JPH083611B2 - Silver halide color photosensitive material - Google Patents

Description

Detailed Description of the Invention

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color photographic light-sensitive material having high sensitivity and excellent image sharpness.

BACKGROUND OF THE INVENTION

A silver halide color photographic light-sensitive material contains a dye-forming compound in order to obtain a color image, but a dye image formed from such a dye-forming compound (that is, an azo or azomethine dye image, etc.) is aged. In addition to discoloration by bleaching, it is known that discoloration occurs when a bleaching agent having strong oxidizing power (for example, swirl salt, hydrogen peroxide, etc.) is used in the silver bleaching process after color development for speeding up processing.
This is an obstacle to speeding up the process. Because of this, heat, light,
There has been a long-standing need for dyes that are stable to humidity and chemicals. On the other hand, it is known that the stability of the dye is increased by complexing the dye with a metal. For example, U.S. Pat.
No. 2,891 discloses a technique for using a metal complexed azo dye for diffusion transfer. However, although metal complex dyes are preferable in terms of dye stability, most metal dyes and dye precursors are
It has the drawback of being colored during exposure. Therefore, when such a dye (or a dye precursor) and silver halide are contained in the same layer in a light-sensitive material, the dye (or dye precursor) acts as an undesirable filter and reaches the silver halide. Absorption of a part of the light to be used causes desensitization (that is, loss of photographic sensitivity). For this reason, a technique is conceivable in which the silver halide and the dye (or the dye precursor) are contained in separate layers and can react with each other, but such a method requires a large number of layers and becomes thick. However, there arises a problem that efficiency in manufacturing and image formation is deteriorated. On the other hand, the color purity of the color-forming dye produced by the coupling reaction of the coupler and the quinonediimine, which is an oxide of the color-developing agent, is greatly involved in color reproduction. However, undesired secondary absorption was reduced, but it is still far from ideal for magenta and cyan. Color negative
In the positive system, if a coloring dye having such secondary absorption is used for both negative and positive photosensitive materials, the effect of color distortion due to secondary absorption is emphasized, vivid brightness is lost, and color reproduction is achieved. The above is a serious problem. Therefore, some kind of masking is applied to the color negative film as an intermediate medium,
It is common practice to substantially eliminate the secondary absorption of color forming dyes. For example, U.S. Pat. No. 2,449,966 describes various color correction methods, but at present, the colored coupler method is most widely used for masking a color negative film. This method uses a colored coupler which is colored by introducing a substituent into a reaction active site of a magenta and cyan dye-forming coupler in which secondary absorption is a problem. Colored couplers, like ordinary couplers, are subjected to color development to form colored dyes. In one example, as a result of color development, a decrease in yellow colored coupler and an increase in yellow secondary absorption accompanying the formation of a magenta coloring dye occur at the same time.However, the colored coupler is itself used as a colorless coupler in an appropriate amount ratio. If the two are controlled so that they are just balanced, the edge-magenta coloring layer can always have equal absorption in the blue portion regardless of the degree of coloring of the magenta dye. When masking is performed in this way, it is necessary to increase the exposure amount of blue light at the time of printing, and it is optically equivalent to the case where a magenta coloring dye having no secondary absorption in the blue part is used. . In order to correct the secondary absorption of the blue part and the green part of the cyan coloring dye by the same principle,
A magenta colored coupler is added to the red-cyan color forming layer. The color masking dyes such as colored couplers ordinarily used for color masking also have the drawback that they are discolored over time, discolored by a bleaching agent having a strong oxidizing power and already colored at the time of exposure. In order to ameliorate various drawbacks of such dye images and color masking dyes, a technique of forming a dye using a ligand-releasing compound or a technique of forming a masking dye is disclosed in U.S. Pat.Nos. 4,555,477 and 4,555,478. There is. It is a substantially colorless, immobile ligand release consisting of a ligand capable of complexing with a metal ion to form a metal complex dye, and a group leaving from the ligand upon silver halide development. Of the red blood salt or EDTD Fe (II
It is a technique of bleaching in a bleaching bath containing I), followed by fixing treatment, and then using a metal ion-containing bath such as ferrous ammonium sulfate to form a metal complex dye with a ligand and a metal ion. This technique, however, has some drawbacks. For example, when the ligand-releasing compound is used in place of the conventional colored colored coupler, there is a defect that the edge portion of the image is blurred. Therefore, the inventors of the present invention achieved the present invention by further developing the techniques shown in US Pat.

[Object of the invention]

An object of the present invention is to provide a silver halide color photographic light-sensitive material having improved image sharpness without causing a decrease in sensitivity.

Configuration of the Invention

 The object of the present invention is to have a silver halide emulsion layer on a support.
A polymer coupler and a compound represented by the general formula [A]
Halogenated by containing and in the same photosensitive layer
It is achieved by a silver color photographic light-sensitive material. General formula [A] LIG-X (where X is a result of silver halide development, and releases the LIG portion.
Represents a group capable of being, and when LIG is bonded to X,
Complexed with metal ions, the metal in the color photosensitive material
Represents a ligand moiety capable of forming a complex dye, LI
G-X itself is a substantially colorless and non-diffusible compound.
It ) Hereinafter, the compound of the general formula [A] according to the present invention will be described.
Will be described in detail. The LIG-X compound is substantially colorless, but substantially
Colorless is a colored pigment that forms a complex with the metal ion at the LIG part.
Before forming, LIG-X has virtually no visible color
That is, LIG-X has a low optical density.
It means indicating a degree (about 0.05 or less). Therefore,
The LIG part forms a complex with the metal ion and only the peak wave of the absorbance
Changing the long λmax to change the hue of the dye
Clearly different from compound, from colorless precursor to colored
It forms a pigment. Metal-LIG complex formation means that LIG is X in the unexposed area of the photographic element.
It happens when they are combined. In the exposed area, LIG is oxidized.
LIG part cleaved from X by the developed developing agent
Are washed away in the treatment process. Therefore, LIG section
Will be washed away from the photographic element once it is cleaved from X
It has sufficient solubility in It remains in the unexposed area
LIG-X compound is a metal ion (for example, divalent iron oxide).
ON) and complex-forming reaction to form a colored mask dye. Dye formed by complex formation of LIG and metal ion
Is a colored dye, that is, the visible region (approx. 400 nm to 700 nm)
It is a dye that absorbs light of wavelength. LIG part and metal ion
Complex formation may be performed with 1: 1 LIG and metal ion
However, complex formation occurs with multiple LIG parts and one metal ion.
You may For example, 2 to 3 LIG molecules
Complexed with metal ions. Representative dyes that can be formed
Are cyan, yellow and magenta dyes. X is preferably an oxidized developing agent (eg oxidized.
Of the color developing agent)
As an embodiment, a color is produced by reacting with an oxidized color developing agent.
Or there are couplers that produce colorless reaction products. This
The two types of couplers in
Known, for example Research Disclosure, No. 17643,
Section VII, December 1978 and references contained therein
It is written in. However, in the present invention, X is the result of silver halide development.
Releases dyes and other photographically useful fragments
Get effective results even with ingredients known in the art
Can be. Redox dye releasing properties
There are compounds and similar compounds, and US Pat. No. 4,053,31
No. 2, No. 4,055,429, No. 4,076,529, No. 4,139,379,
4,139,389, 4,199,354, 4,199,355, 4,2
32, 107 etc. For example, X may contain a ballast group, LIG-X
And X have been de-diffused in the photographic element during processing. rose
The strut group is preferably an organic ballast group, even in non-polymer
A polymer may be used, and a photograph of LIG-X in an alkaline treatment liquid
It is non-diffused within the element. Particularly useful non-polymeric rose
The strut group is a long-chain alkyl group (for example, having 6 to 30 carbon atoms),
Or with it, eg an alkyl group or an alcohol
Aromatic groups substituted with xy groups (phenyl, naphthyl),
Lucoxy group, alkyl sulfonamide, alkyl sulf
Amoyl and alkylamino. Representative ballast group
There are the following. −COC₁₁H_{twenty three}, -COC₆H_Four(t-C₁₂H_{twenty five}), −CON (C₁₂H_{twenty five})₂, -NHSO₂C₁₆H₃₃，-SO₂NHC₁₈H₃₇, -OC₁₂H_{twenty five}， X may be a monomer, a dimer, an oligomer
Or a polymer coupler may be used.
In this case, more than one LIG can be bound to X. LIG is oxidized
As long as it is cleaved from the coupler by reaction with the image base,
It may combine with X at a different position. Preferably LIG is
Is coupled to X at the coupling position, in this case the coupler
When LIG reacts with the oxidized developing agent, LIG becomes
Cleave from X. However, LIG is a non-coupling of X
It can also be combined with X at the
As a result of the reaction between the drug oxide and X, LI
G splits. LIG is bound at the uncoupling position of X
Other group is attached to the coupling position,
Can be, for example, the usual coupling
Group leaving group, LI attached at the above non-coupling position
Same LIG as G or different LIG. Ie book
The LIG-X compound that can be effectively used in the invention is 1 mol.
More than 1 mol of LIG compound can be released per unit.
In this case, LIG may be the same or different,
Cleaves at the same time, or in pieces, i.e. at different rates
May be. LIG and X are bonded by a single bond or an organic connecting part.
In the latter case, when cleaved, LIG
Remains in the protonation according to its pKa
Or ionize. As an effective organic connection
Is -COO-, -CONH-, -O-, -S-, -SO₂-,-
SO₂NH-,-CH₂CO−, −SO₂N (alkyl) -and US special
Timing groups such as those described in Xu 4,248,962
is there. A particularly useful bond is a single bond or a bond by -O-
Is. Examples of groups of X useful in embodiments of the present invention include:
An example is a coupler residue.  Where R₇Is an alkyl group which may have a substituent (preferably
Or having 1 to 20 carbon atoms), optionally substituted
Aryl group (preferably having 6 to 14 carbon atoms)  In these structural formulas, BALL is any of the above ballasts.
It may be a group. (For example -NHSO₂C₁₆H₃₃, -NHCO-Al
Xylene-oxy-aryl, alkyl having 1 to 20 carbon atoms
Group, aryl group having 6 to 14 carbon atoms in the nucleus, etc.)
LINK is a linking group as described above (eg single bond, organic
X) before reacting with oxidized developing agent.
And LIG are connected, and BALL is a polymer skeleton
Good. Also, another useful group of examples of X is polymeric
There are things. The following are preferred as the polymer X.
