JPH01193733A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a red-sensitive emulsion layer having high sensitivity and low fogging by incorporating two kinds of specific compds. into a base. CONSTITUTION:The compd. expressed by formula I is incorporated into the base and at least one kind of the compds. expressed by formula II is incorporated therein. In formula I, R1, R2 respectively denote -COOR5, formula III; R3, R4 denote a hydrogen atom or alkyl group; Q1, Q2 denote an aryl group; X1, X2 denote a divalent combination group or bond; Y1, Y2 denote a sulfo group, carboxyl group, L1-L3 denote a methine group. In formula II, Y3 denotes -NHCO- or -CONH-; R8 denotes an aliphat. group, arom. group, etc., which may be substd.; X3 denotes a hydrogen atom, halogen atom, etc.; R7 denotes an alkyl group or acylamino group or a nonmetallic atomic group which forms 5-7-membered rings with X3 and R7; Z denotes a hydrogen atom or a group which can be eliminated at the time of coupling with the oxidant of a developing agent. In formula III, R5, R6 denote a hydrogen atom, alkyl group. The characteristics including excellent sharpness, high sensitivity and low fogging are thereby obtd.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a silver halide color photographic light-sensitive material, particularly a silver halide color photographic light-sensitive material for printing. Excellent image sharpness (hereinafter referred to as sharpness), and
This invention relates to a silver halide color photographic material with high sensitivity and low fog.

(Prior art) Silver halide color photographic materials are usually spectral sensitized by adding a spectral enhancer to silver halide according to the three primary colors of the subtractive color method, and a yellow dye is formed in the blue-sensitive silver halide emulsion layer. The green-sensitive silver halide emulsion layer contains a magenta dye-forming coupler, the red-sensitive silver halide emulsion layer contains a cyan dye-forming coupler, and after imagewise exposure, an aromatic primary amine is used as a color developer. A color image is obtained by processing using a color developing solution, followed by bleach-fixing.

However, this color image is not necessarily stable against light, heat, humidity, etc. In particular, cyan dye images fade due to heat and humidity more than yellow dye images or magenta dye images, so color balance may be affected. It changes and it takes a long time in practical terms! ! (For example, when saving an album, the printout turned reddish brown.)

As a coupler that forms a cyan image with high durability and can solve such problems, so-called 2, which is a phenol in which the 2.5-position of the benzene ring is substituted with an acylamino group, is used.
5-diacylaminophenol couplers are particularly excellent, as disclosed in JP-A-56-80045 and JP-A-56-10.
No. 4333, Japanese Patent Publication No. 37857-1983, Japanese Patent Publication No. 1987-3785-
It is described in No. 105229 and No. 60-24547. Further, a phenolic cyan coupler having an alkyl group having two or more carbon atoms at the 5-position of the phenol also forms a cyan image with high fastness.

These phenolic cyan couplers have high heat fastness and are extremely useful couplers for obtaining color photographic images with good storage stability. It is known to have stability, particularly less decrease in cyan density during bleach-fixing treatment, and excellent so-called color reversibility.

Thus, phenolic couplers of the type described above are preferred compounds for use as cyan dye-forming couplers in color photographic materials.

In addition, other criteria for selecting a cyan coupler include, for example, light resistance, spectral absorption characteristics of the coloring dye, and influence on photographic performance, and a cyan coupler that satisfies all of these properties is desired. It turns out.

On the other hand, image quality is another important characteristic required of color photosensitive materials for printing, and sharpness in particular has a large effect on image quality.

Two techniques are commonly used to improve the sharpness of color images: One is that the light that is scattered during or after passing through the silver halide emulsion layer is reflected again at the interface between the silver halide emulsion and the support or at the surface of the light-sensitive material on the opposite side of the silver halide emulsion layer. One is to prevent image blur caused by light entering the silver halide emulsion layer, that is, haleysilane, and the other is to prevent image blur caused by light scattering on the silver halide surface in the silver halide emulsion layer. The goal is to prevent blurring, or irradiation.

The latter type of irradiation prevention is generally used in silver halide color photographic materials for printing.

The silver halide emulsion layer is colored to prevent irradiation. These layers to be colored often consist of hydrophilic colloids, and therefore, for coloring them, water-soluble dyes are usually included in the layers. This dye must satisfy the following conditions.

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

(2) It should be photochemically inert, that is, it should not have an acute chemical effect on the performance of the silver halide photographic emulsion layer, such as a decrease in sensitivity, latent image regression, or fog.

(3) No harmful coloration remains on the photographic material after processing by being bleached or dissolved away during the photographic processing process.

Many efforts have been made by those skilled in the art to find dyes that meet these conditions, and the following dyes are known.For example, British Patent No. 506°385;
No. 7.429, No. 1,311.884, No. 1,338
, No. 799, No. 1゜385.371, No. 1. 46-
7, No. 214, No. 1.433.102, No. 1.55
3.516, JP-A-48-85,130, JP-A No. 49-
114゜420, 55-161, 233, 59
-111.640, U.S. Patent Nos. 3.247.127, 3.469.985, and 4,078°933; .472, same 3
, 379,533, other oxonol dyes described in British Patent No. 1.278.621, British Patent No. 5
No. 75,691, No. 680.631, No. 599.62
No. 3, No. 786.907, No. 907.125, No. 1
045.609, US Pat. No. 4.255.326, JP-A-59-211.043, etc.;
247, British Patent No. 2,014.598, British Patent No. 750
, 031, anthraquinone dyes described in U.S. Pat. No. 2,865,752, U.S. Pat.
No. 41, No. 2,538,008, British Patent No. 584゜609, British Patent No. 1,210,252, Japanese Patent Application Publication No. 50-40
．． No. 625, No. 51-3, 623, No. 51-10.9
No. 27, No. 54-118, 247, Special Publication No. 1973-3.
Azomethine dyes described in Japanese Patent Publication No. 286, No. 59-37,303, etc., Japanese Patent Publication No. 28-3,082, No. 44-16
, 594, 59-28.898, etc., British Patent No. 446,583, British Patent No. 1,33
5゜422, triarylmethane dyes described in JP-A-59-228,250, etc., British Patent No. 1゜075
．． No. 653, No. 1,153.341, No. 1.284.
No. 730, No. 1,475.282, No. 1.542.8
Merocyanine dye described in No. 07 etc., U.S. Patent No. 2
．． Examples include cyanine dyes described in No. 843.486 and No. 3.294,539.

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

(Problems to be Solved by the Present Invention) However, some oxonol dyes having two pyrazolone nuclei contain spectral rays in unnecessary areas for the silver halide emulsion itself or for the spectrally sensitized silver halide emulsion. Many of them have drawbacks such as sensitization, a decrease in sensitivity that may be caused by desorption of the spectral sensitizer, and increased fog.

Furthermore, due to the speeding up of development processing that has been carried out in recent years, some residual particles may remain after processing. 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 dry film is insufficient and the concentration decreases over time, resulting in the desired The disadvantage is that the photographic effect cannot be obtained.

In addition, particularly heat-fast materials such as the aforementioned 2.5-
When used in combination with diacylaminophenol couplers, etc., the degree of decrease in sensitivity and increase in fog becomes serious, which is a serious problem in practical use. Japanese Patent Publication No. 60-22515
5 is said to have a sensitive material that combines a 2,5-diacylaminophenol coupler and a specific oxonol dye, which has excellent dark fading resistance, good sharpness, and excellent latent image stability and whiteness (low capri). However, it has been found that the above combination is not sufficient particularly in terms of sharpness and fog.

