JPS62204257A - Silver halide conventional color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain superior sharpness and image fastness and to save silver by using a coupler having a specified group and producing a compound having a dye moiety having maximum absorption wavelength before shift. CONSTITUTION:This photographic sensitive material contains a coupler having a dye moiety whose maximum absorption wavelength has been shifted to the shorter wavelength side by a bond which is directly cleaved by a coupling reaction with the oxidized product of a developing agent. The bond may be cleaved through a timing group. The coupler produces a compound (compound A) having a dye moiety having maximum absorption wavelength before the shift as the result of the reaction. The coupler also has a group capable of fixising the hue of the compound A on the longer wavelength side and /or immobilizing the compound A in a photographic layer in the dye moiety. The preferred difference between the maximum absorption wavelengths before and after the shift is >=20nm, especially >=40nm. Superior sharpness and image fastness are obtd. and silver is saved.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a coupler having a dye moiety with a shifted maximum absorption wavelength. This invention relates to a silver halide conventional color photographic light-sensitive material containing a coupler having a dye moiety having a group capable of fixing the hue of a compound having a dye moiety having a maximum absorption wavelength and/or immobilizing the compound in a photographic layer. It is.

(Prior art) By color-developing a silver halide color photographic material, an oxidized aromatic-amine color developing agent and a coupler react to form indophenol, indoaniline,
It is known that indamine, azomethine, phenoxazine, phenazine and similar dyes can be produced to form color images.

In this method, subtractive color method is usually used for color reproduction.
A silver halide emulsion selectively sensitive to blue, green, and red and color image forming agents (couplers) of yellow, magenta, and cyan, which are complementary colors, respectively, are used.

Many studies have been conducted to improve the performance of color formers (couplers) that form image dyes, and many patents and technical documents have disclosed this. This is because the performance of the coupler used has a large impact on overall photographic performance, such as image quality performance such as sensitivity, color reproducibility, sharpness, or graininess, and color image preservation performance against heat, light, humidity, etc. This is because there is nothing else. For example, if the spectral absorption width of the dye formed when the coupler undergoes a coupling reaction with the oxidized developing agent is broad, or if there is unnecessary side absorption, color turbidity will occur and color reproducibility will be impaired. . In addition, the greater the amount of dye that can be produced from the coupler per unit weight, the less the amount of coupler added to the emulsion layer becomes.As a result, the emulsion film thickness is reduced, color bleeding phenomenon caused by optical factors is suppressed, and sharpness is reduced. The degree is improved. Furthermore, the higher the stability of the dye produced from the coupler against heat, light, humidity, or material components contained in color photographs, the better the storage stability of the image dye will be. Furthermore, the faster the coupler undergoes a coupling reaction with the oxidized developing agent, the more efficiently development occurs and the sensitivity of the light-sensitive material increases.

As specific examples of couplers proposed for the purpose of improving photographic performance as described above, the following are known.

Journal of Chemical 5oci
ety.

Perkin 1. /977, page 4097!
- A coupler has been reported in which the secondary absorption on the short wavelength side of the azomethine dye produced by a pyrazolone type coupler is reduced. US Pat. No. 2,941 discloses a bis-type yellow coupler for the purpose of reducing the molecular weight of the coupler required to form a given dye density. Also, U.S. Pat. No. 3,3//, 4t7 and U.S. Pat. Also, U.S. Pat.
No. 1 discloses a highly color-forming coupler that is advantageous for increasing sensitivity.

In recent years, there have been advances in performance in the molecular design of couplers, but this is not necessarily sufficient.In fact, due to the limitations that inevitably arise as long as conventional couplers are used, even more dramatic advances have been made. It can be said that it is now difficult to improve performance. The inevitable limitation of conventional couplers is that the coupler itself has the function of ``receiving the image information accumulated in silver halide via the oxidized developing agent, and itself becoming a chromophore component of the image dye.'' The point is that it has. For this reason, the properties of the image dye produced are determined by the molecular structure of the coupler, resulting in various contradictions in molecular design.

For example, even if a coupler with a high coupling rate is designed molecularly, the spectral absorption of the resulting image dye may be in an undesirable wavelength range or the side absorption may be large. Even if the coupling rate is low even for Kabu 2-, which has a sharp spectral absorption width and no side absorption, there may be problems with the stability of the coupler. This can be cited as an example. In other words, guidelines for selecting a coupler to achieve an efficient coloring function and guidelines for selecting a coupler to achieve a desired function as an image dye are not necessarily compatible. Under these circumstances, JP-A-141-/
411/3. Jt discloses dye release timed couplers.