Hydrophilic polymers having mer units are mentioned. (A) Copolymerizable ethylenically unsaturated hydrophilic monomer
(Amount sufficient to make LIG-X itself hydrophilic) In the formula, R ′ represents a hydrogen atom or lower alkyl, CO
UP reacts with oxidized color developing agent to produce colored or colorless
Represents the residue of the coupler that produces the reaction product of
Is as described above. LINK is a linking group that connects COUP and LIG (for example, a single bond,
In the above-mentioned organic connecting part), the bonding position with COUP is as described above.
As a result of the reaction of COUP with an oxidized color developing agent, LI
Connect with COUP at any position as long as NK is released from COUP.
You may match. The fact that the polymer is hydrophilic here means that the polymer is
Means water soluble or water dispersible, 100 ml water
It is preferable that 1 g or more of polymer can be dissolved or dispersed in
Good. As a copolymerizable ethylenically unsaturated hydrophilic monomer
Is one or more imino groups, amide groups, sulfonamide groups
(These may have a substituent.) Hydroxy
Group, carboxyl group, sulfo group, phosphono group, quaternary amine
It is preferable to have a monium group and a phosphonium group.
Yes. The following are specific examples of the hydrophilic monomer.
You can Hydroxyalkyl acrylates (eg, 2-hydroxy)
Droxyethyl acrylate), hydroxyalkyl
Tacrylates (eg, 2-hydroxypropylmeta
Acrylate, acrylamides (eg, acrylic acid)
De, N-isopropyl acrylamide, 2-acryl
Mido-2-hydroxymethyl-1,3-propanedio
), Methacrylamides (eg methacrylamide)
De), albonic acid group, phosphoric acid group or sulfonic acid group
And the salts thereof (for example, itacone
Acid, acrylic acid, methacrylic acid, 2-acrylamide-
2-Methylpropanesulfonic acid, 3-methacryloyl ester
Xoxypropane-1-sulfonic acid, styrenesulfonic acid,
Vinyl sulfonic acid and its alkali metal salts,
Ammonium salt), a cationic acid salt (for example, m-N-vinyl)
Rubenzyl-N, N, N-trimethylammonium chloride
P-N-vinylbenzyl-N, N, N-trimethylan
Monium chloride, N- (2-methacryloyloxy
Ethyl-N, N, N-trimethylammonium mesosulfate
Ito) of the copolymerizable ethylenically unsaturated hydrophilic monomer
The ratio is preferably 10-90 mol%, more preferably 40-75.
Mol%. Lower alkyl represented by R'in the monomer unit (b)
The kill group may have a substituent and preferably has 1 to 1 carbon atoms.
3 of them. Specifically, methyl, ethyl, propy
And chloromethyl. Better as R '
Preference is given to hydrogen or methyl, with hydrogen being the most preferred.
Is also preferable. The ratio of the monomer unit (b) is preferably 10 to 90 mol%
And particularly preferably 40 to 75 mol%. The effective LIG portion is preferably a ferroin type metal
A ligand capable of forming a complex, for example, hydrazone
, Tetrazolyl pyridines, pyridyl quinazolines,
Bis-isoquinolines, imines, phenanthroline
, Bipyridines, terepyridines, vidazines, pi
Lysyl diazines, pyridyl benzimidazoles, di
Azyltriazines, o-nitrosoanilines, o-ni
Trosophenols, tetrazines, triazines
Therefore, these are Schilt et al, Talanta, 15, p475-478 (1
968). Besides these, Schilt et al, Tal
anta, 15, p852-855 (1968).
Pyridine derivatives of enazine and quinoxaline, Schilt et
al, Talanta, 15, p1055-1058 (1968)
A benzimidazole derivative having such a substituent, Schi
lt et al, Talanta, 16, p448-452 (1969).
Methyl and phenyl-2-pyridyl ketones having a substituent
Oximes and the like. To give other ligands
Compounds that can be described are listed below in "Talanta"
Has been done. 16, p519-522 (1969), 13, p895-902 (1966), 17, p
649-653 (1970), 19, q1025-1031 (1972), 21, p831
-836 (1974), 22, p915-917 (1975), 23, p543-545
(1976), 24, p685-687 (1977), 26, p85-89 (197
9), p863-865 (1981), 36, p373-376 (1979), 55, p
55-58 (1980), 29, p129-132 (1982), and Blanda
mer et al, J. Chem. Soc. Dalton, p1001-1008 (1978), C
ase, J. Org. Chem, 31, p2398-2400 (1966).
ing. Of these, terpyridine is magenta
It is particularly effective for obtaining a masking dye. A particularly useful LIG moiety is a residue of a compound of the structure
It Where m is a positive integer from 0 to 1 and n and p are
Can independently take 0 or 1, and is not a single bond
S represents a double bond. Z is R1-N =, 0 =, S =, R¹−P
=, (R¹)₂P- or (R¹)₃P = and Z is (R¹)₂P
In the case of −, n is 1, and in other cases, n is 0. Preferred
Preferably m is 0 or 1 and Z is R¹-N =. R¹， R²， R³， R^Four， R^Five， And R⁶Are independent hydrogen
Child, amino group (first, second, or third), hydroxy
Group, mercapto group, alkoxy group (preferably 1 to
Methoxy, chloromethoxy with 20 carbon atoms
Substituted by Si, ethoxy, octyloxy, imino groups
Alkoxy, etc.), alkyl group (preferably 1)
It has 20 carbon atoms and is methyl, ethyl, chloro.
Romethyl, isopropyl, t-butyl, heptyl, imimi
Group substituted with an alkyl group), aryl group
(Preferably having 6 to 14 carbon atoms and
Nyl, naphthyl, xylyl, p-methoxyphenyl, a
Aryl groups substituted by mino groups) or
Terror groups (preferably 5 to 20 carbons, nitrogens in the nucleus,
Having sulfur or oxygen atoms, eg pyridyl, quino
Ril, heterocycles substituted with imino groups, etc.)
It R⁶Is a group as defined above, P is 1 andIs a single bond. Separately, if m is 0, R¹And R²， R²And R³， R³When
R^FourAnd 5 to 5 each independently have a substituent.
20-membered mono- or polycyclic carbocycle or heterocycle (pyridi
Le, quinolyl, triazinyl, phenanthrolinyl, pi
Heteroatoms (such as rimidyl) and the carbon atoms necessary to form
Can be an atom (nitrogen, oxygen, sulfur, selenium, etc.)
Yes. The ring thus formed may contain one or more
Oxo, alkyl, amino, imino, aryl, phosph
Inno (eg diphenylphosphino), alkoxy,
Amide, sulfonamide, thio or sulfo group or
Heterocyclic groups (pyridyl, pyrimidyl, thiazolyl, imi
Dazolyl, thienyl, etc.) and the like. If m is 1, 2 or 3, then R¹And R²， R^FiveAnd R⁶， R³
And R^FourAre paired and described independently when m is 0
A 5- to 20-membered monocyclic ring which may have a substituent such as
Are the carbon atoms and the atoms necessary to form the polycyclic heterocyclic nucleus.
Even terror atoms (nitrogen, oxygen, sulfur, selenium, etc.)
Good. R^FiveAnd R⁶When is a double bond when
For example, p is 0, and P is 1 when is a single bond. Preferably
Was cleaved from X, LIG being sufficiently soluble in the treatment solution
Sometimes it's like being washed out of the elements. If required, LIG is soluble in one or more
Have a group such as a hydroxy group to impart moderate solubility
Can be Useful LI that forms color dye complex salts with divalent iron ions
Examples of the G part include the following. These structures
In the construction, the binding site with X is shown as incomplete binding.
is there. Λ of iron (II) ion-complex salt dyes obtained from each
max is also shown at the same time, but depending on X, it may be a little (10-15n
m) shift.  The reaction product of the X part and the oxidant of the developing agent is not yellow.
In the case of diffusible dye, LIG used in combination with the X part
As a part, it forms a complex with a metal ion to form a magenta metal complex.
What forms the body pigment is also a magenta non-diffusible pigment
In some cases, it forms a yellow or cyan metal complex dye
If the LIG part to be used is a cyan non-diffusible dye,
Forms a yellow, magenta or red metal complex dye
The LIG portion is preferably used. Representative of LIG-X compounds useful in the present invention
Is shown below.  Practically effective LIG-X compounds in the present invention are
Simple synthesis using chemical reactions known in true chemistry
However, in general, derivatives of LIG and induction of X
Made by the reaction with the body. Synthesis example of LIG-X compound
Is shown below. As a preferred embodiment, the following general preparation method is used.
Can be (A) a hydroxy group-containing LIG group and a leaving group (for example,
Halogen, tosylate, mesylate, sulfonium salt
And LIG group by reaction with a coupler having
A LIG-X compound with a coupler attached at -O- was obtained.
It In the LIG group having a mercapto group, LIG and X are-
An L-X compound linked with S- is obtained. (B) a coupler having a hydroxy group and the coupler shown above.
The same LIG-X as in (a) in the reaction with a LIG group having a degroup
The compound is obtained. In another aspect, the LIG-X compounds useful in the present invention
Carboxylic acid halide or sulfonic acid halide
Having a LIG group, a hydroxy group, a mercapto group or
Is a condensation reaction with a coupler having an amino group at the active site.
Can also be obtained, in which case LIG and X are ester, amino
LI linked with amide, sulfonamide or thioester
A GX compound is obtained. An example of the synthesis of a typical LIG-X compound is shown below.
You Synthesis Example 1. Synthesis of Exemplified Compound A-2 12.5 g of 1,4-dihydroxy-N- [4-
(2,4-di-t-bentylphenoxy) butyl] -2-
Naphthamide, 3.1 g of 2,6-di-2-pyridyl-4-me
Tylsulfonopyridine and 100 ml dry N, N-dimethylphore
Lumamide (100ml) little by little with 50% sodium hydroxide
Ride (50 mmol) was added. After the generation of gas subsided, the mixture was heated to 90 ° C for 2 hours.
Pour the reaction mixture into 2 liters of dilute potassium phosphate-potassium buffer solution.
It was After distilling off the solvent, the suspension was washed with cyclohexane and washed with 9 g of yellow.
Brown crystals were obtained. Combination of desired structures by mass spectroscopy
I confirmed that it was a thing. Synthesis Example 2. Synthesis of Exemplified Compound A-4Is mixed with 100 ml of ethanol and under argon atmosphere overnight
Reflux. Cool to room temperature, separate the oil part and remove the solvent.