(Objective of the present invention) Therefore, the object of the present invention is to provide a silver halide emulsion layer with excellent decolorization by processing without harmfully affecting the photographic properties of the silver halide emulsion layer;
By using a new water-soluble dye that is stable over time, this silver halide color photographic light-sensitive material provides color images that are stable over a long period of time, has excellent sharpness, and has a red-sensitive emulsion layer with high sensitivity and low capri. The goal is to provide the following.

(Means for Solving the Problems) The object of the present invention is to contain a compound represented by the following general formula [I] on a support, and at least one of the compounds represented by the following formula (n). This was achieved using a silver halide color photographic light-sensitive material characterized by the following.

General formula (1) % formula %) In the formula, R,, R, each represent -COORs, a hydrogen atom, or an alkyl group, and R3 and R6 each represent a hydrogen atom,
Represents an alkyl group or an alkyl group. Q, , Qg each represent an aryl group.

X, + X represents a divalent linking group or bond, and Y
+-Yz represents a sulfo group and a carboxyl group, L
+, Lx, and L-3 each represent a methine group@”
I, mz is l or 2, n is Oll or 2, p
l,p! are 0, l, 2.3 or 4, respectively! , ,S
R represents 1 or 2, respectively.

- Numerical formula [■] In the formula, Y represents -NHCO- or -CON H-, R1 represents an optionally substituted aliphatic group, aromatic group, hetero[group or Ryarylamino group, X3 is a hydrogen atom,
represents a halogen atom, an alkoxy group, or an acylamino group; R1 represents an alkyl group (having 2 or more carbon atoms) or an acylamino group; represents a hydrogen atom or a group that can be separated during color purging with an oxidized product of a developing agent.

Next, the dye represented by the general formula [1] will be explained in detail.

In the formula, RI SR2 represents a hydrogen atom, an alkyl group (e.g., methyl group, ethyl group), and R,
, R, is a hydrogen atom, an alkyl group (e.g., methyl group, ethyl group, isopropyl group, butyl group, etc.), a substituted alkyl group (as a substituent, a sulfo group (e.g., sulfomethyl group, sulfoethyl group, etc.), a carboxyl group (e.g., carboxymethyl group, etc.) group, carboxyethyl group, etc.), hydroxy group (e.g. hydroxyethyl group, 1,2-dihydroxypropyl group, etc.), alkoxy group (e.g. methoxyethyl group, ethoxyethyl group, etc.), halogen atom (fluorine atom, chlorine atom, bromine atom, atoms (e.g. 2-chloroethyl, 2
-bromoethyl, 2.2.2-trifluoroethyl, etc.), cyano groups (e.g., nanoethyl, etc.), sulfonyl groups (e.g., methanesulfonylethyl), nitro groups (e.g., 2-nitrobutyl, 2-nitro-2- methylpropyl group, etc.), amino group (e.g. dimethylaminoethyl group, diethylaminopropyl group, etc.), aryl group (e.g. benzyl group, p-chlorobenzyl group, etc.),
Phenyl group, substituted phenyl group (substituents include sulfo group (e.g. p-sulfophenyl X, o, p-disulfophenyl group, etc.), carboxyl group (e.g. p-carboxyphenyl group, m-carboxyphenyl group, etc.), Hydroxy groups (e.g. p-hydroxyphenyl group, m-hydroxyphenyl group, etc.), alkoxy groups (e.g. p-methoxyphenyl group, m-ethoxyphenyl group, etc.), halogen atoms (e.g. p-chlorophenyl'f, I)-bromo phenyl group, p-fluorophenyl group, etc.), cyano group (e.g. p-cyanophenyl group, O-cyanophenyl group, etc.), nitro group (e.g. p-nitrophenyl group,
m-nitrophenyl group, etc.), amino groups (e.g. p-dimethylaminophenyl group, p-diethylaminophenyl group, etc.), alkyl groups (e.g. p-methylphenyl, 0
- methylphenyl group, etc.)).

When R,,Rx represents -COORs, when Rs is a hydrogen atom, R,,R1 represents a carboxyl group, but not only the free acid but also salts (e.g. Na salt, K salt, ammonium salt, quaternary ammonium salt, etc.) may be formed.

Further, Rs and Ra may form a 5- or 6-membered ring (for example, a morpholino group, a piperidino group, etc.). Q, ,
Q is an aryl group (e.g. phenyl group, naphthyl group),
Substituted phenyl group (substituents include alkyl group having 1 to 4 carbon atoms, alkoxy group having 1 to 4 carbon atoms, halogen atom (chloro, bromo, fluoro), carbamoyl group (e.g. ethylcarbamoyl group), sulfamoyl group (e.g. ethylsulfamoyl group, etc.), cyano group, nitro group, alkylsulfonyl group (e.g., methanesulfonyl group, etc.), irisulfonyl group (e.g., Hensensulfonyl group, etc.), amino group (e.g., dimethylamino group, etc.), Acylamino group (e.g. acetylamino group),
Xt and Xt each represent a divalent linking method.

For more details, see 10-1 R, R, R.

-N-1-N-C0-2-3O! -1-N-3OI -
or a bond, R1 is a hydrogen atom, an alkyl group having 5 or less carbon atoms, a substituted alkyl group having 5 or less carbon atoms (substituents include an alkoxy group having 3 or less carbon atoms, a sulfo group (e.g. sulfoethyl group, sulfopropyl group, etc.) ), carboxyl group (e.g. carboxyethyl group, etc.), cyano group, hydroxy group, amino group (e.g. hydroxyethyl group etc.), sulfonamide group (e.g. methanesulfonamide group etc.), carbonamide group (e.g. acetylamino group etc.) , carbamoyl group (eg, ethylaminocarbonyl group, etc.), sulfamoyl group (eg, ethylaminosulfonyl group, etc.). Y, ,Y.

represent a sulfo group and a carboxyl group, respectively, and these may form not only a free acid but also a salt (for example, Na salt, K salt, ammonium salt, quaternary ammonium salt, etc.). L+, Lx, and Ls are Methine group, substituted methine group, (
Substituents include methyl group, ethyl group, phenyl group, etc.)
represents. m l and mz are each 1 or 2, n is 0
．． 1 or 2, R3 and R2 each represent 0.1, 2.3 or 4.3+, and sfi represents 1 or 2, respectively.

Among the substituents represented by the general formula (1), Rs and Ra are preferably hydrogen atoms and methyl groups, and R, and R4 are hydrogen atoms, alkyl groups with 4 or less carbon atoms, substituted alkyl groups with 6 or less carbon atoms ( Substituents include sulfo group, carboxyl group,
Hydroxy group, alkoxy group having 2 or less carbon atoms, chlorine atom, cyano group, amino group, alkylamino group having 4 or less carbon atoms are preferred), phenyl group, substituted phenyl group (substituents include sulfo group, carboxyl group, An alkoxy group having 4 or less carbon atoms, a chlorine atom, a cyano group, an alkyl group having 4 or less carbon atoms, an amino group, and an alkylamino group having 4 or less carbon atoms are preferable. For example, it is preferable to form a morpholino ring, a pyrrolidine ring, a piperidine ring).

Q+, Qz are phenyl groups, substituted phenyl groups (substituents include alkyl groups with 4 or less carbon atoms, alkoxy groups with 4 or less carbon atoms, halogen atoms (chloro, bromo, fluoro), dialkylamino groups with 4 or less carbon atoms) , etc.) are preferred.