The method of this patent utilizes the hue of the anion structure of the hydroxy-substituted aromatic azo dye produced by development. By the way, since the pH of the film is weakly acidic after the normal development process, a part of the azo dye released by the coupling reaction with the oxidized product of the aromatic primary amine developing agent remains. is discolored by protonation, resulting in a decrease in image density. or,
Since the counter cation of the azo dye is a metal ion in the developer, the storage stability of the image cannot be said to be sufficient. To solve these problems, the patent uses a high pH (approx. It can also be said that it has practical problems because it requires special processing.

- On the other hand, as a way to solve this problem of image density reduction, Japanese Patent Application No. 1997-27♂? No. gθ proposes the combined use of dye-releasing couplers with basic compounds and quaternary salts. Although this method has excellent effects in terms of image density stability, it is still not a fully developed technology in terms of layer thinning.

(Problems to be Solved by the Invention) Therefore, the first object of the present invention is to provide a color photographic material that provides excellent sharpness.

A second object of the present invention is to provide a color photographic material with excellent image fastness.

A third object of the present invention is to provide a color photographic material with reduced silver.

(Means for Solving the Problems) The object of the present invention is to provide a dye whose maximum absorption wavelength is shifted to the short wavelength side by a bond that is cleaved directly or via a timing group by a coupling reaction with an oxidized form of a developing agent. and as a result of the reaction, produce a compound (hereinafter referred to as compound A) that has a dye moiety that has a maximum absorption wavelength before shifting, and fix the hue of compound A to the long wavelength side. , or/and a silver halide conventional color photographic light-sensitive material containing a coupler having a group in the dye moiety that can immobilize the compound A in the photographic layer.

In the present invention, "fixing the hue" refers to biasing the hue of the aforementioned compound A toward the long wavelength side at a certain rate (not necessarily /θ0chi).

In the present invention, the term "immobilized within the photographic layer" means that Compound A is rendered resistant to diffusion through intermolecular interaction and substantially remains within the photographic layer. Therefore, the above-mentioned "fixation of hue" is not necessarily synonymous.

In the present invention, it is preferable that the difference between the maximum absorption wavelengths before and after the shift is greater than or equal to θnm, and particularly preferably
nm or more.

In the present invention, the term "conventional" refers to
It means that Compound A produced by photographic processing is utilized in a photographic layer.

However, the photographic layer in the present invention includes an image-receiving layer in the so-called diffusion transfer method (for example, U.S. Patent No. 9♂3, tOt
Peel-a (e)) type or special public show 4t as described in the issue 1/go 3! No. 4t/-J, ?
Ni9ri No. 9, JP-A Showo θ-/3θri No. 0 and British Patent/
, 330.124 as described in No. 330.124 (
Integrated) type, JP-A-Shoj7-//93411
The image-receiving layer in a peel-free film unit such as that described in this issue is not included.

That is, the silver halide color photographic light-sensitive material of the present invention has the ability to fix the hue of the image-receiving layer (compound A to the long wavelength side) before, during, and during exposure and photographic processing. A layer containing a compound that can be immobilized by a photosensitive layer does not involve a peeling operation between the photosensitive layer, and even if a peeling operation is not involved, there is no light-impermeable layer between the image-receiving layer and the photosensitive layer. and/or no light reflective layer is provided.

91 The coupler of the present invention is capable of producing a total of 1 and - dyes, including the azomethine dye produced by the coupling reaction and the dye produced from the previously shifted dye. Here, both dyes can be used to form a color image, or the azomethine dye that is initially formed can be made alkali-soluble so that it flows out into the processing solution during development, or it can be made colorless. By using coupler residues, only the dye generated from the shifted dye can be used for color image formation.

When the above-described couplers of the present invention are used as color image forming agents, they need not be completely colorless in the shifted dye state. Shifting the wavelength by blocking the auxochrome is generally advantageous because it changes the molar extinction coefficient from a few minutes to a few tens of minutes. For example, the compound of the present invention can be used as a yellow image forming agent by adding it to a blue-sensitive emulsion layer. Further, the compound of the present invention can be used as a magenta or cyan image forming agent by being added to the green-sensitive and red-sensitive emulsion layers, respectively. When a magenta or cyan dye is blocked with an auxochrome to shorten the wavelength, it is converted into a yellow-colored coupler and a magenta-colored coupler, respectively, using conventional color correction (
It is very convenient to have the function as a coupler for masking).