Was slowly distilled off. Crystallized from isopropanol
Recrystallization gave 1.70 g of pale yellow crystals. Structure of interest by IR, NMR and mass spectroscopy
Was confirmed. Synthesis Example 3. Synthesis of Exemplified Compound A-3 1.4 ml of triethylamine in 100 ml of dry acetonitrileWas added. Refluxed for 24 hours under an argon atmosphere. After cooling
Precipitated white crystals (2.5 g) were collected by filtration. By IR, NMR, and mass spectroscopy,
It was confirmed that the compound was Synthetic Example 4. Synthesis of Exemplified Compound A-5 2,6-di-2- (2-di-2- (2-di-2-hexyl) -2-fluorohexyl-amino-pyroxan) dissolved in 100 ml of tetrahydrofuran
Pyridyl-4-β-aminoethyloxypyridine 0.58 g
And 0.43 dry triethylamine to 1.33 g 1-hydro
Xy-N [4- (2,4-di-t-pentylphenoxy)
Butyl] 4- (4'-chlorosulfonylphenoxy)-
1.33 g of 2-naphthamide in 20 ml of tetrahydrofuran
The dissolved solution was added. The mixture was stirred at room temperature for 2 hours
It was The triethylamine / hydrochloride formed is filtered off and the filtrate
0.5 ml glacial acetic acid was added, the filtrate was dried and then methylene chloride was added.
Extracted and washed with 1N acetic acid, water, and saturated saline
It was then dried. Distill off methylene chloride under reduced pressure and remove ethyl acetate.
Redissolved in tellurium and evaporated to dryness to give 1.7 g of fluffy white crystals.
Obtained. Targeted by IR, NMR and mass spectroscopy
It was confirmed to be a compound. Synthesis Example 5. Synthesis of Exemplified Compound A-1 0.5 g (2 mmol) of 2,6-di-2-pyridyl-4-
Hydroxypyridine, 0.53 g (3.75 mmol) tetra
Methylguanidine, 5 ml acetonitrile and 1.8 g (2.7
Mmol of N- [4-chloro-3- (2-chloro-4,
4-dimethyl-3-oxopentanamide) phenyl]
Hexadecanesulfonamide was added. Heat to 40 ℃ 6
After stirring for hours, the solvent was distilled off. The residue is silica gel
It was separated and purified by column chromatography. Expansion is salt
Start with methylene chloride and gradually mix with ethyl acetate.
It was Evaporate the solvent from the eluate with 10-50% ethyl acetate
The obtained crystal is the target substance by mass spectroscopy.
It was confirmed that there was (0.78g). The type of metal ion complexed with LIG-X is
In other words, as long as it is
As long as it seems to stay in the formed form,
Can be used. In general, the formation of such complexes
The logarithmic value of the growth constant is in the range of approximately 10 to 30, preferably
It is in the range of approximately 15 to 25. The effective metal ion is Fe⁺⁺， Co⁺⁺， Cu⁺， Cu⁺⁺， Ru⁺⁺， O
s⁺⁺In the practice of this invention, Fe⁺⁺Is preferred
New In the practice of this invention, cleavage of LIG from X results in LIG
Caused by the reaction of the -X compound with the oxidized developing agent
It In the practice of this invention, silver halide development is used.
Any development that can react with LIG-X when oxidized
The main drug can also be used. Particularly effective developing agents are color developing agents, which
Is aminophenols, phenylenediamines, tet
There are lahydroquinolines and similar ones.
For example, Research Disclosnre, 17643, No. XX, cited earlier.
It is described in the section. Other effective developing agents include hydroquinones and carboxylic acids.
Includes techols and pyrazolidones. LIG-X is a feeling
In optical materials, in silver halide emulsion layers, and in other layers (e.g.
It can be added to the agent adjacent layer). The photosensitive material is
One or more silver halide emulsion layers, and
With combined LIG-X. And after the exposure
Where oxidant of the developing agent is generated during the processing step,
X and the oxide product are produced and the LIG part is released.
Be done. Where the oxidant does not form, LIG-X LIG
The part is complexed with metal ions to form a metal vinegar pigment. The product of X and the oxidant is colorless or outside the light-sensitive material.
In case of spillage, the light-sensitive material is usually
Have a combination of ingredients (eg couplers) with the emulsion layer
It When the light-sensitive material of the present invention is used for multiple colors,
The material is a red sensitive halo that provides a cyan dye image on a support.
A silver sensitized emulsion layer, which is a green-sensitive layer that supplies a magenta dye image
Blue silver-sensitive emulsion layer, providing blue dye image
A silver halide emulsion layer and a LIG-X compound. LIG
-X is combined with at least one silver halide emulsion layer.
Passed on and used. Complexes with one metal ion to form a yellow metal complex dye
The LIG-X compound to be formed is preferably green-sensitive and / or
Or when used in combination with a red-sensitive silver halide emulsion layer.
Those forming a magenta metal complex dye are preferably
Is used in combination with a blue-sensitive and / or red-sensitive emulsion layer.
Those that form cyan metal complex dyes are preferred.
It is used in combination with a green-sensitive emulsion layer to produce a red metal complex.
Those forming a body dye are preferably combined with a red-sensitive emulsion layer.
Used in combination. Metal ions that form a complex with LIG-X are used in the photosensitive material.
Although it can be added, it is preferable to add it to the processing solution.
Can be. The treatment liquid may be a bleaching liquid or a metal complex type.
An original processing solution for the purpose of use is mentioned. The polymer coupler according to the present invention comprises a coupler monomer.
Not only those polymerized alone, but other than couplers
Obtained by co-polymerization with
What is mentioned can also be used preferably. Above, examples of coupler monomers are shown.
This is the coupler monomer used in the rimer coupler.
It is not limited. Formula [1]; Examples of yellow coupler monomer In the formula, Q is an ethylenically unsaturated group or an ethylenically unsaturated group.
Represents a group having a saturated group, where X is a hydrogen atom or a color developing group.
Can be removed by a coupling reaction with the oxidant of the image drug
Represents a group. R¹Is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group
Si group, halogen atom, sulfo group, carboxy group, sulfo group
Amide group, carbamoyl group, sulfamoyl group, sialic group
Represents a group. R²Is an alkyl group or a substituted or unsubstituted
Represents an aryl group. Specifically, Q is represented by the general formula [II]. Where R⁶Is hydrogen atom, halogen atom or alkyl
A group, preferably a lower alkyl group having 1 to 4 carbon atoms (eg,
, A methyl group, an ethyl group, a t-butyl group, etc.),
This alkyl group may have a substituent. L is -CO
NH-, -NHCONH-, or -NH- represents a divalent group,
P is -CONH-, -SO₂-Or -COO- divalent group
Preferably a -CONH- or -COO- divalent group
Is. A is an alkylene group (preferably having 1 to 10 carbon atoms)
Alkylene group), or a divalent group such as a phenylene group
And the alkylene group may be straight or branched.
Well, for example, methylene group, methylmethylene group, dimethylene
Group, decamethylene group, etc., and the above alkylene groups
The phenylene group may have a substituent. m and
And n each represent 0 or 1. In the above general formula [II], L is preferably -CONH-
Or —NH—, where n is 1 and A is m—
Phenylene, when m is 1 and P is -CONH-
R³Is a lower alkyl group. Even more preferably, L is -CONH-, m and
When n is 0 and R³Is a lower alkyl group, especially
This is the case of a chill group. Position of alkylene group or phenylene group represented by A
Examples of the substituent include an aryl group (eg, phenyl group) and nit
Group, hydroxyl group, cyano group, sulfo group, alkoxy group,
(Eg ethoxy group), acyloxy group (eg aceto group
Xy group), acylamino group (eg acetylamino
Groups), sulfonamide groups (eg methanesulfonamide)
Group), a sulfamoyl group (eg, methylsulfamoyl)
Group), halogen atom (eg fluorine atom, chlorine atom, odor)
Elementary atom, etc.), carboxyl group, carbamoyl group (eg,
Methylcarbamoyl group), alkoxycarbamoyl group
(Eg methoxycarbamoyl group etc.), sulfonyl group
(For example, a methylsulfonyl group and the like), and the like. This
It does not matter if these substituents have two or more kinds.
In these cases, these substituents may be the same or different.
Good. In the general formula [I], a color developing agent represented by X
A group capable of leaving during a coupling reaction with an oxidant of a drug
Is, in detail, the following general formulas [IIIa], [IIIb] and
It is represented by [IIIc]. General formula [IIIa] -0-R^Four General formula [IIIb] -SR^Five General formula (IIIc) Where R^Four, R^FiveIs an alkyl group, aryl group, acyl group, etc.
Represents R⁶Is a 5- or 6-membered heterocycle (eg imida
Azole ring, pyrazole ring, piperidine ring, morpholine
Ring, succinimide ring, triazole ring, etc.)
Represents a group of non-metal atoms necessary for. Then represented by the general formula [IIIa], [IIIb] and [IIIc]
Preferred examples of X are shown below, but the present invention is
It is not limited to this. (1) -OR of the general formula [IIIa]^FourSpecific examples corresponding to (2) -SR of general formula [IIIb]^FiveSpecific examples corresponding to (3) of the general formula [IIIc]Specific examples corresponding to Formula [IV]: Examples of magenta coupler monomers In the formula, Y represents an electron-withdrawing group, and l is 0 to 3
Represents an integer, and when l is 2 or more, Y is the same or different.
May be. The electron withdrawing group Y represented by the general formula [IV] is phenyl
It may be substituted at any position of the group, but is particularly preferred.
Kuha is selected from 2nd, 3rd, 4th, 5th and 6th.
When it is replaced with l represents an integer of 0 to 3 as described above, but is preferable.
It is preferably 0 to 2. When l is 2 or more, Y is the same or different electron attracting
May be sex. Here, the electron-withdrawing group means "fizz.
Sikal Organic Chemistry MacGlow
Hill Book ”(Physical Organic Chemistry McGraw
-Hill Book) Co. New York (1940)
Σ value defined by Hammett et al.
Or described in J. Amer Chem, Soc., 90, 4328 (1968).
Swein and Lupton (LuPto
n) a substituent having an F value greater than zero, derived by
And be regularly scheduled. Specific electron withdrawing groups include halo.
Gen atom, halogen alkyl group, carboxyl group, sulfur
E group, nitro group, cyano group, alksulfonyl group, ar group
Killcarbonyl group, alkoxycarbonyl group, alkyl
Sulfamoyl group, arylsulfamoyl group, alkyl
Group including sulfone amide group and aryl sulfonamide group.
, J.Med.Chem.16,1207 (1973), 2
Using substituents such as those described in 0,304 (1977)
Can be The electroattractive group used in the present invention
The preferred one is an alkylsulfamoyl group.