For X, ,X, -〇-1 噸-N- or a bond is preferable, and R? Examples include a hydrogen atom, an alkyl group having 5 or less carbon atoms, a substituted alkyl group having 5 or less carbon atoms (as a substituent, an alkoxy group having 3 or less carbon atoms,
(cyan group, hydroxy group, alkylamino group having 4 or less carbon atoms, etc.) are preferred.

Furthermore, among the dyes represented by the general formula (+), rn.

=ml=1 is more preferred.

Next, specific examples of the compound of general formula (1) used in the present invention will be shown, but the present invention is not limited thereto.

+-1 1-6CH.

C11゜ ■-11 CH,C)I.

C1, C) I.

SOsK SO:J■ -14 CIll C1z0(CI
lx)asOJa 0(Cut)asOs
Nal-15! -18ICl12co.

CIlt　　　　　　　　cH.

SOs SO3 -22 I CHz GHz - 2
4 CχH3 ■ −25 ■ −27 SO3Na 5OiNaI −2
9! -31 SO3Na 5U3Na■ -
33 ■ -34 SO3Na SOsNal -35 C11゜! -37 SO3Na SO3Na■ -39 ■ -42 SO3Na SOJa■ -
43! -46 SOJa 5OJaHs CI, C
I+3! -49 CH,' ■ -51 C)1. Cl13
cHil 1
The compound shown in 1-C formula (1) can be synthesized by various synthetic methods, but for example, as shown in the reaction formula below, pyrazolone (n) and (Ill
It can be synthesized by condensing a), (I[lb), (Idle), ([[Id) or (nle)] in the presence of a base.

(R3CH)−+ 〇+−(−X+ −(CHt)P+−Yl)! +([I
Ia) (I[Ib) HC(OCzHs)i (Illc) R@ (Illd) ([[Ie) where R1, R8, Ql, xl, Yl, Ll, L□, L
. ethyl, etc.), phenyl group, X represents an anion (e.g. chloride, bromide, iodide, perchlorate, methyl sulfate, ethyl sulfate, p-)luenesulfonate, etc.)
represents.

Synthesis examples of compounds according to the present invention are described below, but the present invention is not limited thereto.

Synthesis Example 1 (Compound 3) 3-ethoxycarbonyl-1-(2-sulfobenzyl)
Add 5.2 g of pyrazolin-5-one to 50 mf of ethanol, then add 4.2 ml of triethylamine, and further add 1.5 g of malondialdehyde cyanyl salt, and heat under reflux for 3 hours to form a homogeneous solution. A solution of 1.2 g of sodium acetate in 15 ml of methanol is added to this hot solution while stirring.

Next is isoproper tool 25m! When 1 is added, dark purple crystals are precipitated. The crystals were separated, washed with isopropanol, and dried to obtain 2 g of Compound 3.

Melting point 300°C or higher 0 λs+ax 551nm t6.73
j! , triethylamine? , 5mf and cool on ice. In this, glutaraldehyde cyanyl hydrochloride 2
．． Add 8g and stir for 3 hours 4.2g of sodium acetate
When 50 ml of methanol solution was added and 25 ml of isopropanol was further added, dark purple crystals were precipitated. The crystals were collected in a furnace, washed with isopropanol, and dried to obtain 5.4 g of Compound 8.

λa+ax 626nm g7.89X10' Synthesis Example 3 (Compound 10) 3-(2-hydroxyethylcarbamoyl)-1-(2
-Sulfobenzyl)pyrazoline 8g 1 methanol 30m
1. Mix 3.8 ml of triethylamine and cool. 3 g of glutaraldehyde cyanyl salt are added to this solution, followed by 2 ml of acetic anhydride. After reacting for 1 hour at room temperature, 20 ml of isopropanol was added to precipitate black crystals.

The crystals were washed with hearth bottom isopropanol and dried to obtain 6.1 g of Compound 10.

Melting point 300℃ or higher λ-ax 633nm ε 8.8X1
0' Synthesis Example 4 (Compound 18) 3-carboxy-1-+2- (4-sulfophenyl)
ethyl) pyrazolin-5-one 6g 1 methanol 50m
1. Combine 7 ml of triethylamine, then add N, N'
- Add 1.6g of diphenylformamidine hydrochloride 2
After heating for a while, it becomes a homogeneous solution. To this solution was added 5 QmJ of a methanol solution of 4.5 g of sodium acetate, and then 20 mJ of isopropanol! When added, yellow crystals precipitate. The crystals were boiled, washed with isopropanol, and dried to obtain 4 g of Compound 18.

λ+wax 452nm +2. 10XIO' Synthesis Example 5 (Compound 12) Compound 12 is obtained by the same operation as in Synthesis Example 2 using 3-ethoxycarbonyl-1-(2,4-disulfobenzyl)pyrazolin-5-one.

λax 640nm ε 7. 0
2X10' Synthesis Example 6 (Compound 20) Synthesis Example 2 using 3-carboxy-1-+2- (4-sulfobutyloxy)benzyl)pyrazolin-5-one
Compound 20 is obtained by the same operation as above.

λ steel aX 628 nm ε7.39X10' Next, general formula [11] will be explained in detail.

- In formula [1], R@ is a chain or cyclic aliphatic group preferably having 1 to 32 carbon atoms (e.g., methyl group, butyl group, pentadecyl group, cyclohexyl group, etc.), aromatic group (e.g., phenyl group) , naphthyl group, etc.), a heterocyclic group (e.g., 2-pyridyl group, 3-pyridyl group, 2-furanyl group, 2-oxazolyl group, etc.), or a substituted amino group; Aryloxy group (e.g. methoxy group, dodecyloxy group, methoxyethoxy group, phenyloxy group,
2,4-de-tert-amylphenoxy group, 3-te
rt-butyl-4-hydroxyphenyloxy group, naphthyloxy group, etc.), carboxy group, alkyl or arylcarbonyl group (e.g. acetyl group, tetradecanoyl group, benzoyl group, etc.), alkyl or aryloxycarbonyl group (e.g. methoxycarbonyl group, benzyloxycarbonyl group, phenoxycarbonyl group, etc.), acyloxy group (e.g., acetyl group, benzoyloxy group, phenylcarbonyloxy group, etc.),
Sulfamoyl groups (e.g., N-ethylsulfamoyl group, N-octadecylsulfamoyl group, etc.), carbamoyl groups (e.g., N-ethylcarbamoyl group, N-methyl-dodecylcarbamoyl group, etc.), sulfonamide groups (e.g., methanesulfonamide group, benzenesulfonamide group, etc.), acylamino group (e.g., acetylamino group, benzamide group, ethoxycarbonylamino group, phenylaminocarbonylamino group, etc.), imide group (e.g., succinimide group, hydantoinyl group, etc.), Sulfonyl group (e.g. methanesulfonyl group, etc.)
, a hydroxy group, a cyano group, a nitro group, and a halogen atom.

In the present specification, the term "aliphatic group" refers to a linear, branched or cyclic aliphatic hydrocarbon group, such as alkyl, alkenyl,
It may be either saturated or unsaturated, such as an alkynyl group.

In the general formula [11, R is an alkyl group having 2 to 20 carbon atoms (e.g., ethyl group, butyl group, pentadecyl group, etc.) or an acylamino group (e.g., tetradecanoylamino group, benzoylamino group, 2-( 2,4-diTERT
-amylphenoxy)butanamide group, etc.).

In the general formula [■], X is a hydrogen atom, a halogen atom,
It represents an aliphatic group (eg, methyl group, propyl group, allyl group, etc.), an alkoxy group (eg, methoxy group, butoxy group, etc.), or an acylamino group (eg, acetamido group, etc.).