Colored couplers are generally used in combination with couplers used only to form color images, but they can also be used alone in the compounds of the present invention. This is because, in the case of a shifted dye, its molar extinction coefficient increases when it is restored, so if the ratio of the molar extinction coefficient of the dye matches the mixing ratio of conventional colored couplers, it is possible to mix other color image-forming couplers. This is because there is no longer any need for it.

That the compounds of the invention achieve the objects of the invention is supported by the principles set forth below.

That is, in the compound of the present invention, as a first method, the part that reacts with the oxidized developing agent and the part that becomes a dye can be functionally separated. In the second method and i~, two dyes can be produced from one oxidized developing agent. Both of these two methods are impossible with conventional couplers, and the fact that they are made possible explains the excellent effects of the present invention.

In addition, the blocking group in the part where the dye reaches is cleaved from 1 to
The structure can be designed by taking into account the performance of the dye that is produced after the reaction.

Therefore, the degree of freedom in selecting color images is greater than before, and as a result, it is possible to select a relatively wide range of dyes, such as dyes that do not easily fade, dyes with excellent spectral absorption, or dyes with large molecular extinction coefficients. . As a result, improvements in color reproducibility, image storage stability, and sharpness due to thinning of the layer can be achieved.

Furthermore, the structure of the portion that reacts with the oxidized developing agent may be designed by focusing only on its reactivity. When a dye is released from a coupler, if the color of the dye produced by coupling from the coupler is made to substantially match the desired color,
It can be used in conjunction with dyes produced from shifted dyes.

At this time, compared to conventional color image-forming couplers, the compound of the present invention can be added in an extremely small amount, resulting in improved sharpness. On the other hand, even if it becomes necessary to use a coupler core that produces a dye of a color different from the desired color in order to emphasize structural design that increases the color development rate, the azomethine dye produced by the coupling can be made water-soluble. There is no problem at all as long as it does not remain on the photosensitive material after processing. This makes it possible to design the structure of a color image forming agent with a high color development speed more freely than before, and a highly sensitive photosensitive material can be achieved.

It has a dye moiety whose maximum absorption wavelength is shifted to the shorter wavelength side due to a bond that is cleaved directly or via a timing group upon a coupling reaction with an oxidized form of the developing agent used in the present invention, and which As a result, it is possible to generate a compound (hereinafter referred to as compound A) having a dye moiety having a maximum absorption wavelength before the shift, and to fix the hue of the compound A to the long wavelength side, or/and to produce a compound A by photographing the compound A. Couplers having a group in the dye moiety that can be immobilized in the layer include those represented by the following general formula (1).

Cp-+TIMEqX-Dye+LtW (1)-/
In formula 3, Cp represents a coupler residue that releases -(-TIMEiX-Dye +LiW) through a coupling reaction with an oxidized product of an aromatic primary amine developing agent. TIME is
represents a timing group, and n represents θ or a positive integer.

Dye is a dye residue and X represents an auxochrome residue of the dye.

L represents a linking group, and W represents an amine group or ammonium salt. m represents θ or /.

Therefore, the coupler residue represented by Cp can form a dye through a coupling reaction with the oxidized product of an aromatic primary amine developing agent, or it can form a colorless substance ( There are so-called colorless coupler residues).

When Cp has a diffusion-resistant group, it has a diffusion-resistant group.
In some cases, it has no alkali solubilizing group.

When n≧/, the timing group represented by TIME is C
It represents a divalent or trivalent organic group that connects the coupling part of p and -X-Dye. When n=θ, -X-D
When ye directly binds to the coupling-7 goo portion of Cp, it becomes K.

As a mechanism for releasing -X-D y e when TIME is present, for example, a photographically useful group (hereinafter referred to as PUG
Examples include those disclosed as release timing type couplers.

A method for releasing PUG by an intramolecular nucleophilic substitution reaction after elimination, as described in US Pat. Kuko 3 da, and the same 2nd -/♂♂θ3! Due to the electron movement along the conjugated system after separation, as described in ! 11 Method of releasing PUG, JP-A-1
7-jl,! ? 37, and the method described in the same O♂-Co θ97410, in which, after detachment, an intramolecular nucleophilic substitution reaction is caused by a nucleophilic group newly generated by electron transfer along a conjugated system to release PUG. Gansho 9-734174
Examples include the method of releasing PUG by cleavage of hemiacetal after detachment, as described in 9-♂97/9.

The coupler of the present invention includes not only the case where the coupler has a timing group represented by the general formula (1) but also the case where the coupler has the following trivalent timing group.