Alkylsulfamoyl having 1 to 4 carbon atoms in the kill part
Groups such as dimethylsulfamoyl group, ethylsulfamoyl group
Halogenoalkyl group such as moyl group, carbon of alkyl part
Halogenoalkyl groups with a prime number of 1 to 2, such as triflu
Halogen source such as oromethyl or trichloromethyl
And the number of carbon atoms in the alkyl part of the alkoxycarbonyl group
1 to 4, such as methoxycarbonyl group, eth
Xycarbonyl group, propoxycarbonyl group, butoxy
A carbonyl group and the like, particularly preferred are halogen radicals.
I am a child. Among the halogen atoms, the particularly preferable one is
It is a chlorine atom. Examples of magenta coupler monomers include those represented by the general formula [I
V] in addition to the monomers of JP-A-59-171956 and 59-228.
Nos. 252 and 60-35732
Etc. General formula [VII]; examples of cyan coupler monomersGeneral formula [VIII] R in the general formula [VII]⁹, R^TenAre each R³, R¹Same as
Righteous. Further, Q and X are the same as Q and X in the general formula [I].
Are synonymous. In the general formula [VIII], R¹¹Is hydrogen atom, alkyl
Group, alkenyl group, alkoxy group, alkoxycarbonyl
Group, halogen atom, alkoxycarbonyl group, aliphatic group
Amido group, alkylsulfamoyl group, alkylsulfo
Group, alkylureido group, arylcarbamoy group
Group, arylamido group, arylsulfamoyl group,
Aryl sulfonamide group or aryl ureido group
Represent. a represents an integer of 0 to 3. X is a general formula
It is synonymous with [I]. Q has the same meaning as in formula [I]. Below are specific examples of coupler monomers and coupler polymers.
Examples are shown below, but the compounds used in the present invention are not limited to these.
It is not something that will be done. Specific examples of coupler monomers  Subsequently, the present invention obtained from the above various monomers
Specific polymer examples of the polymer coupler concerned are shown below.
The present invention is not limited to these. Specific examples of polymer couplers  Polymer coupler latex is a commonly used non-polymer
-Type coupler part or all of polymer coupler
It may be replaced with latex. The amount of the coupler is the amount of the polymer coupler latex and its
Including the other couplers in the photosensitive silver halide emulsion layer
2 × 10 per mol of silver halide^-3~ 5 x 10^-1
Mol (polymer coupler latex has one coupler structure
The unit is 1 mol. ) Is suitable and preferred
Is 1 × 10^-2~ 5 x 10^-1It is in the molar range. Included in the middle layer
A light-sensitive silver halide emulsion layer adjacent to the layer
Range based on the amount of silver halide in
It should be cheap. Including a coupler in the photosensitive silver halide emulsion layer
As the method, a known method may be applied. Is the support a layer structure that can particularly exert the effect of the present invention?
Sequentially colloidal silver antihalation layer (intermediate layer) red sensitivity
Layer (intermediate layer) Green-sensitive layer (intermediate layer) Colloidal silver yellow fill
Tar layer Blue-sensitive layer (intermediate layer) Coating with a protective layer
Colloidal silver antihalation layer (intermediate from support)
Layer) Red-sensitive layer (intermediate layer) Green-sensitive layer (intermediate layer) Blue-sensitive layer
(Intermediate layer) Red-sensitive layer (Intermediate layer) Green-sensitive layer (Colloid silver yellow)
Color filter layer) Blue sensitive layer (intermediate layer) protective layer was applied
It is a layered structure. The layer in parentheses may be omitted. Up
The red-sensitive layer, the green-sensitive layer and the blue-sensitive layer have low sensitivity and high sensitivity.
It may be divided into layers. In addition, Japanese Patent Publication Sho 49-15495
There are few red-sensitive layers, green-sensitive layers, and blue-sensitive layers as seen in
Layer structure in which one is divided into three partial layers
High-sensitivity emulsion layer unit and low-sensitivity emulsion layer unit as seen in 7
It is also possible to preferably use a layer structure in which the layers are separated. For silver halide emulsions, silver bromide as silver halide,
Silver iodobromide, silver iodochloride, silver chlorobromide, silver chloroiodobromide and chloride
Any of those used for ordinary silver halide emulsions such as silver
Can be used, but especially silver bromide, silver iodobromide, chloroiodo
It is preferably silver halide. The silver halide grains used in the silver halide emulsion are
Obtained by any of the acidic method, neutral method and ammonia method
May be The particles may be grown at one time, or seed particles
You may grow after having a child. How to make seed particles
The growth method may be the same or different. A silver halide emulsion contains halide and silver ions.
Even if they are mixed at the same time, if one of the
The two may be mixed. Also, the critical growth of silver halide crystals
Mix the halide and silver ions while considering the speed.
Sequential and simultaneous addition while controlling pH and pAg in the pot
It may be generated by Crystals by this method
Silver halide grains with regular shape and nearly uniform grain size
Is obtained. Conversion at any step of AgX formation
Method may be used to change the halogen composition of the grains. During the growth of silver halide grains, ammonia and thioeth
Presence of known silver halide solvents such as phenol and thiourea
be able to. The silver halide grains may be formed by the process of forming grains and / or
During the process of growing, cadmium salt, zinc salt, lead salt, thallium
Umium salt, iridium salt (including complex salt), rhodium salt (complex
A small amount selected from salt (including salt) and iron salt (including complex salt)
Metal ions were added using one of them and spread inside the particles.
And / or containing these metal elements on the particle surface
And by placing them in a suitable reducing atmosphere,
Reduction sensitization nuclei can be provided inside and / or on the surface of the grain. Silver halide emulsion is the end of silver halide grain growth
Unnecessary soluble salts may be removed later, or
You can leave it as it is. When removing the salts,
Search Disclosure (below Research Disclosure
Abbreviated as RD) Performed based on the method described in Item 17643, Section II.
You can A silver halide grain has a uniform halogen content within the grain.
Even if it has a silver halide composition distribution,
Core / shell grains having different silver halide compositions
Good. A latent image is mainly formed on the surface of silver halide grains.
May be particles such as
It may be particles that are formed. Silver halide grains are cubic, octahedral or tetradecahedral.
It may have a regular crystal shape, such as a sphere or a plate.
It may have an irregular crystal form such as. these
Any ratio of {100} planes to {111} planes in the grain
Can be used. It also has a composite form of these crystal forms
Alternatively, particles of various crystal shapes may be mixed. Halo
The size of the silver genide grains is 0.05 to 30μ, preferably
Those of 0.1 to 2.0 μ can be used. Silver halide emulsions have any grain size distribution
You may use the thing. Emulsion with wide grain size distribution
(Also referred to as polydisperse emulsion) may be used, or grain size
An emulsion with a narrow distribution (referred to as a monodisperse emulsion.
An emulsion is the standard deviation of the grain size distribution divided by the average grain size.
Sometimes the value is less than 0.20. Where the particle size is
In the case of spherical silver halide, change the diameter to a non-spherical shape.
In the case of particles in the shape of a circle, convert the projected image into a circular image of the same area.
Indicates the diameter when ) May be used alone or as a mixture of several kinds.
Yes. Also, a mixture of polydisperse emulsion and monodisperse emulsion may be used.
Yes. A silver halide emulsion consists of two or more halos that are formed separately.
You may mix and use a silver genide emulsion. A silver halide emulsion may be chemically sensitized by a conventional method.
it can. That is, sulfur sensitization, selenium sensitization, reduction sensitization
Method, precious metal sensitization method using gold and other precious metal compounds, etc.
Can be used alone or in combination. Silver halide emulsions are used as sensitizing dyes by photographers.
Using a known dye,
Can be sensitized. The sensitizing dyes may be used alone, but two or more
The above may be used in combination. It with sensitizing dye
A dye that does not have a spectral sensitizing effect or visible light
A compound that does not absorb qualitatively, and the sensitizing action of sensitizing dyes
A supersensitizer that enhances the composition may be contained in the emulsion. Sensitizing dyes include cyanine dyes and merocyanine dyes.
Element, complex cyanine dye, complex merocyanine dye, holopo
-Lar cyanine dye, hemicyanine dye, steryl dye
And hemioxanol dyes are used. Particularly useful dyes are cyanine dyes and merocyanine dyes.
Elementary and complex merocyanine dyes. The silver halide emulsion contains the light-sensitive material manufacturing process and storage.
Prevention of fog during or during photographic processing, or photographic performance
During the chemical aging for the purpose of keeping stable
At the end and / or after the completion of chemical ripening, silver halide milk
In the photographic industry, the antifoggant or
Can add compounds known as stabilizers
It Binder (or protective colloid) for silver halide emulsion
It is advantageous to use gelatin as the
Derivatives, graft polymers of gelatin and other polymers,
Other proteins, sugar derivatives, cellulose derivatives, single
Alternatively, the hydrophilicity of synthetic hydrophilic polymer substances such as copolymers
Sex colloids can also be used. Photographic milk of a light-sensitive material using the silver halide emulsion of the present invention
The agent layer and other hydrophilic colloid layers are used as a binder (or
(Curing protective colloid) Hardener that crosslinks molecules to increase film strength
By using one kind or two or more kinds, it is possible to harden the film.
Wear. Hardener does not need to be added to the processing solution
The light-sensitive material can be added to the extent that it can be hardened.
However, it is also possible to add a hardening agent to the processing liquid. For example, aldehydes (formaldehyde, glyoxy)
Sar, glutaraldehyde, etc.) N-methylol conversion
Compound (dimethylol urea, methylol dimethyl hydanto
In, etc.), dioxane derivatives, (2,3-dihydroxy
Dioxane), active vinyl compounds (1,3,5, -tria
Cryloyl-hexanehydro-_Five-Triazine, 1,3-bi
Nylsulfonyl-2-propanol, etc.), active halogen
Compounds (2.4-dichloro-6-hydroxy-_Five− Thoria
Gin, etc., mucohalogenates (mucochloric acid, mukov
Enokicyclo acid, etc.), etc., alone or in combination
Can be used. Silver halide emulsion layer and / or other hydrophilicity of light-sensitive material
A plasticizer may be added to the colloid layer for the purpose of increasing flexibility.
It Preferred plasticizers are those described in RD17643, Section XII, A.
Compound. For photographic emulsion layers and other hydrophilic colloid layers of light-sensitive materials
Water-insoluble or sparingly soluble for the purpose of improving dimensional stability
A dispersion of synthetic resin (latex) should be contained.
You can For example, alkyl (meth) acrylate, alkoxyl
Rutile (meth) acrylate, glycidyl (meth),
Acrylate, (meth) acrylamide, vinyl ester
(Eg vinyl acetate), acrylonitrile, olefin
Or styrene, alone or in combination, or with these
Acrylic acid, methacrylic acid, α, β-unsaturated dicarboxylic acid
Acid, hydroxyalkyl (meth) acrylate, sulfo
Alkyl (meth) acrylate, styrene sulfonic acid, etc.