-i In formula [n], R1 and X are different from the above in 5.6.
It may be a nonmetallic atomic group forming any ring of 7, examples of which include a benzene ring and a lactam ring.

In -IIQ formula [■], Z represents a hydrogen atom or a coupling-off group, such as a halogen atom (e.g., fluorine atom, chlorine atom, bromine atom, etc.), an alkoxy group (e.g., ethoxy group, dodecyloxy group,
methoxycarbamoylmethoxy group, carboxypropyloxy group, methylsulfonyl ethoxy group, etc.), aryloxy group (e.g., 4-chlorophenoxy group, 4-methoxyphenoxy group, 4-carboxyphenoxy group, etc.), acyloxy group (e.g., acetoxy group) , tetrazokayloxy group, benzoyloxy group, etc.), sulfonyloxy group (e.g., methanesulfonyloxy group, toluenesulfonyloxy group, etc.), amide group (e.g.,
dichloroacetylamino group, heptabtyrylamino group, methanesulfonylamino group, toluenesulfonylamino group, etc.), alkoxycarbonyloxy group (e.g.
ethoxycarbonyloxy group, benzyloxycarbonyloxy group, etc.), aryloxycarbonyloxy group (e.g., phenoxycarbonyloxy group, etc.), aliphatic or aromatic thio group (e.g., ethylthio group, phenylthio group, tetrazolylthio group, etc.), imide group (e.g., succinimide group, hydantoinyl group, etc.), N
-heterocycles (e.g., 1-pyrazolyl group, 1-penztriazolyl group, etc.), aromatic azo groups (e.g., phenylazo group, etc.); these leaving groups include photographically useful groups; You can stay there.

In the general formula [■], R7 is preferably an alkyl group having 2 to 15 carbon atoms, more preferably 2 to 4 carbon atoms.

In the general formula [111, Z is preferably a hydrogen atom or a halogen atom, and a halogen atom is particularly preferred.

In the general formula [11F, preferred X3 is a halogen atom.

-a In formula [11], when R1 and X are closed to form a ring, it is preferably a 5-membered oxindole ring.

Next, specific examples of the compound of the general formula [■] used in the present invention will be shown, but the present invention is not limited thereto.

(C-1) (C-2) (C-3) H (C-4) OH (C-5) (C-6) (C-7) l1 (C-8) (C-9) (C -10) (C-11) OH CsH++ (t) (C-12) OH (C-13) (C-14) (C-15) (C-16) \ CsL+ (t) (C-18) ( C-19) (c-20) CaH+, (t) (C-22) (C-23) (C-24) CSHr+ (t) (C-25) (C-26) (C-27) NllSUzL; nHq (C-28) Cl (C-29) When using the dye represented by general formula (1) as a filter dye, anti-irradiation dye or antihalation dye, any effective amount can be used. ,
It is preferable to use it so that the optical fourth degree is in the range of 0.05 to 3.0.

The addition time may be 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.

(2) A method in which the dye of the present invention is directly dissolved or dispersed 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 an aqueous solution or solvent and then used in an emulsion layer or a hydrophilic colloid layer. Suitable solvents, e.g. Eva, methyl alcohol, ethyl alcohol, propyl alcohol, methylcellosolve, JP-A-48-9715, U.S. Pat. No. 3,75
It can also be added to the emulsion in the form of a solution dissolved in a halogenated alcohol, acetone, water, pyridine, etc., or a mixed solvent thereof, as described in No. 6.830.

■ A method in which a hydrophilic polymer with a charge opposite to that of the dye ions 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.

The polymer mordant is a polymer containing a secondary and tertiary amino group, a polymer having a nitrogen-containing heterocyclic moiety, a polymer containing a quaternary cation group, etc., and a molecular weight of 5,000 or more, particularly preferably 10,000 or more. .

For example, vinyl pyridine polymers and vinyl pyridinium cationic polymers disclosed in U.S. Pat. No. 2,548,564, etc.; vinylimidazolium cationic polymers disclosed in U.S. Pat. No. 4,124.386, etc.; U.S. patents Polymer mordant 7flIH crosslinkable with gelatin etc. disclosed in No. 3゜625.694 etc.
U.S. Patent No. 3,958.995, Japanese Patent Application Publication No. 1152-1983
Aqueous sol-type mordants disclosed in US Pat. No. 28, etc.; water-insoluble mordants disclosed in US Pat. No. 3,898,088; dyes disclosed in US Pat. No. 4,168,976, etc. Reactive mordants capable of carrying out covalent bonding; polymers derived from ethylenically unsaturated compounds having dialkylaminoalkyl ester residues as described in British Patent No. 685.475; British Patent No. 850.
Products obtained by the reaction of polyvinyl alkyl ketones with aminoguanidine as described in U.S. Pat. No. 281; derived from 2-methyl-1-vinylimidazole as described in U.S. Pat. Examples include polymers.

■ 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 (filed by Fuji Photo Film on January 26, 1980), 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.

-a The cyan coupler represented by formula (II) is used in an amount of 0.1 to 1 mol, preferably 0.2 to 0.5 mol, per 1 mol of S halide in the photosensitive silver halide emulsion layer to be introduced.

-IG The cyan coupler represented by formula (II) is dissolved in a high boiling point organic solvent (e.g. phthalate ester, phosphate ester, fatty acid ester) and dispersed in a hydrophilic colloid medium to form silver halide. Can be added to emulsions.

Furthermore, to improve storage stability, a benzotriazole ultraviolet absorber may be used simultaneously, or a substantially water-insoluble organic solvent-soluble polymer may be used in combination.In particular, the latter polymer is particularly effective in improving fading resistance. It is valid. Particularly useful products include those described in Japanese Patent Application No. 1983.

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

In the present invention, any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, and silver chloride may be used as the silver halide. Especially when the purpose is rapid processing, silver chlorobromide containing 90 mol% or more (preferably 98 mol% or more) of silver chloride is preferable, and this silver chlorobromide contains a small amount of silver iodide. However, it is preferable that all (not included) be included.

The silver halide grains used in the present invention may have regular crystal shapes such as cubic or octahedral, or irregular crystal shapes such as spherical or plate-like.
ular) crystal form, or a composite form of these crystal forms. It is also possible to use a mixture of particles of various crystal forms, but it is preferable to use regular crystal forms.

The silver halide grains used in the present invention may have different phases inside and on the surface, or may consist of a uniform phase.
For example, it may be a negative-tone emulsion), or it may be a grain that is mainly formed inside the grain (for example, an internal latent image type emulsion, a pre-fogged direct reversal type emulsion), and preferably,
These are particles on which a latent image is formed primarily on the surface.

The silver halide emulsion used in the present invention has a thickness of 0.
Is it a tabular grain emulsion in which grains with a diameter of 5 microns or less, preferably 0.3 microns or less, preferably 0.6 microns or more, and an average aspect ratio of 5 or more occupy 50% or more of the total projected area? A monodisperse emulsion having a theoretical coefficient of variation (value S/d, which is the standard deviation S divided by the diameter d in a distribution expressed by a diameter when the projected area is approximated by a circle) of 20% or less is preferred. Further, two or more kinds of tabular grain emulsions and monodispersed emulsions may be mixed.