For example, Tokukai Akira! t/? -, 2θ As described in No. 97, Cp and TIME also have a bond at the non-coupling site of Cp, and even after the coupling reaction with the oxidized form of the developing agent and the subsequent reaction, Cp and TIME
There are cases where and have a bond. Also, Tokugan Showo 9
-♂97/9 issue, same j? -9θ&,? No. 7, J-9-
9.2 oj issue, and same j9-9.2 o! As described in No. 7, cases where TIME and Dye further have a bond that does not cleave even after the coupling reaction with the oxidized form of the developing agent and subsequent reactions are also included. In each of the above cases, a bond between Cp and I that will not be cleaved even after the coupling reaction with the oxidized form of the developing agent and subsequent reactions is established.
)ye may further be present. Alternatively, the structure of general formula (I) may further have such an uncleavable bond between Cp and TIME and between TIME and Dye.

Examples of the auxochrome residue represented by X include heteroatoms such as oxygen atom, nitrogen atom, or sulfur atom.

The dye residue represented by Dye has an auxochrome group blocked by Cp or TIME, so that its maximum absorption wavelength is on the shorter wavelength side.

These pigments include, for example, J Fabia 7,
:Ltsuf-ha/l/Thoma7 (J, Fabian,
H.

Hartmann), 'Light Abduction'
Op Organic Kararan” (LightAb
sorption of Organic Co1or
ants).

(Springer Verlag)
Verlag), but is not limited to these.

More desirable dyes are those that have an appropriate hue when the auxochrome is dissociated.

Preferred dyes having a hue fixing group or a dye immobilization group include the following general formula (IIA) or (II
Examples include hydroxy group-substituted aromatic azo dyes and hydroxy group-substituted heterocyclic aromatic azo dyes represented by B).

General formula [% formula %) In the formula, X, L, W, and m represent the same meanings as defined in general formula (1) 1~, Y is an unsaturated bond in a conjugated relationship with the azo group 2 represents an atomic group that contains at least one unsaturated bond and is connected to X in the atom constituting the unsaturated bond, 2 represents an atomic group that contains at least one unsaturated bond that can be conjugated with an azo group, and the number of carbon atoms contained in Y and Z are 70 or more in total.

In the general formula (HA) and r[IB:], X is preferably an oxygen atom. In the general formulas [11A) and [2B], Y and 2 are preferably aromatic groups or unsaturated heterocyclic groups. The aromatic group is preferably a substituted or unsubstituted phenyl group or naphthyl group. The unsaturated heterocyclic group is preferably a 2-membered heterocyclic group having a hetero atom selected from a nitrogen atom, a sulfur atom, or an oxygen atom, and may be a benzene-fused ring. Examples of heterocyclic groups include groups having a ring structure such as pyrrole, thiophene, furan, imidazole, /, 2,4t-)lyazole, oxazole, thiadiazole, pyridine, indole, benzothiophene, benzimidazole, or benzoxazole. It is.

Y may have a substituent in addition to X and the azo group, and examples of the substituent include an aliphatic group, an aromatic group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acylamino group, an alkylthio group, and an arylthio group. group, heterocyclic group, sulfonyl group, halogen atom, nitro group, nitroso group, cyano group, carboxyl group, hydroxyl group, sulfonamide group, alkoxy group, aryloxy group, acyloxy group, and further carbamoyl group, ureido group,
They are a sulfamoyl group, a carbamoylsulfonyl group, or a hydrazinyl group. These groups may be further substituted.

When Z represents a substituted aromatic group or a substituted unsaturated heterocyclic group, the substituents and i to include those listed for Y above.

When Y and 2 contain an aliphatic group moiety as a substituent,
It may be substituted or unsubstituted, saturated or unsaturated, straight-chained or branched, chain-like or cyclic, and has a carbon number of 32 to 32, preferably 7 to -0.

When Y and 2 contain an aromatic group moiety as a substituent,
It has a carbon number of t to /θ, and is preferably a substituted or unsubstituted phenyl group.

Among the groups represented by general formula (II), preferred examples are as follows.

(D-/) W (D-, 2) (D-J) (D-4t) (D-j) (D-, <) 2-1V2 (D-, r) (D-9) (D -7) (t,) -W -2 In the set, X' represents an oxygen atom or a sulfur atom, and G
represents a substituent selected from those listed as substituents for Y and 2 in general formulas [IIA) and [I[B], n represents θ, l, or co, and q represents 0. /,
or 3, r FiO.

or represents an integer from / to da. B1, B2, B3 and B4 each represent a hydrogen atom or a substituent as explained for G, or B1 and B2, and B3 and B4 may be connected to represent a benzene condensed ring. When a benzene condensed ring is represented, the moiety may be substituted with a substituent represented by G.

