triazole Add 0.5g water 1000 bridge lp H6
,50 pH was adjusted with acetic acid or aqueous ammonia.

These results are listed in Table 1 based on the added layer and amount of each dye used in each sample.

According to Table 2, it can be seen that Samples 12 to 18 of the present invention produced prints with excellent color reproduction without causing any contamination after processing.

(Effects of the Invention) According to the present invention, a silver halide color photographic material with significantly improved color reproducibility can be obtained.

Moreover, the above-mentioned photosensitive material has extremely reduced residual color after processing, making it suitable for practical use.

Claims (1)

[Claims] (1) In a photographic light-sensitive material having at least one silver halide emulsion layer on a support, the maximum absorption wavelength in the gelatin film is from 480 nm to 5.
A silver halide color photographic material comprising at least one dye having a wavelength of 30 nm and a dye having a maximum absorption wavelength of 580 nm to 630 nm in a gelatin film.