The photographic emulsion used in the present invention is P.
, Glafkides), Chimie er P.
hysiquePhotographeque) (
Beaumontel Publishing, 1967), G. F. Duffin, Photographic Emulsion Chemistry (Photogr.
aphic Emulsion Chesistr
y) (Focal Press, 1966), Bui El Zelikman (V, L, Zelika+an)
Making and Coating Photographic Ink Emulsion
CoatingPhotographic Emul
sion) (Focal Press, 1964).

In addition, during the formation of silver halide grains, silver halide solvents such as ammonia, rhodanpotash, rhodanammonium, thioether compounds (for example, U.S. Pat. No. 3,271,157, U.S. Pat. No. 3,574, U.S. Pat. No. 628, No. 3.704,130, No. 4.297.439, No. 4.276.374, etc.), thione compounds (e.g., JP-A No. 144319/1983)
No. 53-82408, No. 55-77737, etc.), amine compounds (for example, JP-A-54-100717, etc.) can be used.

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

Silver halide emulsions are usually chemically sensitized.

For chemical sensitization, for example H, Friesel (H.

Fr1eser) W, Die Grundlagen der Fotografisien Prozesse Mitu Zilberhalogenden
derPhotographischen Proz
esse wit Silberhalogeni
The method described in den) (Académie Societe Fellerlagus Gesellschacht 1968), pages 675-734, can be used.

That is, sulfur-enhanced methods using sulfur-containing compounds that can react with activated gelatin and silver (e.g., thiosulfates, thioureas, mercapto compounds, rhodanines); reducing substances (e.g., stannous salts, reduction sensitization using noble metal compounds (e.g., gold complex salts,
A noble metal sensitization method using complex salts of metals of group 1 of the periodic table such as pt, lr, pd, etc. can be used alone or in combination.

The silver halide photographic emulsion used in the present invention may contain various compounds for the purpose of preventing capri during the manufacturing process, storage, or photographic processing of light-sensitive materials, or for stabilizing photographic performance. can. That is, azoles such as benzothiazolium salts, nitroindazoles, triazoles, benzotriazoles, benzimidazoles (particularly nitro- or halogen-substituted);
Heterocyclic mercapto compounds such as mercaptothiazoles, mercaptohendithiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazoles (especially l-phenyl-5-mercaptotetrazole), mercaptopyrimidines; The above-mentioned heterocyclic mercapto compounds having a water-soluble group; thioketo compounds such as oxazolinthione; azaindenes such as tetraazaindene (particularly 4-hydroxy 1210 (1°3.
Many compounds known as anti-capri agents or stabilizers can be added, such as (3a, 7) tetraazaindenes); benzenethiosulfonic acids; benzenesulfinic acid; etc.

The silver halide photographic emulsion of the present invention can contain color pigments such as cyan coupler, magenta coupler, yellow coupler, etc.
It can include a coupler and a compound that disperses the coupler.

That is, it may contain a compound that can develop color by oxidative camping with an aromatic primary amine developer (eg, phenylene diamine derivative, aminophenol derivative, etc.) in color development treatment. For example, magenta couplers include 5-pyrazolone couplers, pyrazolobenzimidazole couplers, cyanoacetylcoumarone couplers, pyrazolotriazole couplers, open-chain acylacetonitrile couplers, and yellow couplers include acylacetamide couplers (e.g., benzoylacetanilides, baloylacetanilides), etc.

These couplers are preferably non-diffusible and have a hydrophobic group called a ballast group in the molecule.

The coupler may be either 4-equivalent or 2-equivalent to one ion, or it may be a colored coupler that has a color correction effect or a coupler that releases a development inhibitor during development (so-called DIR coupler). good.

In addition to the DIR coupler, the coupling reaction product may include a colorless DIR coupling compound which is colorless and releases a development inhibitor.

Also, cinnamic acid ester and 2-(2-hydroxyphenyl)
Ultraviolet absorbers and anti-fading agents represented by benzotriazole may be added.

These anti-fade agents include compounds described in the following special specifications: U.S. Pat. No. 3,432,300;
No. 3,574,627, No. 3.700.455, No. 3.764,337, No. 3935.016,
4.254,216, 4.268.593, 4,430,425, 4,465.757, 4
, 465,765, 4.518.679, British Patent No. 1.347.556, British Patent Publication No. 2,066.9
No. 75, JP-A-52-152.225, JP-A No. 53-17
．． No. 729, No. 53-20.327, No. 54-145
．． No. 530, No. 55-6321, No. 55-21,00
No. 4, No. 61-12.246, No. 61-73, 152
No. 61-90.155, No. 61-90.156, No. 61-145゜554 The photographic emulsion of the present invention contains, for example, polyalkylene oxide or its It may also include derivatives such as ethers, esters, and amines, thioether compounds, thiomorpholines, quaternary ammonium salt compounds, urethane derivatives, urea derivatives, imidazole derivatives, 3-pyrazolidones, and the like.

The silver halide photographic emulsion of the present invention may contain known aqueous dyes other than the dyes disclosed in the present invention (for example, oxonol dyes; hemioxonol dyes and merocyanine dyes) as filter dyes or for various purposes such as preventing irradiation. It may also be used in combination with known cyanine dyes, merocyanine dyes, and hemicyanine dyes other than the dyes shown in the present invention as spectral sensitizers.

The photographic emulsion of the present invention may contain various surfactants for various purposes such as coating aids, antistatic properties, improving slipperiness, dispersing emulsions, preventing adhesion, and improving photographic properties (for example, accelerating development, increasing contrast, and sensitizing). But that's fine.

In addition, the photosensitive material of the present invention contains anti-fading agents, hardening agents, anti-color capri agents, ultraviolet absorbers, protective colloids such as gelatin, and various additives, as detailed in Research Disclosure Vol. 1.176 ( 197B, XII)R
D-17643 etc.

The finished emulsion is coated onto a suitable support such as baryta paper, resin coated paper, synthetic paper, triacetate film, polyethylene terephthalate film, other plastic bases or glass plates.

The silver halide photographic light-sensitive materials of the present invention include color positive films, color papers, color negative films, color reversals (which may or may not contain couplers), and photographic materials for platemaking (for example, lithium film, lithography), and color reversal films (which may or may not contain couplers). eup film, etc.), photosensitive materials for cathode ray tube displays (e.g., photosensitive materials for emulsion X-ray recording, materials for direct and indirect projection using screens), silver salt diffusion transfer process (Silver 5alt diffusion transfer process)
transfer process) photosensitive materials,
Photosensitive material for color diffusion transfer process, Gui transfer process (1sbibitiontransfe)
Direct Pr1nti■
(age) photosensitive materials, photosensitive materials for thermal development, photosensitive materials for physical development, etc.

Exposure to obtain photographic images may be carried out using conventional methods: natural light (sunlight), tungsten lamps, fluorescent lamps, mercury lamps, xenon arc lamps, carbon arc lamps, xenon flash lamps, cathode ray tube flying spots. Any of a variety of known light sources can be used. The exposure time is usually 1/1000 seconds to 30 seconds, but an exposure shorter than 1/1000 seconds, such as 1/10' to 1/10'' seconds using a xenon flash lamp or cathode ray tube, may be used. Alternatively, an exposure longer than 30 seconds can be used.If necessary, the spectral composition of the light used for exposure can be adjusted with a color filter.Laser light can also be used for exposure.Also, an electron beam can be used. , X-ray,
Exposure may be performed by light emitted from a phosphor excited by T-rays, α-rays, or the like.