In the formula, when s Q or r represents a number of 2 or more,
G may be the same or different.

vl represents an oxygen atom, a sulfur atom, or an imino group which may have a substituent.

v2 represents an aliphatic hydrocarbon residue, an aryl group, and a petroproduct residue. When v2 represents an aliphatic hydrocarbon residue, it may be saturated or unsaturated. - It may be chained, branched, or cyclic. Preferably carbon number/~
, 2.2 alkyl groups (eg, methyl, ethyl, impropyl, butyl, dodecyl, octadecyl, cyclohexyl, etc.), and alkenyl groups (eg, allyl, octenyl, etc.).

Aryl groups are preferably phenyl groups and naphthyl groups, and heterocyclic groups are preferably pyridinyl, quinolyl,
These include chenyl, piperidyl, imidazolyl, etc.

Examples of the substituents introduced into these aliphatic hydrocarbon residues, aryl groups, and heterocyclic groups include those listed for Y in the general formulas CIIA) and CIFB).

Za, Zb, and Zc are methine, substituted methine, =N
-2tlf-NH-4[, Za-Zb bond and Zb
One of the -Zc bonds is a double bond, and the other is a single bond. However, Za, Zb.

Zc cannot be N at the same time. Zb-Zc is carbon-
In the case of a carbon double bond, it may constitute a part of an aromatic ring, and this aromatic ring may have a substituent listed for part t- of Y above.

Further, any one of Za, Zb, and Zc is bonded to X' to form -X/-C-.

In the general formulas [IIA) and [IIB:], W is preferably represented by the following general formulas [■] and [■].

CI[l] (IV) In the formula, R21 represents an aliphatic group, an aryl group or a heterocyclic group, and R22 or R23 represents a hydrogen atom, an alkyl group or an aryl group. R21, R22 or R2
3 may be condensed with each other in the form of ml-.

When R21 represents an aliphatic group, this aliphatic group represents a linear or branched alkyl group, aralkyl group, alkenyl group, cycloalkyl group, cycloalkenyl group, or alkynyl group having 7 to 3 carbon atoms; These include halogen atoms (e.g., chlorine atom, fluorine atom, etc.), aryl groups (e.g., phenyl group, α- or β-naphthyl group, co-, goudichlorophenyl group, 3-antadecylphenyl group, co-,
4t-di-t-amylphenyl group, etc.), heterocyclic group (
For example, -pyridyl group, cobenzothiazolyl group, -
(furyl group, N-piperidyl group, N-7 talimide group, etc.), cyano group, alkoxy group (e.g. methoxy group, butoxy group, coethylhexyloxy group, -1methanesulfonylethoxy group, 3-phenoxypropoxy group) , hexadecyloxy group, etc.), aryloxy group (e.g., phenoxy group, cuchlorophenoxy group 1.2.
4t-di-tert-butylphenoxy group, 3-methanesulfonamidophenoxy group, gucyanophenoxy group, cornamethoxy group, etc.), acylamino group (e.g.
acetamido group, benzamide group, (,2,<t-di-tert-amylphenoxy, acetamido group 1.2-
(,2-chlorophenoxy)tetradecanamide group, 3
-[co(2,googie-tert-hexyl)butyramide]benzamide group, etc.), imide group (e.g., succinimide group, phthalimide group, N-hydantoynyl group, etc.), anilino group (e.g., phenylamino group, cochloroaniline group, etc.), lino group, N-methylanilino group, cochloro!-tetradecanamideanilino group, q-methoxyanilino group, etc.), alkylamino group (e.g., methylamino group, N,N-diethylamino M, N-(2-ethoxy ethoxy)amine group, etc.), peterocyclic amine group (e.g., co-biridylamino group, co-imidazolylamino group, co-pyrimidylamino group, etc.), urei, do group (e.g., methylureido group, N, N-di propylureido group, phenylureido group, darkchlorophenylureto group, goopropanesulfonylphenylureate group, etc.),
Sulfamoylamino group (e.g. N.

N-dimethylsulfamoylamino group, N-methyl-N
-phenylsulfamoylamino group, N.