It is possible to use a polymer with a combination of
Wear. During the color development process, the emulsion layer of the light-sensitive material contains a fragrance
Group primary amine developers (eg p-phenylenediamine)
Derivative, aminophenol derivative, etc.)
Dye-forming couplers that form a dye through a pulling reaction
Is used in combination with the polymer coupler according to the present invention
Can be. The dye-forming coupler is for each emulsion layer
A dye is formed that absorbs light in the light-sensitive spectrum of the emulsion layer.
Is usually selected as the blue-sensitive emulsion layer.
The yellow dye-forming coupler is magenta in the green-sensitive emulsion layer.
Dye-forming coupler forms cyan dye in red-sensitive emulsion layer
A coupler is used. However, depending on the purpose,
Silver halide color photography with different combinations and uses
You may make a photosensitive material. These dye-forming couplers are called ballast groups in the molecule.
Has a group with 8 or more carbon atoms that makes the coupler non-diffusing
Is desirable. Also, these dye-forming couplers are 1 minute
4 molecules of silver ions are reduced to form child pigments.
2 molecules of silver ion, even if they are 4 equivalence
It may be either dimeric, which only needs to be reduced. color
Coupling with the oxidant of the developing agent in the element-forming coupler
Development inhibitor, development accelerator, bleaching accelerator, development
Agent, silver halide solvent, toning agent, hardener, fog agent, fog
Anti-blur agent, chemical sensitizer, spectral sensitizer, and desensitizer
Compounds that release photographically useful fragments such as
To be Among these, a development inhibitor or a development inhibitor
DIR compounds capable of releasing antagonist precursors
Is preferably used in order to further enhance the effect of the present invention.
Can be DI that can be particularly preferably used
The R compound is a diffusible DIR compound described below. The diffusible DIR compound is represented by the following general formula.
It Diffusible DIR compound General formula (1) A- (Y) m In the formula, A represents a coupler component, and m represents 1 or 2.
I, Y is bonded to the coupling position of coupler component A and
Diffuses with a group that is released by the reaction with the oxidant of the Ra-developer
A development inhibitor with a high property or a development inhibitor can be released
Represents a compound. It is sufficient that A has the properties of a coupler, and
It is not necessary to make the dye by pulling. Diffusible DIR compound In the general formula (1), Y is the following general
It represents formulas (2A) to (5). Diffusible DIR compound general formula (2A)Diffusible DIR compound general formula (2B)Diffusible DIR compound general formula (2C)Diffusible DIR compound general formula (2D)Diffusible DIR compound general formula (2E)Diffusible DIR compound general formula (3)Diffusible DIR compound general formula (4)Diffusible DIR compound general formula (5) In the above general formulas (2A) to (2D) and (3), R¹
Is an alkyl group, alkoxy group, acylamino group, halogen
Atom, alkoxycarbonyl group, thiazolidene amine
Group, aryloxycarbonyl group, acyloxy group,
Carbamoyl group, N-alkylcarbamoyl group, N, N-
Dialkylcarbamoyl group, nitro group, amino group, N-
Arylcarbamoyloxy group, sulfamoyl group, N
-Alkylcarbamoyloxy group, hydroxy group, ar
Coxycarbonylamino group, alkylthio group, aryl
Thio group, aryl group, heterocyclic group, cyano group, alkyl
Sulfonyl group or aryloxycarbonylamino
Represents a group. n represents 1 or 2, and when n is 2, R₁
Can be the same or different, and n R₁Carbon number contained in
Is 0-10. R in the above general formula (2E)₂Is R from (2A) to (2D)₁Synonymous with
And X represents an oxygen atom, a sulfur atom, or a selenium atom.
And R in the general formula (4)₂Is an alkyl group, aryl
Represents a group or a heterocyclic group. R in the general formula (5)₃Is a hydrogen atom, alkyl group,
Represents a reel group or a heterocyclic group, R_FourIs a hydrogen atom,
Alkyl group, aryl group, halogen atom, acylamino
Group, alkoxycarbonylamino group, aryloxy group
Rubonylamino group, alkanesulfonamide group, cyano
Group, heterocyclic group, alkylthio group or amino group
I forgot. R₁， R₂， R₃Or R_FourIs an alkyl group,
Whether substituted or unsubstituted, straight chain or branched chain
Or may be cyclic alkyl. The substituent is
Rogen atom, nitro group, cyano group, aryl group, alcohol
Xy group, aryloxy group, alkoxycarbonyl group,
Aryloxycarbonyl group, sulfamoyl group, cal
Vamoyl group, hydroxy group, alkanesulfonyl group, a
Reel sulfonyl group, alkylthio group or aryl
For example, a thio group. R₁， R₂， R₃Or R_FourWhen represents an aryl group,
The reel group may be substituted. As a substituent,
Kill group, alkenyl group, alkoxy group, alkoxycal
Bonyl group, halogen atom, nitro group, amino group, sulf
Amoyl group, hydroxy group, carbamoyl group, aryl
Oxycarbonylamino group, alkoxycarbonylami
Group, acylamino group, cyano group or ureido group.
How is it? R₁， R₂， R₃Or R_FourIs a heterocyclic group,
Contains nitrogen, oxygen, and sulfur atoms as terror atoms
Represents a 5- or 6-membered monocyclic or condensed ring,
Dil group, quinolyl group, furyl group, benzothiazolyl group,
Oxazolyl group, imidazolyl group, thiazolyl group, tri
Azolyl group, benzotriazolyl group, imide group, oxa
Gin group, etc.
It may be substituted by the substituents listed for the group. In the general formulas (2E) and (4), R₂Carbon contained in
The number is 1-15. In the above general formula (5), R₃And R_FourCharcoal contained in
The sum of prime numbers is 1 to 15. In the above general formula (1), Y represents the following general formula (6).
I forgot. Diffusible DIR compound General formula (6) -TEME-INHIBIT In the formula, the TEME group is bonded to the coupling position of the coupler,
A group that can be cleaved by reaction with a color developing agent,
After cleavage from the puller, the INHIBIT group is appropriately controlled and released.
It is a group that can. The INHIBIT group is a development inhibitor. In the general formula (6), the -TIME-INHIBIT group is the following general
Expressions (7) to (13) are represented. Diffusible DIR compound general formula (7)Diffusible DIR compound general formula (8)Diffusible DIR compound general formula (9)Diffusible DIR compound general formula (10)Diffusible DIR compound general formula (11)Diffusible DIR compound general formula (12)Diffusible DIR compound general formula (13) In the general formulas (7) to (13), R_FiveIs a hydrogen atom, halo
Gen atom, alkyl group, alkenyl group, aralkyl group,
Alkoxy group, alkoxycarbonyl group, anilino group,
Acylamino group, ureido group, cyano group, nitro group, sulfur
Lefonamide group, sulfamoyl group, carbamoyl group,
Aryl group, carboxy group, sulfo group, hydroxy group,
Represents an alkanesulfonyl group, represented by the general formulas (7), (8), (9), (11) and (13)
In the formula, 1 represents 1 or 2, and has the general formula (7), (11), (12) and (13)
And k represents an integer of 0 to 2, and in the general formulas (7), (10) and (11), R₆A
Alkyl group, alkenyl group, aralkyl group, cycloalkyl group
Represents an aryl group or an aryl group, and in the general formulas (12) and (13), B is an oxygen atom or
Or(R₆Has the same meaning as previously defined. )
However, the INHIBIT group is represented by the general formula (2A), (2B), (3), (4)
And the same meaning as the general formula defined in (5) except for the carbon number
Represents However, in the general formulas (2A), (2B) and (3),
Each R in one molecule₁The total number of carbon atoms contained in
Yes, in the general formula (4), R₂Contains 1 carbon
To 32, and in the general formula (5), R₃And R_FourIncluded in
The total number of carbon atoms is 0 to 32. R_FiveAnd R₆Is an alkyl group, substituted or not
It may be substituted, linear or cyclic. Substituent
As R₁~ R_FourThe substituents listed when is an alkyl group
Is mentioned. R_FiveAnd R₆Is an aryl group, the aryl group is
The substituent that may be substituted is R₁~ R_FourIs aryl
The substituents enumerated above as the groups can be mentioned. Of the above diffusible DIR compounds, the general formula (2A), (2
B), having a leaving group represented by (2E) to (5)
Particularly preferred is a yellow image represented by A in the general formula (1).
The forming coupler residue is pivaloyl acetanilide.
Type, benzoylacetanilide type, malon diester
Type, malondiamide type, dibenzoylmethane type, benzo
Thiazolyl acetamide type, malon ester monoamide
Type, benzothiazolyl acetate type, benzoxazoli
Luacetamide type, benzoxazolyl acetate type,
Malon diester type, benzimidazolyl acetamide
Type or benzimidazolyl acetate type coupler
Residues, heterocycle-substituted substituents contained in U.S. Pat.
Derived from Cetamide or Heterocyclic Substituted Acetate
Coupler residue or U.S. Patent 3,770,446, UK Patent 1,4
59,171, West German Patent (OLS) 2,503,099, JP-A-50-13
No. 9738 or Research Disclosure No. 15737
And the like derived from acylacetamide
Residues or heterocyclic type moieties described in U.S. Pat.
Examples include puller residues. As a magenta image-forming coupler residue represented by A
Is a 5-oxo-2-pyrazoline nucleus, pyrazolo- [1,5-
a] Benzimidazole nucleus or cyanoacetophenone type
A coupler residue having a coupler residue is preferred. The cyan image forming coupler residue represented by A is
Coupler residue having phenol nucleus or α-naphthol nucleus
Group, indazolone-based or pyrazolotriazole-based coupler
-Residues are preferred. Furthermore, the coupler is coupled with the oxidized product of the developing agent.
No substantial dye formation after release of development inhibitor
However, the effect as a DIR coupler is the same. Represented by A
This type of coupler residue is described in U.S. Pat.
No. 4,088,491, 3,632,345, 3,958,993
Include coupler residues described in No. 3,961,959.
It Hereinafter, specific examples of the diffusible DIR compound of the present invention will be given.
It is not limited to these. [Exemplified compound]  These compounds are disclosed in U.S. Patents 4,234,678 and 3,227,554.
Issue 3,617,291, Issue 3,958,993, Issue 4,149,886,
3,933,500, JP-A-57-56837, JP-B-51-13239
No., British Patents 2,072,363, 2,070,266, Research Data
Is closure Described in December 1981, No. 21228, etc.