For photographic processing of light-sensitive materials made using the present invention, for example, Research Disclosure (Re5earch)
Disclosure) No. 176, No. 28-30
Any of the known methods and known treatment liquids, such as those described on page RD-17643, can be applied. This photographic processing may be either photographic processing that forms a silver image (black and white photographic processing) or photographic processing that forms a dye image (color photographic processing), depending on the purpose. The processing temperature is usually chosen between 18 and 50°C, but 1
The temperature may be lower than 8°C or higher than 50°C.

There are no particular restrictions on the color photographic processing method, and any method can be applied.For example, a typical method is to perform color development, bleach-fixing processing after exposure, and further washing with water and stabilization processing as necessary. , After exposure, color development, bleaching and fixing are performed separately, and if necessary, washing with water and stabilization processing are performed. After exposure, development is performed with a developer containing a black and white developing agent, and -line exposure is applied. After that, color development and bleach-fixing are carried out, and if necessary, washing with water and stabilization are carried out, or after exposure, development is carried out with a developer containing a black and white developing agent, and then a fogging agent (
For example, there is a method in which the image is developed with a color developing solution containing (for example, sodium borohydride) and then subjected to bleach-fixing treatment, followed by further washing with water and stabilization treatment as required.

The aromatic primary amine color developing agents used in the color developing solution of the present invention include known ones that are widely used in various color photographic processes. These developing agents include amine phenol and p-phenylene diamine derivatives. Preferred examples are p-phenylenediamine derivatives, and representative examples are shown below, but the invention is not limited thereto.

D-IN, N-diethyl-p-phenylenediamine D-22-amino-5-diethylaminotolu-32
-amino-5-(N-ethyl-N-laurylamino)toluene D-44-(N-ethyl-N-(β-hydroxyethyl)aminocoaniline D-52-methyl-4-[N-ethyl-N -(β-hydroxyethyl)aminocoaniline D-6N-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-4-aminoaniline D-7N-(2-amino-5-diethylaminophenylethyl) Methanesulfonamide D-8N, N-dimethyl-p-phenylenediamine D-94-amino-3-methyl-N-ethyl-N-methoxyethylaniline D-104-amino-3-methyl-N-ethyl-N- β
-Ethoxyethylaniline D-114-amino-3-methyl-N-ethyl-N-β
-butoxyethylaniline These p-phenylenediamine derivatives may also be salts such as sulfate, hydrochloride, sulfite, p-)luenesulfonate, etc. The above compounds are described in U.S. Pat.
．． No. 015, No. 2,552゜241, No. 2,566.
No. 271, No. 2,592.364, No. 3,656.9
No. 50, No. 3゜698.525, etc.

The amount of the aromatic primary amine color developing agent used is about 0.1 g to about 20 g per liter of developer solution, and more preferably about 0.1 g to about 20 g per liter of developer solution.
Concentrations range from 5g to about Log.

As is well known, the color developer used in the present invention may contain hydroxylamines.

Although hydroxylamines can be used in the free amine form in color developers, it is more common to use them in the aqueous acid salt form. Common examples of such salts are sulfates, oxalates, chlorides, phosphates, carbonates, acetates, and others. Hydroxylamines may be substituted or unsubstituted, and the nitrogen atom of hydroxylamines may be an alkyl group! may have been replaced.

The amount of hydroxylamine added is 0g per 1z of color developer.
The amount added is preferably from 10 g to 10 g, more preferably from 0 to 5 g, as long as the stability of the color developing solution is maintained.

In addition, as a preservative, it is preferable to contain sulfites such as sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metasulfite, potassium metasulfite, and carbonyl sulfite adducts. The amount is preferably from 0 to 20 g/l, and more preferably from 0 to 5 g/l, and as long as the stability of the color developing solution is maintained, the smaller the amount is, the more preferable it is.

Other preservatives include JP-A Nos. 52-49828, 56-47038, 56-32140, and 59-
Aromatic polyhydroxy compounds described in US Pat. No. 1,601,42 and US Pat. No. 3,746,544: US Pat. No. 3,615.5
03 and British Patent No. 1.306.176; α-aminocarbonyl compounds described in JP-A-52-143020 and JP-A-53-89425; JP-A-57-44148 and JP-A-57-5374
Various metals described in No. 9 etc.; JP-A-52-102727
Various I listed in the issue! Hydroxamic acids described in No. 52-27638; α, α” described in No. 59-160141
-°dicarbonyl compounds; salicylic acids described in No. 59-180588; alkanolamines described in No. 54-3532; poly(alkyleneimines) described in No. 56-94349; gluconic acid described in No. 56-75647 Derivatives etc. can be mentioned. Also, hydrazine
N,N-diacetic acid is also preferred, and two or more of these preservatives may be used in combination, if necessary. Particularly preferred are 4,5-dihydroxy-m-henzendisulfonic acid, poly(ethyleneimine), triethanolamine, and the like.

The pH of the color developer used in the present invention is preferably 9 to 12, more preferably 9 to 11, and the color developer may contain other known developer component compounds. can.

For details on the types and amounts of preservatives, buffers, chelating agents, development accelerators, antifoggants, and fluorescent brighteners that can be added to color developers, see Patent L1i dated March 18, 1988. (A) (Fuji Photo Film ℃ Preferably 30-40℃. Processing time is 20 seconds ~
5 minutes, preferably 30 seconds to 4 minutes. Although it is preferable that the amount of replenishment is small, the amount of replenishment is preferably small. (30~100100 per hit
O is preferably 60 to 400 m1.

Next, the desilvering step in the present invention will be explained.

The desilvering step may generally include any process such as a bleaching step-fixing step, a fixing step-bleach-fixing step, a bleaching step-bleach-fixing step, or a bleach-fixing step. The desilvering step takes 2 minutes or less, more preferably 15 seconds to 90 seconds.

Further, as for the bleaching solution, bleach-fixing solution, and fixing solution used in the present invention, as well as the additives and amounts thereof to these solutions, those described on pages 20 to 25 of the above-mentioned application specification can be applied, for example. .

Furthermore, the matters described on page 25 to page 29, line 12 of the application specification can also be applied to the water washing and/or stabilization treatment performed after the desilvering treatment.

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

Example 1 A multilayer color print sample (1) having the layer structure shown below was prepared on a paper support laminated on both sides with polyethylene.

The composition of each layer is shown below. The numbers are coating ffi (g/m
), however, for silver halide emulsions, the coating amount is in terms of silver, and for cyan couplers and dyes, it is mol/n? It was shown in