N-diisopropylsulfamoylamino group, etc.), alkylthio group (e.g., butylthio group, dodecylthio group, 3-phenoxypropylthio group, cyclopentylthio group, benzylthio group, etc.), arylthio group (e.g.,
phenylthio group, 2-methylphenylthio group, cudodecylphenylthio group, coptyloxy-j-tert
-octylphenylthio group, [, &-dodecyloxyphenylthio group, etc.), heterocyclic thio group (e.g., cobenzooxazolylthio group, l-ethyltetrazole-!=bonylamino group (e.g., methoxycarbonylamino group,
butoxycarbonylamino group, etc.), aryloxycarbonylamino group (e.g., phenoxycarbonylamino group, etc.), sulfonamide group (e.g., methanesulfonamide group, benzenesulfonamide group, dodecanesulfonamide group, goododecyloxybenzenesulfone) amide group, etc.), carbamoyl group (e.g., N-methylcarpamoyl group, N,N-dibutylcarbamoyl group, N-
phenylcarbamoyl group, N-methyl-N-phenylcarbamoyl group, etc.), sulfamoyl group (e.g. N
-butylsulfamoyl group, N-phenylsulfamoyl group, N,N-dipropylsulfamoyl group, N-methyl-N-phenylsulfamoyl group, etc.), sulfonyl group (e.g. methanesulfonyl group, dodecane sulfonyl group, benzenesulfonyl group, &-)luenesulfonyl group, etc.), sulfinyl group (e.g. methanesulfinyl group, benzenesulfinyl group, etc.), acyl group (e.g. acetyl group, pro-ξnoyl group, dodecanoyl group, benzoyl group, pivaloyl group, <'-methoxybenzoyl group, etc.), alkoxycarbonyl group (e.g., methoxycarbonyl group, tetradecyloxycarbonyl group, etc.)
, aryloxycarbonyl group (e.g., phenoxycarbonyl group, etc.), phosphonyl group (e.g., methoxyphosphonyl group, butylphosphonyl group, phenylphosphonyl group, etc.), imino group (e.g., propylidenimino group,
), cyanothio group, acyloxy group (e.g., acetoxy group, octanoyloxy group, benzoyloxy group,
etc.), carbamoyloxy groups (e.g., N-acetylaminooxy group, N-benzoylaminooxy group, etc.)
, a silyloxy group (e.g., trimethylsilyloxy group, diptylmethylsilyloxy group, etc.), a sulfonyloxy group (e.g., methanesulfonyloxy group, benzenesulfonyloxy group, etc.), a silyloxy group (e.g., /- A phenyltetrazole-oxy group, a cochtrahydropyranyloxy group, etc.), a hydroxy group, or a nitro group may be substituted.

When R21 represents an aryl group, this aryl group represents an aryl group having t to 31 carbon atoms, and these are phenyl groups, α- or β-naphthyl groups, or the substituents or groups mentioned above for the aliphatic group of R21. It represents an aryl group which may be substituted with a straight chain or branched alkyl group, an aralkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, or an alkynyl group.

When R21 represents a heterocyclic group, this ring may be saturated or unsaturated and contains at least 7 nitrogen, oxygen or sulfur atoms as heteroatoms,
The atom bonded to the nitrogen atom in the general formula [drunk] or [■] is a nitrogen atom or a carbon atom, and is a substituent or a linear or branched alkyl group or an aralkyl group as described above for the aliphatic group of R21. is a heterocyclic group which may be substituted with a group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, or an alkynyl group.

R22, R23 in general formula [■] and CIV)
To explain in more detail, the aliphatic group and aryl group of R22 and R23 have the same meaning as the aliphatic group and aryl group described in detail for R21.

θ In the general formula [■], E represents an anion, such as a halogen ion (e.g., chloride ion, bromide ion, iodide ion, etc.), a sulfate ion (e.g., methyl sulfate ion, ethyl sulfate ion, etc.) , alkyl or aryl sulfonate ion (e.g. methanesulfonate ion, ethanesulfonate ion, benzenesulfonate ion, p) luenesulfonate ion,
), acetate ion, sulfate ion, etc.

Among these, chloride ions, alkyl sulfate ions,
and aryl sulfate ions are particularly preferred.

Furthermore, the present invention is particularly effective in the general formula (1)
, Cp is the following general formula (V), (M), (■), (
■), (DOl(X), (XI), (Xll), (Xn
l), (XW>-! or (XV)) These couplers are preferred because they have a high coupling rate.

General formula (V) General formula (M) -3 Goo general formula (■) I General formula (■) General formula (IX) General formula (X) General formula (M) General formula (Xir) General formula (XIII) General Formula (XV) General formula (XV) RlO-CH-R11 In the above formula, the free bond derived from the coupling position represents the bonding position of the coupling-off group. In the above formula, R1, R2, R3, R4, R5, R6, R7,
When R8, R9, Rlo or 1Rtt contains a diffusion-resistant group, it has a total number of carbon atoms of ♂ to 3.2, preferably /θ
~, 2.2; otherwise, the total number of carbon atoms is preferably /j or less.