It can be easily synthesized by the method. In addition, an aromatic primary amine developer oxidant and coupling agent
Colorless couplers that undergo a reaction but do not form dyes (competitive
(Also called couplers) in combination with dye-forming couplers
You can also. To be used in combination with the polymer coupler according to the present invention
Known as a yellow dye-forming coupler,
Preferable use of acylacetanilide type coupler
Can be. Of these, benzoylacetanilides
Pivaloyl acetanilide compounds are advantageous.
Specific examples of yellow color-forming couplers that can be used include, for example, US Pat.
No. 2,875,057, No. 3,265,506, No. 3,408,194,
No. 3,551,155, No. 3,582,322, No. 3,725,072
No. 3,891,445, West German patent 1,547,868, West German application
Published 2,219,917, 2,261,361, 2,414,006, UK
National Patent No. 1,425,020, Japanese Patent Publication No. 51-10783, JP-A No. 47-
26133, 48-73147, 50-6341, 50-87650
50, 123-342, 50-130442, 51-21827
No. 51-102636, No. 52-82424, No. 52-115219
No. 58-95346, etc. As a magenta dye-forming coupler, a known 5-pyra
Zolone type coupler, pyrazolobenzimidazole type cap
Ra, pyrazolotriazole couplers, open chain acylors
Setonitrile-based couplers, indazolone-based couplers, etc.
Can be used. Of magenta color couplers that can be used
Specific examples are, for example, U.S. Patent Nos. 2,600,788 and 2,982.
3,608, 3,062,653, 3,127,269, 3,3
No. 11,476, No. 3,419,391, No. 3,519,429, No. 3,
558,319, 3,582,322, 3,615,506, and
3,834,908, 3,891,445, West German patent 1,810,464
Issue, West German patent application (OLS) 2,408,665, 2,417,945
No. 2, 2,418,959, 2,424,467, Japanese Patent Publication No. 40-6031
No. 49-74027, 49-74028, 49-129538.
No. 50-60233, 50-159336, 51-20826,
51-26541, 52-42121, 52-58922, 53
-55122, Japanese Patent Application No. 55-110943, etc.
Can be Cyan dye forming couplers include phenol or
Naphthol couplers are commonly used. Can be used
Specific examples of cyan color forming couplers include, for example, U.S. Pat.
No. 730, No. 2,474,293, No. 2,801,171, No. 2,89
5,826, 3,476,563, 3,737,326, 3,7
58,308, 3,893,044, JP-A-47-37425
No. 50, No. 50-10135, No. 50-25228, No. 50-112038,
No. 50-117422, No. 50-130441, etc.
And those described in JP-A-58-98731.
Pullers are preferred. Dye form that does not need to be adsorbed on the surface of silver halide crystals
Coupler, Colored coupler, DIR coupler, DIR compound
Objects, image stabilizers, antifoggants, UV absorbers, fluorescent
Among the whitening agents, hydrophobic compounds are solid dispersion method, LATEC
Dispersion method, oil-in-water emulsion dispersion method, etc.
This is the chemistry of hydrophobic compounds such as couplers.
It can be appropriately selected depending on the structure and the like. Oil-in-water type
The emulsion dispersion method disperses hydrophobic additives such as couplers.
A conventionally known method can be applied, and a boiling point of about 150 ° C or higher is usually used.
Low boiling point and / or water-soluble as needed for high boiling point organic solvent
Dissolves in combination with an organic solvent, giving hydrophilicity such as gelatin aqueous solution.
Stirrer and homogenizer using a surfactant in a hydrophilic binder
Nizer, colloid mill, flowgit mixer, supersonic
After emulsifying and dispersing with a dispersing device such as a wave device,
It may be added to the hydrophilic colloid solution. Dispersion or
Even if a step of removing the low boiling point organic solvent is added at the same time as the dispersion
Good. As a high boiling point solvent, a solvent that does not react with the oxidant of the developing agent.
Enol derivative, phthalic acid alkyl ester, phosphoric acid
Ester, citric acid ester, benzoic acid ester, al
Killamide, fatty acid ester, trimesic acid ester, etc.
An organic solvent having a boiling point of 150 ° C. or higher is used. Low boiling point or water soluble with or instead of high boiling point solvent
Organic solvents can be used. Low boiling point, virtually insoluble in water
Ethyl acetate, propyl acetate as organic solvent
Butyl acetate, butanol, chloroform, four
Carbon chloride, nitromethane, nitroethane, benzene, etc.
is there. Dye forming coupler, DIR coupler, Colored coupler
ー, DIR compound, image stabilizer, anti-fog agent, UV
Absorbents, optical brighteners, etc., such as carboxylic acid and sulfonic acid
When it has an acid group, it can be used as an alkaline aqueous solution.
It can also be incorporated into an aqueous colloid. Hydrophobic compounds used in low boiling point solvent alone or in combination with high boiling point solvent
Dissolve in a suitable solvent and submerge in water using mechanical or ultrasonic waves.
As a dispersion aid when dispersed, an anionic surfactant,
Nonionic surfactant, cationic surfactant and amphoteric
Surfactants can be used. The emulsion layers of the light-sensitive material (the same color-sensitive layers and / or different layers)
Between the color sensitive layers), the oxidant of the developing agent or the electron transfer agent.
Move to cause color turbidity, deteriorate sharpness, and
Uses a color antifoggant to prevent the condition from standing out
Can be The color antifoggant may be contained in the emulsion layer itself.
If an intermediate layer is provided between adjacent emulsion layers,
You may let me. Image stabilizers that prevent the deterioration of dye images in light-sensitive materials
Can be used. Preferred use
The compound is described in RD17643, Item VII J. Hydrophilic colloid layers such as protective layers and intermediate layers of light-sensitive materials are
The optical material is charged due to friction, etc.
To prevent blurring and to prevent deterioration of images due to ultraviolet rays
It may contain an ultraviolet absorber. Magenta dye form due to formalin during storage of light-sensitive materials
In order to prevent deterioration of the coupler, etc.
Marine scavengers can be used. Paint, UV absorber, etc. on the hydrophilic colloid layer of the photosensitive material
When they contain, they are
It may be mordanted with a mordant. Silver halide emulsion layer and / or other parent of light-sensitive material
Developability of development accelerator, development retarder, etc. in the aqueous colloid layer
Changing compounds and bleaching accelerators can be added. Development promotion
The compound that can be preferably used as the agent is RD17643
And a development retarder.
Is a compound described in Item XXI, Item E of 17643. Development promotion
Black-and-white developing agent and / or its
A curser may be used. The emulsion layer of the photographic light-sensitive material has increased sensitivity and contrast.
Polyalkylene oxide or
Derivatives of ethers, esters, amines, etc.
Ter compounds, thiomorpholines, quaternary ammonium compounds
Compound, urethane derivative, urea derivative, imidazole derivative
It may include the body and the like. The light-sensitive material emphasizes the whiteness of the white background and
It is possible to use an optical brightener for the purpose of making the coloring of the
it can. Can be preferably used as a fluorescent whitening agent
The compounds are described in Section V of RD17643. The photosensitive material includes a filter layer, an antihalation layer,
An auxiliary layer such as an anti-irradiation layer can be provided
It In these layers and / or emulsion layers, during development processing
Contains dyes that are bleached or bleached from light-sensitive materials
You may be allowed to. Such dyes include oxonol
Dye, hemioxonol dye, styryl dye, merocyan
Examples include nin dyes, cyanine dyes, azo dyes, etc.
Wear. Silver halide emulsion layer and / or other parent of light-sensitive material
Reduction of the gloss of the photosensitive material and improvement of the writing property on the aqueous colloid layer
Good, mat for the purpose of preventing sticking of photosensitive materials to each other
Agents can be added. Any matting agent may be used.
For example, silicon dioxide, titanium dioxide, diacid
Magnesium oxide, aluminum dioxide, barium sulfate,
Polymers of calcium carbonate, acrylic acid and methacrylic acid
And their esters, polyvinyl resins, polycarbonate
And styrene polymers and their copolymers
Can be given. The matting agent has a particle size of 0.05μ to 10μ.
preferable. The amount to be added is 1 to 300 mg / m²Is preferred. Lubricants added to photosensitive materials to reduce sliding friction
it can. Addition of antistatic agent to the photosensitive material for the purpose of antistatic
it can. The antistatic agent is on the side of the support where the emulsion is not laminated.
It may be used in the antistatic layer, and in the emulsion layer and / or the support.
On the other hand, the protective layer other than the emulsion layer on the side where the emulsion layers are stacked
It may be used for the Lloyd layer. Charge used preferably
The inhibitor is a compound described in RD17643 XIII.
It Photographic emulsion layer of photosensitive material and / or other hydrophilic colloid
The coating layer has improved coatability, antistatic properties, improved slipperiness, and emulsified content.
Scattering, adhesion prevention, photographic characteristics (development acceleration, film hardening, sensitization, etc.)
It is possible to use various surfactants for the purpose of improvement.
it can. The support used in the light-sensitive material of the present invention includes α-ole
Fin polymers (eg polyethylene, polypropylene
And ethylene / butene copolymer)
Flexible reflective support such as paper and synthetic paper, cellulose acetate, glass
Acid cellulose, polystyrene, polyvinyl chloride, polyethylene
Tylene terephthalate, polycarbonate, polyamide
Films made of semi-synthetic or synthetic polymers such as
Flexible support with a reflective layer on glass, glass, gold
Includes genus and pottery. If necessary, the photosensitive material may be corona-discharged or purple-colored on the support surface.
After directing external rays, flame treatment, etc., directly or on the surface of the support
Surface adhesion, antistatic property, dimensional stability, wear resistance, hardness
Anti-halation properties, friction properties, and / or other
Applied through one or more subbing layers to improve the properties of
May be done. When coating a photosensitive material, increase it to improve coatability.
A sticky agent may be used. It is also reactive like hardeners.
Because it is fast, if it is added to the coating solution in advance, it will
Static mixers
It is preferable to mix them just before coating by using a mixer or the like. The coating method is to coat two or more layers simultaneously.
Extrusion coating and curtain
Coatings are especially useful, but for some purposes they are packaged
Coating is also used. Also, select the coating speed arbitrarily.
Can be. Although the surfactant is not particularly limited, for example, a surfactant
Natural surfactants such as nin, alkylene oxides, green
Nonionic surfactants such as serine and glycidol,
Higher alkylamines, quaternary ammonium salts, pyri
Gin and other heterocycles, phosphonium or sulfonium
Cationic surfactants such as mums, carboxylic acids, sulfones
Acidic group such as acid, phosphoric acid, sulfuric acid ester, phosphoric acid ester
Anionic surfactants containing, amino acids, amino sulfo
Acids, sulfuric acid or phosphoric acid esters of amino alcohols
You may add both surfactants, such as a class. Also similar eyes
For this reason, it is possible to use a fluorosurfactant.
is there. Exposure to obtain a dye image using the light-sensitive material of the present invention
After that, color photograph processing is performed. Color processing is color development
Processing process, bleaching process, fixing process, washing process and
And a stabilization process if necessary, using a bleaching solution.