Support polyethylene laminate paper [the polyethylene on the first layer side contains a white pigment (Ti02) and a blue dye (ulmarine blue)] -th layer (blue-sensitive silver halide emulsion layer) Spectral sensitizer (Sen-1) Monodisperse silver chlorobromide emulsion (EM-1) with the addition of 0.16 spectral sensitizer (3en-1) Monodisperse silver chlorobromide emulsion (EM-2) with the addition of 0.16 spectral sensitizer (3en-1) 0.10 Anticapri agent (Cpd -1) 0.004 Gelatin 1.83 Yellow coupler (ExY) 0.83 Dye stabilizer (Cpd-
2) 0.03 polymer (Cpd-3)
0.08 Solvent (Solv-1 and 5olv-2 volume ratio 1:1) 0.35 Hardener (Hd
) 0.02 Second layer (color mixing prevention layer) Gelatin 1.25 Color mixing prevention agent (Cpd-4) 0.04 Solvent (Sol
v-3 and 5olv-4 volume ratio 1:1) 0.20 hardener (H
d) 0.02 third layer ()3 malignant silver halide emulsion layer) spectral sensitizer (Sen-1,2)
Monodisperse silver chlorobromide emulsion (EM-3) with added 0.05 monodisperse silver chlorobromide emulsion (EM-4>0.11 with added spectral sensitizer (Sen-2, 3)) (Cpd-5) 0.001 gelatin
1.79 magenta coupler (E
xM) 0.32 color image stabilizer (Cpd-6)
0.20 color image stabilizer (Cpd-7)
0.03 color image stabilizer (Cpd-8)
0.03 ton capacity (3o1v-3 and 5olv-5
Volume ratio 1:2) 0.65 Hardener (H
d) 0.01 Fourth layer (ultraviolet absorption layer) Gelatin 1.58 Ultraviolet absorber (tJV-1/2/3 molar ratio 1:4:4) 0.62 Color mixing inhibitor (Cpd-4) 0.05 Solvent (Solv-6) 0.34 Dye (D
y-1) 1.8xlO-'mol dye (Dy
-2) 2.0xlO-'molar hardener (Hd
) 0.01 Fifth layer (red angry silver halide emulsion layer) Monodispersed silver chlorobromide emulsion (EM-5) with added spectral sensitizer (Sen-4, 5) 0.07 Spectral sensitizer (Se
Monodisperse silver chlorobromide emulsion (EM-6
) 0.15 Capri inhibitor (Cpd-9)
0.0002 gelatin 1.
34 Cyan coupler Table 2 6.7X10-'mol Ultraviolet absorber (UV-1/3/4 molar ratio 1:3:3) o, 17 Polymer (Cpd-3) 0.33 Solvent (
Solv-1) 0.23 Hardener (H
d) 0.01 Sixth layer (ultraviolet absorbing layer) Gelatin 0.53 Ultraviolet absorber (tJV-1/2/3 molar ratio 1:4:4) o, 21 Solvent (Solv-6) 0.08 Hardening layer Agent (Hd) -0,01 Seventh layer (protective layer) Gelatin 1.33 Acrylic modified copolymer of polyvinyl alcohol (degree of modification 17%) 0.17 Liquid paraffin 0.03 Silver halide emulsion used in the above sample (EM-1) was prepared as follows.

(1i'&) H201000m 1 NaCl 5.5 g Gelatin 25 g (2 liquids) Sulfuric acid (IN)
20 ml χ3 solution) The following compound (1%) 2 ml CH.

CH.

(4?&)KBr 2.8
0g NaC10,34g H! Add O and 140 ml (5 liquids) Ag
Add NOi 5 gHzO to 140 ml (6 liquids) KBr
67.20g NaC18,26g Kg I rC16 (0,001χ) 0.7
Add m1H and O to make 320 ml (7 liquids)
AgNOs 120 gNH,NC
320 ml (1 solution) was heated to 74 °C by adding 2 ml of h (50%) 1 HzO, and (2? &) and (3 solutions were added. Then, (47 ml and (5 N) Added at the same time.Additionally 10
After 5 minutes, liquid (6) and liquid (7) were added simultaneously over a period of 45 minutes. After 5 minutes, the temperature was lowered and desalted. Add water and dispersed gelatin, adjust the pH to 6.2, average particle size 0.96 μm, coefficient of variation (standard deviation divided by average particle size; s/d) 0.08, silver bromide 80 mol. % monodispersed cubic silver chlorobromide emulsion was obtained. This emulsion was optimally chemically sensitized with sodium thiosulfate.

Other silver chlorobromide emulsions (EM-2) to (EM-6) were prepared in the same manner by varying the amount of chemicals, temperature, and time.

The details are shown in the table below.

Table - Coefficient of variation = standard deviation/average particle diameter (Sen-1) 5x1o-' mol/Ag mol (
Sen-2) 4xto-' mol/Ag mol (S
en-3) 5xto-' mol/Ag mol (CH
z) JOJ-N(CJs)s (Sen-4) 1.8X10-' mol/Ag mol (Sen-5) 3X10-3 mol/Ag mol (
ExY) IL (ExM) YN Na (Cpd-1) (Cpd-2) (Cpd-3) -+-CI□ -CH-] C0NHC,H, (t) Molecular weight approximately 60000 (Cpd-4) ( Cpa-5) (Cpd-6) (Cpd-7) (Cpd-8) (Cpd-9) (I C4119(L) CsL+(t) (UV-3) (UV-4) H (3oj!v 1 ) C,11,, -C11-C11 (-CL-1toyCO
OCsll+t(n)~1 (So 1 v-2) 0 = P(-OCq H+* (iso))
3 (Sol v-3) (Sot) v-4) (Soffv-5) (Sol v ~6) COOCH2CH (C, Hl) C, l! .

(CH2)1 COOCHzCH(CzHs)C4H9(Dy-1
) (Dy-2) S03K Samples (2) to (7) were prepared by using the above sample S03 and changing the dye in the fourth layer and the cyan coupler in the fifth layer. The composition is shown in Table 2. Note that the dye and cyan coupler numbers correspond to those added to the specific examples in the text. In addition, the following cyan coupler (C) was used for comparison.

(C) Cyan coupler for comparison Table 2 For samples (2) to (7), photosensitive needle (Fuji Photo Film Co., Ltd.!!!FWH type, color temperature of light source 3200K)
was used to provide gradation exposure for sensitometry through a red filter. At this time, exposure was performed at an exposure time of 0.1 seconds and an exposure amount of 250 CMS. As for sharpness, the cyan density was set to 1.5, and exposure was applied through an optical wedge for sharpness.

After exposure, processing consisting of the following steps of color development, bleach-fixing, and water washing was performed.

Toro Uni■ Direct skin Bright color development 33℃ 3 minutes 30 seconds Bleach fixing 33℃ 1 minute 30 seconds Washing with water
Dry for 3 minutes at 24-34℃ 70-8
0°C for 1 minute The composition of each treatment solution is as follows.

Advance J■1 Yosui 800
mf diethylenetriaminepentaacetic acid Acetic acid 1.0g Nitrilotriacetic acid 1.5g Benzyl alcohol 15 ml! Diethylene glycol 10 ml Sodium sulfite
2.0g potassium bromide
0.5g potassium carbonate 30
gN-ethyl-N-(β-methanesulfonamidoethyl)-3 monomethyl-4-aminoaniline sulfate 5.0 g hydroxylamine sulfate 4.0 g Fluorescent brightener (WH
ITEX 4B.

Add water and get 1000+sj! pH
(25℃) 10.20! Sako 4'
Tatsumizu 400
m1 ammonium thiosulfate (70%) 150mj
! Sodium sulfite 18g Iron ethylenediaminetetraacetate ([[I] Ammonium 55g Add water to 1000mlp1000℃)
6.70 The above sample (1
) to (7) were evaluated for sensitivity, fog, sharpness, and dark fading. Sensitivity is concentration -1
, 0 was taken. However, for convenience, sample (1)
The relative sensitivity of was set as 100. Regarding fog, the value of so-called press fog when the development time was 7 minutes was also tested. Sharpness was expressed by a numerical value defined as follows.

Sharpness: C at 15 spatial frequencies/8m,
T, F, (%) The higher the sharpness value, the better.

In addition, the dark fading property was determined by testing the developed sample at 80°C and 70% RH.
The sample was left for 14 days and evaluated as a percentage of the color density reached after the test with respect to the color density of 2.0 before the test. The results are shown in Table 3.

Table 3 As is clear from the results shown in Table 3, the dye obtained by combining the cyan coupler and dye of the present invention has a high frequency range and low fog;
It can also be seen that it is a sensitive material with excellent sharpness and dark fading resistance.