Next, R1-R11,11 of the general formulas (V) to (XV)
q and p will be explained.

In the formula, R1 represents an aliphatic group, an aromatic group, an alkoxy group, or a heterocyclic group, and R2 and R3 each represent an aromatic group or a heterocyclic group.

In the formula, the aliphatic group represented by R1 preferably has a carbon number/
- λ may be substituted or unsubstituted, linear or cyclic. Preferred substituents for the alkyl group include an alkoxy group, an aryloxy group, an amino group, an acylamino group, and a halogen atom, which may themselves have further substituents. Specific examples of aliphatic groups useful as R1 are: isoprobyl, isobutyl, tert-butyl, isoamyl, te.
rt-amyl group, /, /-dimethylbutyl group, /, /-
Dimethylhexyl group, /, /-diethylhexyl group, dodecyl group, hexadecyl group, octadecyl group, cyclohexyl group, 2-methoxyisopropyl group, cophenoxyisopropyl group, --p-tert-butylphenoxyisopropyl group, α -aminoisozorobyl group, α-(
These include diethylamino)isopropyl group, α-(succinimide)isopropyl group, α-(phthalimido)isopropyl group, α-(benzenesulfonamido)inpropyl group, and the like.

When R1, R2 or R3 represents an aromatic group (especially a phenyl group), the aromatic group may be substituted. Aromatic groups such as phenyl groups are alkyl groups having 3 or less carbon atoms,
alkenyl group, alkoxy group, alkoxycarbonyl group, alkoxycarbonylamino group, aliphatic amide group, alkylsulfamoyl group, alkylsulfonamide group,
It may be substituted with an alkylureido group, an alkyl-substituted succinimide group, etc. In this case, the alkyl group may have an aromatic group such as phenylene interposed in its chain. The phenyl group may also be substituted with an aryloxy group, an aryloxycarbonyl group, an arylcarbamoyl group, an arylamido group, an arylsulfamoyl group, an arylsulfonamide group, an arylureido group, etc., and the aryl group of these substituents The moiety may be further substituted with one or more alkyl groups having a total number of carbon atoms of /~J, 2.

The phenyl group represented by R11R2 or R3 may further include an amine group, a hydroxy group, a carboxyl group, a sulfo group, a nitro group, a cyano group, a thiocyano group or・May be substituted with a rogen atom.

R1, R2 or R3 may also represent a substituent in which a phenyl group is fused with another ring, such as a naphthyl group, a quinolyl group, an isoquinolyl group, a chromanyl group, a chromanyl group, a tetrahydronaphthyl group, etc. These substituents may themselves have further substituents.

When R1 represents an alkoxy group, the alkyl moiety represents a linear or branched alkyl group, an alkenyl group, a cyclic alkyl group, or a cyclic alkenyl group having from / to 32 carbon atoms, preferably from / to λ; may be substituted with a halogen atom, aryl group, alkoxy group, etc.

When R1, R2 or R3 represents a heterocyclic group, the heterocyclic group is connected to the carbon atom of the carbonyl group of the acyl group in alpha acylacetamide or the nitrogen atom of the amide group, respectively, through one of the carbon atoms forming the ring. Combine with.

Examples of such unstretched rings include thiophene, furan, biran, virole, pyrazole, pyridine, pyrazine, pyrimidine, pyridazine, indolizine, imidazole, thiazole, oxazole, triazine, thiadiazine, and oxazine. These may further have a substituent on the ring.

In the general formula (■), R5 is a linear or branched alkyl group having 7 to 3 carbon atoms, preferably / to 2.2 carbon atoms (e.g., methyl, isopropyl, tert-butyl, hexyl, dodecyl group, etc.); Alkenyl group (e.g. allyl group, etc.), cyclic alkyl group (e.g. t is cyclopentyl group, cyclohexyl group, norbornyl group, etc.), aralkyl group (e.g. benzyl, β-phenylethyl group, etc.)
, represents a cyclic alkenyl group (e.g. cyclo-enthenyl, cyclohexenyl group, etc.), and these represent a norogen atom, nitro group, cyan group, aryl group, alkoxy group, aryloxy group, carboxyl group, alkylthiocarbonyl group, arylthio carbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, sulfo group, sulfamoyl group, carbamoyl group, acylamino group, diacylamino group, ureido group, urethane group, thiourethane group, sulfonamide group, heterocyclic group, arylsulfonyl group, Alkylsulfonyl group, arylthio group, alkylthio group, alkylamino group, dialkylamino group, anilino group, N-arylanilino group, N-al-4t/- kylanilino group, N-acylanilino group, hydroxy group, mercapto group, etc. May be replaced.