1 bath instead of the treatment process and the treatment process using the fixer
You can also use the bleach-fix solution to perform the bleach-fix processing process
Color development, bleaching and fixing can be done in one bath
Monobath processing process using 1 bath development bleach-fixing solution
You can also do it. In combination with these treatment steps, the pre-dural treatment step,
Neutralization process, stop fixing process, post-hardening process, etc.
You may. In these processes, the color development process
Instead, color developing agent or its precursor
And the developing process is performed with an activator solution.
You may carry out the process of the citivator or its monobus
An activator treatment of the treatment can be applied. This
Among these processes, a typical process is shown below. (These places
The final process is the washing process, the washing process and
Perform one of the stabilization treatment steps. ) ・ Color development processing step-bleaching processing step-fixing processing step-Color development processing step-bleach fixing processing step-Pre-hardening processing step-color development processing step-stop fixing processing step
Process-washing process-bleaching process-fixing process-washing
Processing step-Post-hardening processing step-Color development processing step-Water washing processing step-Supplementary color development processing
Process-Stopping process-Bleaching process-Fixing process-Activator process-Bleaching process-Activator process-Bleaching process-Fixing process
・ Monobath treatment process The treatment temperature is usually selected in the range of 10 ℃ to 65 ℃.
The temperature may exceed ℃. Preferably at 25 ° C to 45 ° C
It is processed. Color developing solutions are generally alkaline containing color developing agents.
It consists of an aqueous solution. Color developing agent is aromatic primary amine
Color developing agents, aminophenol and p-phenyl
Resin amine derivatives are included. These color developers
The drug can be used as salts of organic and inorganic acids, eg
For example, salt acid, sulfate, p-toluenesulfonate, sulfite
Acid salt, oxalate, benzene sulfonate, etc.
You can These compounds are generally about 0.
Concentration of 1 to 30 g, more preferably about 1%
Used at a concentration of about 1 to 15 g. Addition less than 0.1g
If the amount is sufficient, sufficient color density cannot be obtained. Examples of the aminophenol-based developer include o-
Aminophenol, p-aminophenol, 5-amino
2-oxy-toluene, 2-amino-3-oxy-to
Ruene, 2-oxy-amino-1,4-dimethyl-benze
Are included. Particularly useful primary aromatic amine color developing agents are N, N-
A dialkyl-p-phenylenediamine compound,
Alkyl group and phenyl group may be substituted or not
May not be replaced. Among them, especially useful
As an example of compound, N-N-dimethyl-p-phenylenedia
Min hydrochloride, N-methyl-p-phenylenediamine hydrochloride
Salt, N, N-dimethyl-p-phenylenediamine hydrochloride,
2-amino-5- (N-ethyl-N-dodecylamino)
-Toluene, N-ethyl-N-β-methanesulfonami
Doethyl-3-methyl-4-aminoaniline sulfate, N
-Ethyl-N-β-hydroxyethylaminoaniline,
4-amino-3-methyl-N, N-diethylaniline, 4
-Amino-N- (2-methoxyethyl) -N-ethyl-
3-methylaniline-p-toluene sulfonate etc. on top
I can do it. The above color developing agents may be used alone or in combination of two or more.
You may use it. Furthermore, the color developing agent is colored
-It may be incorporated in the photographic material. In this case, halogen
Instead of silver halide color photographic light-sensitive material, color developer
It is also possible to treat with re-solution (activator solution)
After the alkaline solution treatment, the bleach-fixing treatment is carried out immediately. The color developing solution used in the present invention is usually used as a developing solution.
Alkaline agents such as sodium hydroxide, potassium hydroxide
Aluminum, ammonium hydroxide, sodium carbonate, potassium carbonate
, Sodium sulfate, sodium metaborate or borax
Etc., and various additives such as benzine.
Alcohol, alkali metal halides, eg bromide
With potassium, potassium chloride, etc., or a development regulator
Then, for example, citrazinic acid, etc.
It may contain amine or sulfite. Furthermore each
Seed defoamers and surfactants as well as methanol and dimethyl
Organic solvents such as lumamide or dimethylsulfoxide
Can be appropriately contained. The pH of the color developer used in the present invention is usually 7 or higher,
It is preferably about 9 to 13. If necessary, the color developing solution used in the present invention
Diethylhydroxyamine, tetro as antioxidant
Acid, tetronimide, 2-anilinoethanol, dihi
Droxyacetone, secondary aromatic alcohol, hydroxa
Mumic acid, bentose or hexose, pyrogallol-1,
3-dimethyl ether and the like may be contained. The color developer used in the present invention contains a sequestering agent
As the above, various chelating agents can be used in combination. An example
For example, as the chelating agent, ethylenediaminetetraacetic acid, diamine
Amine polycarboxylic acid such as ethylenetriaminopentaacetic acid,
1-hydroxyethylidene-1,1'-diphosphonic acid, etc.
Organic phosphonic acid, aminotri (methylenephosphonic acid)
Aminopolyphos such as ethylenediaminetetraphosphoric acid
Oxical such as sulfonic acid, citric acid or glycon vinegar
Boric acid, 2-phosphonobutane 1,2,4-tricarboxylic acid
Such as phosphonocarboxylic acid, tripolyphosphoric acid or hex
Polyhydroxy compounds such as polyphosphoric acid such as sametaphosphoric acid
Etc. are raised. The bleaching process is the same as the fixing process as described above.
It may be carried out either separately or individually. As a bleach
For example, metal complex salts of organic acids are used.
Organics such as acids, aminopolycarboxylic acids or oxalic acid, citric acid
Acid that is coordinated with metal ions such as iron, cobalt, and copper
Is used. Most preferred organic of the above organic acids
As the acid, polycarboxylic acid or aminopolycarboxylic acid
Is mentioned. Specific examples of these include ethylenedia
Mintetraacetic acid, diethylenetriaminepentaacetic acid,
Tolylenediamine-N- (β-oxyethyl) -N, N ′,
N'-triacetic acid, propylenediaminetetraacetic acid, nit
Lilotriacetic acid, cyclohexanediaminetetraacetic acid, a
Minodiacetic acid, dihydroxyethylglycine citric acid (or
Tartaric acid), ethyl ether diamine tetraacetic acid, glyco
Ether diamine tetraacetic acid, ethylene diamine
Trapropionic acid, phenylenediamine tetraacetic acid, etc.
Can be mentioned. These polycarboxylic acids are
Limetal salt, ammonium salt or water-soluble amine salt
You may. These bleaching agents are more preferred than 5-450 g / l
Is used at 20 to 250 g / l. In the bleaching solution, in addition to the bleaching agent as described above, keep it as necessary.
A liquid having a composition containing sulfite is used as a preservative.
Also, ethylenediaminetetraacetate iron (III) complex salt bleaching agent
Containing a large amount of halide such as ammonium bromide
A bleaching solution having the composition added may be used. The halo
As the genide, hydrogen chloride may be used in addition to ammonium bromide.
Acid, hydrobromic acid, lithium bromide, sodium bromide, bromide
Potassium, sodium iodide, potassium iodide, ammonium iodide
Ni, etc. can also be used. The bleaching solution used in the present invention includes JP-A-46-280,
Japanese Patent Publication Nos. 45-8506 and 46-556, Belgian Patent No. 770,9
No. 10, JP-B-45-8836, JP-B-53-9854, JP-A-54-71
Various bleaching described in 634 and 49-42349
Accelerators can be added. The bleaching solution is used at a pH of 2.0 or higher, but generally 4.0-
Used in 9.5, preferably 4.5-8.0, most
It is preferably 5.0 to 7.0. Use a fixer with a commonly used composition.
Can be. Used as a fixing agent in normal fixing processing
React with silver halides such as to form water-soluble complex salts
Compounds such as potassium thiosulfate, sodium thiosulfate
Thiosulfate such as ammonium thiosulfate, thiocyanate
Potassium acid salt, sodium thiocyanate, thiocyanic acid
Thiocyanates such as ammonium, thiourea, thioe
Ether is a typical example. These fixatives
5g / l or more, in an understandable amount, but generally
Use at 70-250g / l. A part of the fixing agent is a bleaching tank.
Can be contained in and on the contrary fix some of the bleach
It can also be contained in the layer. The bleaching solution and / or fixing solution should contain boric acid, borax, and hydroxide.
Sodium, potassium hydroxide, sodium carbonate, carbonate
Lithium, sodium bicarbonate, potassium bicarbonate, acetic acid, vinegar
Various pH buffering agents such as sodium acid and ammonium hydroxide
Must be contained alone or in combination of two or more
Can be. In addition, various optical brighteners and defoamers or
Can also contain a surfactant. Also, hydro
Bisulfite of xylamine, hydrazine and aldehyde compounds
Preservatives such as acid adducts and organic compounds such as aminopolycarboxylic acids.
Stabilizing agent, nitro alcohol, nitrate, etc.
Agents, hardeners such as water-soluble aluminum salts, methanol,
Organic such as dimethyl sulfamide, dimethyl sulfoxide
A solvent and the like can be contained as appropriate. The fixer is used at a pH of 3.0 or higher, but generally 4.5-
Used at 10, preferably used at 5-9.5, most preferred
It is preferably 6-9. As the bleaching agent used in the bleach-fixing solution
The metal complex salts of organic acids described above can be mentioned as
The compound and the concentration in the processing solution should be the same as the above bleaching process.
It is the same as in. As described above, the bleach-fix solution contains silver halide in addition to the bleaching agent.
Contains a fixing agent and, if necessary, sulfite as a preservative
A liquid having the composition contained is applied. Also, ethylene diami
Iron (III) tetraacetate complex salt bleach and the silver halide
Other small amount of halide such as ammonium bromide
A bleach-fix solution composed of the added composition, or conversely, a brominated solution.
From the composition in which a large amount of halide such as ammonium is added
Bleach-fixing solution, and further ethylenediaminetetraacetate iron
(III) Complex salt bleach and a large amount of ammonium bromide
Special bleaching composition with a combination of rogenides
A landing liquid or the like can also be used. As the halide
In addition to ammonium bromide, is hydrochloric acid, hydrobromic acid,
Lithium bromide, sodium bromide, potassium bromide, sodium iodide
Thorium, potassium iodide, ammonium iodide, etc. are also used.