Example-2 A sample (8) having the following layer structure was prepared in the same manner as in Example-1.

-th layer (blue-sensitive silver halide emulsion N) Monodisperse silver chlorobromide emulsion (EM-7) added with a spectral sensitizer (Sen-6) 0.27 Gelatin 1.86 Yellow coupler (ExY) 0. 82 solvent (Solv-4
) 0.35 Hardener (Hd)
0.02 Secondary N (Color mixture prevention 11 gelatin 0.99 Color mixture prevention agent (Cpd-4) 0.06 Solvent (Solv
-3 and 5olv-4 volume ratio 1:1) 0.12 Hardener (Hd
) 0.02 Third layer (green-sensitive silver halide emulsion N) Monodispersed silver chlorobromide emulsion (EM-8) with added spectral enhancer (Sen-7,3) 0.45 Gelatin 1.24 Magenta coupler (ExM) 0.35 color image stabilizer (Cpd-
6) 0.20 color image stabilizer (Cpd-7)
0.03 color image stabilizer (Cpd-8)
0.03 Solvent (Solv-3 and 3o1v-5 volume ratio 1:2) 0.65 Hardener (H
d) 0.01 Fourth layer (ultraviolet absorption layer) Gelatin 1.58 Ultraviolet absorber (LJV-1/2/3 molar ratio 1:474) 0.62 Color mixing inhibitor (Cpd-4) 0.05 Solvent ( Solv-6) 0.34 dye (D
y-1) 1.8xlO-'mol dye (Dy
-2) 2.0xlO-'molar hardener (Hd
) 0.01 Fifth N (red-sensitive silver halide emulsion layer) Monodispersed silver chlorobromide emulsion (EM-9) with added spectral sensitizer (Sen-4, 5) 0.20 Gelatin
0.92 cyan coupler (Table 5)
6.7X10-'mol polymer (Cpd-3)
0.30 UV absorber (LIV-1/3/4 molar ratio 1:3:3) o, 17 Solvent (Solv-4) 0.20 Hardener (Hd) 0.01 Sixth layer (UV absorbing layer ) Gelatin 0.53 Ultraviolet absorber (UV-1/2/3 molar ratio 1:4:4) o, 21 Solvent (Solv-6) 0.08 Hardener (Hd) 0.01 Seventh layer (
Protective layer) Gelatin 1.33 Acrylic modified copolymer of polyvinyl alcohol (degree of modification 17%) 0.17 Liquid paraffin 0.03 Details of the silver halide emulsion used in the above sample are shown in Table 4.

Table 4 Coefficient of variation - standard deviation/average particle diameter (Sen-5) 5O3H-N(C*Hs)a (Sen-7) In the above sample, the dye in the fourth layer and the cyan coupler in the fifth layer were changed. Samples (8) to (12) were prepared. The composition is shown in Table 5.

Samples (8) to (12) in Table 5 were exposed for evaluation in the same manner as in Example-1, and the following treatments were performed.

1 degree plate color development 35℃ 45 seconds bleach fixing
Rinse for 45 seconds at 30-35℃■ 30
～35℃ Rinse for 20 seconds ■ 30～35℃
Rinse for 20 seconds ■ Rinse for 20 seconds at 30-35°C ■ Dry for 30 seconds at 30-35"C
70-80℃ 60 seconds (rinse→
■It is a 3-tank countercurrent force type. ) The composition of each treatment liquid is as follows.

Mitatezato 1 Okasui 800+*
j! Ethylenediamine-N,N.

N”,N'-tetramethylenephosphonic acid 1.5 g Triethylenediamine (l,4 diazabicyclo(2,2,2) octane) 5.0 g Sodium chloride 1.48 Potassium carbonate
25 gN-ethyl-N-(β
-Methanesulfonamidoethyl)-3-methyl-4-aminoaniline sulfate s,OgN,N-diethylhydroxylamine 4.2gFluorescent brightener (
UV I TEX CK Ciba Geigi)
Add 2.0g water 1
0100O! pH (25℃>10
．． 10th base Wataru Kisui 400
sj! Ammonium thiosulfate (70%) 100m
1Sodium sulfite 18gIron(III) ethylenediaminetetraacetate Ammonium 55gDisodium ethylenediaminetetraacetate 3gAmmonium bromide
40g glacial acetic acid
Add 8g water 1
0100O! pH (25℃) 5.5 Yuesu Kai ion exchange water (calcium, magnesium 3pp each
m or less) The developed samples (8) to (12) were evaluated in the same manner as in Example-1. However, the sensitivity is based on the relative sensitivity of sample (8) by 10
0, and the value of press fog was taken when the development time was 90 seconds. The results are shown in Table 6.

Table 6 As is clear from the results shown in Table 6, the sample in which the cyan coupler and dye of the present invention were combined was a sensitive material with high sensitivity, low fog, and excellent sharpness and dark fading resistance.

Example-3 In order to examine the stability of the dye of the present invention in the film, Example-1
and 2 samples (2), (4), (7),
(9) and (11) were left at 35° C.-80% for 2 weeks, and the residual rate of the dye was measured and evaluated. The results are shown in Table 7.

As is clear from the results in Table 7, it can be seen that the dye of the present invention has excellent stability in the membrane.

(Effects of the Invention) According to the present invention, a hydrophilic colloid layer containing a novel dye that does not adversely affect the photographic properties of a photographic emulsion, particularly on fog and fog, is excellent in decolorization by processing, and is stable over time. A silver halide color photographic light-sensitive material can be obtained. Further, according to the present invention, it is possible to obtain a silver halide color photographic material having a red-sensitive emulsion layer that is excellent in dark fading resistance and sharpness, and has high sensitivity and low fog.

Patent applicant: Fuji Photo Film Co., Ltd. Procedural Amendment (8)
Gutu 1, Incident Display 1986 Patent Application No. 17777
No. 2. Name of the invention Silver halide color photographic light-sensitive material 3. Relationship with the case of the person making the amendment Patent applicant Address: 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Name (520) Fuji Photo Film Co., Ltd. zu 藍↓ Date of amendment order ← Hassha 曾 → ＆ Subject of amendment We will submit a revised version of Specification 6, the details of the amendment (no changes to the content).

2nd day of the month of 1963 age

Claims (1)

[Scope of Claims] A silver halide color characterized by containing a compound represented by the following general formula [I] on a support and at least one compound represented by the following general formula [II] Photographic material. General formula [I] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ In the formula, R_1 and R_2 are respectively -COOR_5, ▲ Mathematical formula,
There are chemical formulas, tables, etc. Represents ▼. R_3 and R_4 each represent a hydrogen atom or an alkyl group, and R_5 and R_
6 represents a hydrogen atom, an alkyl group, or an aryl group, respectively. Q_1 and Q_2 each represent an aryl group. X_1 and X_2 represent a divalent linking group or bond,
Y_1 and Y_2 represent a sulfo group and a carboxyl group, respectively. L_1, L_2, and L_3 each represent a methine group. m_1, m_2 are 1 or 2, n is 0, 1 or 2, p_1, p_2 are each 0, 1, 2, 3 or 4,
s_1 and s_2 each represent 1 or 2. General formula [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, Y_3 represents -NHCO- or -CONH-, and R_8 is an optionally substituted aliphatic group, aromatic group, heterocyclic group, or represents an arylamino group;
It represents a nonmetallic atomic group forming a membered ring, and Z represents a hydrogen atom or a group that can be separated upon coupling with an oxidized product of a developing agent.