Can be Silver halide content that can be included in bleach-fix solutions
Examples of the fixing agent include the fixing agents described in the fixing processing step.
be able to. Fixer concentration and bleach-fix solution
For the pH buffer and other additives that can
It is the same as in the fixing process. The pH of the bleach-fix solution is 4.0 or higher, but
Used in 5.0-9.5, preferably used in 6.0-8.5
Most preferably 6.5 to 8.5.

【Example】

Specific examples of the present invention will be described below, but embodiments of the present invention are not limited to these. In all of the following examples, the addition amount in the silver halide photographic light-sensitive material is per 1 m ² unless otherwise specified. Also, silver halide and colloidal silver are shown in terms of silver. [Example-1] A multi-layer color photographic element sample 1 was prepared by sequentially forming each layer having the composition shown below from the support side on a triacetyl cellulose film support. Sample-1 (Comparison) First layer: Antihalation layer (HC-1) Gelatin layer containing black colloidal silver. Second layer: intermediate layer (IL) A gelatin layer containing an emulsified dispersion of 2,5-di-t-octylhydroquinone. Third layer; low-sensitivity red-sensitive silver halide emulsion layer (RL-1) (average grain size) 0.35 μm, containing AgI 8 mol%
Monodispersed emulsion consisting of AgBrI (Emulsion I) ... Silver coating amount 1.5 g / m ² Sensitizing dye I ... 6 × 10 ^-5 mol per 1 mol of silver Sensitizing dye II ... 1.0 against 1 mol of silver × 10 ^-5 mol Cyan coupler (EC-1) …… 0.06 mol for 1 mol of silver Colored cyan coupler (ECC-1)… 0.003 mol for 1 mol of silver DIR compound (ED-1) …… 1 silver 0.0025 mol per mol 4th layer; High-sensitivity red-sensitive silver halide emulsion layer (RH-1) Average grain size () 0.57 μm, Ag containing 8.5 mol% Ag
Monodisperse emulsion consisting of BrI (emulsion II) ... Silver coating amount 1.3 g / m ² Sensitizing dye I ... 3 × 10 ^-5 mol per mol silver sensitizing dye II ... 1.0 per mol silver × 10 ^-5 mol Cyan coupler (EC-1) …… 0.02 mol for 1 mol of silver Colored cyan coupler (ECC-1) …… 0.0015 mol for 1 mol of silver DIR compound (ED-1) …… Silver 0.002 mol per mol 5th layer; intermediate layer (IL) Gelatin layer, same as 2nd layer. Sixth layer: low-sensitivity green-sensitive silver halide emulsion layer (GL-1) Emulsion-I ... Coating silver amount 1.5 g / m ² Sensitizing dye III: 2.5 × 10 ^-5 mol increase per 1 mol silver Sensitizing dye IV: 1.2 × 10 ^-5 mol / mol of silver Magenta coupler (EM-1): 0.050 mol / mol of silver Colored magenta coupler (ECM-1): 0.009 / mol of silver Molar DIR compound (ED-1) ... 0.0030 mol per 1 mol of silver 7th layer; high-sensitivity green-sensitive silver halide emulsion layer (GH-1) Emulsion-II ... increase in coated silver amount by 1.4 g / m ² Sensitizing dye III: 1.5 × 10 ^-5 mol per 1 mol of silver Sensitizing dye IV: 1.0 × 10 ^-5 mol per 1 mol of silver Magenta coupler (EM-1): 1 mol of silver 0.020 mol Colored magenta coupler (ECM-1) ... 0.002 mol per mol of silver 8th layer; yellow filter layer (YC-1) Yellow colloidal silver and 2,5-di-t-octyl ha A gelatin layer containing an emulsified dispersion of idroquinone. Ninth layer; low-sensitivity blue-sensitive silver halide emulsion layer (BL-1) Monodisperse emulsion (Emulsion III) consisting of AgBrI with an average grain size of 0.40 μm and AgI 6 mol% ... Silver coating amount 0.9 g / m ² sensitization Dye V: 1.3 × 10 ^-5 mol per mol of silver Yellow coupler (EY-1): 0.29 mol per mol of silver 10th layer: High-sensitivity blue-sensitive emulsion layer (BH-1) Average grain Monodisperse emulsion consisting of AgBrI containing 0.8 μm in diameter and 10 mol% AgI (Emulsion IV) ... Silver coating amount 0.5 g / m ² Sensitizing dye V …… 1.0 × 10 ⁻⁵ mol per 1 mol of silver Yellow coupler (EY -1) ... 0.08 mol for 1 mol of silver DIR compound (ED-1) ... 0.0015 mol for 1 mol of silver 11th layer; first protective layer (Pro-1) Silver iodobromide (1 mol of AgI) % Average particle size 0.07 μm) Silver coating amount 0.5 g / m ² Gelatin layer containing UV absorbers UV-1 and UV-2. 12th layer; 2nd protective layer (Pro-2) Polymethylmethacrylate particles (diameter 1.5μ
m) and gelatin layer containing formalin scavenger (HS-1) In addition to the above composition, a gelatin hardening agent (H-1) and a surfactant were added to each layer. The compounds contained in each layer of Sample 1 are as follows. Sensitizing dye I; Anhydro 5,5'-dichloro-9-ethyl-
3,3'-di- (3-sulfopropyl) thiacarbocyanine hydroxide sensitizing dye II; anhydro 9-ethyl-3,3'-di- (3-
Sulfopropyl) -4,5,4 ', 5'-dibenzothiacarbocyanine hydroxide Sensitizing dye III; anhydro 5,5'-diphenyl-9-ethyl-3,3'-di- (3-sulfopropyl) Oxacarbocyanine hydroxide sensitizing dye IV; anhydro 9-ethyl-3,3'-di- (3-
Sulfopropyl) -5,6,5 ', 6'-dibenzoxacarbocyanine hydroxide Sensitizing dye V; anhydro 3,3'-di- (3-sulfopropyl) -4,5-benzo-5'-methoxy Thiacyanine With respect to the sample-1 thus prepared, as shown in Table-1, an image forming coupler (EM-1) and a colored coupler (ECM-1) were prepared according to the sample, respectively, according to the present invention. Samples 2 to 8 were prepared in the same manner as sample 1 except that the compound represented by the general formula [A] according to the present invention was used. The amount of the polymer coupler according to the present invention is an amount which gives almost the same magenta image density as that of Sample-1, and the amount of the compound represented by the general formula [A] of the present invention gives almost the same masking density as that of Sample-1. Is the amount. Furthermore, the DIR compound of the sixth layer is added to ED-2 and ED- of diffusible DIR.
Samples 9 and 10 in place of 3 were prepared. The amounts used are equimolar to the comparison. Each of the sample Nos. 1 to 10 thus prepared was exposed through a wedge exposure and a sharpness measurement chart using white light, and then subjected to the following development processing. Processing step (38 ℃) Color development 3 minutes 15 seconds Bleach 6 minutes 30 seconds Water washing 3 minutes 15 seconds Fixing 6 minutes 30 seconds Water washing 3 minutes 15 seconds LIG color development 3 minutes 15 seconds Water washing 3 minutes 15 seconds Dry Used in each processing step The composition of the treatment liquid is as follows. [Color developer] 4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) -aniline ・ sulfate 4.75g anhydrous sodium sulfite 4.25g hydroxylamine ・ 1/2 sulfate 2.0g anhydrous potassium carbonate 37.5g Sodium bromide 1.3g Nitrilotriacetic acid trisodium salt (monohydrate) 2.5g Potassium hydroxide 1.0g Add water to make 1. [Bleach] Ethylenediaminetetraacetic acid ammonium salt 100.g Ethylenediaminetetraacetic acid diammonium salt 10.0g Ammonium bromide 150.0g Glacial acetic acid 10.0ml Add water to make pH 1 and use ammonia water to adjust pH = 6.0.
Adjust to. [Fixing solution] Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.5 g Sodium metasulfite 2.3 g Water is added to make 1 and pH is adjusted to 6.0 using acetic acid. [Stabilizer] Formalin (37% aqueous solution) 1.5 ml Conidax (Konishi Rokusha Kogyo Co., Ltd.) 7.5 ml Add 1 to add water. [LIG color developing solution] Ferrous ammonium sulfate 1 mmol / l aqueous solution For each of the obtained samples, blue light (B), green light (G), and red light (R) were used to obtain relative sensitivity (S) and sharpness. Degree (MTF) was measured. The results are shown in Table 2. Note that the relative sensitivity (S) is the relative value of the reciprocal of the exposure dose that gives the fog density +0.1, and is shown as a value with the sensitivity measured with each light of B, G, and R of sample No. 1 being 100. It was The sharpness improving effect is due to the MTF (Modulation Transfer Functio) of dye images.
n) was determined and shown as the relative value of MTF at 40 lines / mm (the BGR measurement value of sample No. 1 is 100). The following things are clear from Table-2. That is, sample-1,2
From the comparison, when the compound of the general formula [A] according to the present invention is used, the sensitivity is increased but the sharpness is largely deteriorated. Sample-1
From the comparison with 3 and 4, the use of the polymer coupler according to the present invention improves the sharpness but does not improve the sensitivity. However, Samples 5 to 8 in which both of them were used together had high sensitivity and excellent sharpness, and further improved sharpness as compared with Samples 3 and 4. Samples using diffusible DIR-
It can be seen that this effect is very large in 9,10 and is preferable. That is, the sample of the present invention has high sensitivity and can improve sharpness. [Example-2] ED-1 of the third layer and the fourth layer was replaced with ED-3, ECC-1 was replaced with A-2, and EC-1 was replaced with PC-9.
Example 1 except that ECM-1 in the layer was replaced with A-7, EM-1 was replaced with PM-3, and ED-1 in the sixth layer was replaced with ED-3.
Sample-11 was prepared in the same manner as Sample-1. The amount of the replaced compound used is the same as that described in Example-1. The samples-1 and 11 thus produced were treated in the same manner as in Example-1 to obtain the results shown in Table-3. From Table 3, it is clear that the samples of the present invention have high sensitivity and excellent sharpness.

Claims (1)

[Claims] 1. A silver halide color photographic light-sensitive material having a silver halide emulsion layer on a support and containing a polymer coupler and a compound represented by the general formula [A] in the same light-sensitive layer. material. General formula [A] LIG-X (In the formula, X represents a group capable of releasing the LIG moiety as a result of silver halide development, and LIG forms a complex with a metal ion when bonded to X, LIG represents a ligand moiety capable of forming a metal complex dye in the color light-sensitive material.
-X itself is a substantially colorless and non-diffusible compound. )