Furthermore, R5 may represent an aryl group (eg, phenyl group, α- or β-naphthyl group, etc.). The aryl group may have 7 or more substituents, such as an alkyl group, an alkenyl group, a cyclic alkyl group, an aralkyl group, a cyclic alkenyl group, a halogen atom, a nitro group, a cyan group, an aryl group, and an alkoxy group. group, aryloxy group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, sulfo group, sulfamoyl group, carbamoyl group, acylamino group, diacylamino group, ureido group, urethane group, sulfo/amide group, heterocyclic group, aryl Sulfonyl group, alkylsulfonyl group,
Arylthio group, alkylthio group, alkylamino group,
It may have a dialkylamino group, anilino group, N-alkylanilino group, N-arylanilino group, N-acylanilino group, hydroxy group, mercapto group, etc. R
More preferred among 5-4t, 2- and j7 is phenyl in which at least seven ortho positions are substituted with an alkyl group, an alkoxy group, a halogen atom, etc. It is useful because it does not change color due to light or heat.

Furthermore, R5 is a heterocyclic group (for example, a j-membered or di-membered heterocyclic group containing a nitrogen atom, an oxygen atom, or a sulfur atom as a hetero atom, a fused heterocyclic group, such as a pyridyl group, a quinolyl group, a furyl group, a benzothiazolyl group, oxasilyl group, imidazolyl group, naphthoxacylyl group, etc.), a heterocyclic group substituted with the substituents listed for the above-mentioned aryl group, an aliphatic or aromatic acyl group, an alkylsulfonyl group, an arylsulfonyl group, an alkylcarbamoyl group, It represents an arylcarbamoyl group, an alkylthiocarbamoyl group or an arylthiocarbamoyl group, and may be 1 to 1.

In the formula, R4 is a hydrogen atom, a linear or branched alkyl, alkenyl, cyclic alkyl, aralkyl, or cyclic alkenyl group having from 1 to 3.2 carbon atoms, preferably 1 to 22 carbon atoms (these groups are the same as those listed above for R5). ), aryl groups and heterocyclic groups (these may have substituents such as R
5), alkoxycarbonyl groups (e.g. methoxycarbonyl group, ethoxycarbonyl group, stearyloxycarbonyl group, etc.)
, aryloxycarbonyl group (e.g., phenoxycarbonyl group, naphthoxycarbonyl group), aralkyloxycarbonyl group (e.g., benzyloxycarbonyl group, etc.), alkoxy group (e.g., methoxy group, ethoxy group, heptadecyloxy group, etc.), aryloxy Group (
For example, phenoxy group, tolyloxy group, etc.), alkylthio group (for example, ethylthio group, dodecylthio group, etc.),
Arylthio group (e.g. phenylthio group, α-naphthylthio group, etc.), carboxyl group, acylamino group (e.g. acetylamino group, 3-[(,2,4t-di-ter
t-amylphenoxy)acetamido]benzamide group, etc.), diacylamino group, N-alkylacylamino group (e.g. N-methylpropionamide group, etc.), N-
Aryl acylamino groups (e.g. N-phenylacetamide group), ureido groups (e.g. ureido, N-arylureido, N-alkyl ureido groups, etc.), urethane groups, thiourethane groups, arylamino groups (e.g. phenylamino, N-methylanilino group, diphenylamino group, N-acetylanilino group, cochloro!-tetradecanamideanilino group, etc.), alkylamino group (e.g. n-butylamino group, methylamine group, cyclohexylamino group, etc.), cycloamino groups (e.g., lydino, pyrrolidino, etc.), heterocyclic amino groups (e.g., goupyridylamino, cobenzoxazolylamine, etc.), alkylcarbonyl groups (e.g., methylcarbonyl), arylcarbonyl groups (e.g., phenyl), carbonyl group, etc.), sulfonamide group (e.g. alkylsulfonamide group, arylsulfonamide group, etc.), carbamoyl group (e.g. ethylcarbamoyl group, dimethylcarbamoyl group, N-methyl-phenylcarbamoyl group,
N-phenyl<zr-carbamoyl), sulfamoyl group (e.g. N-
Alkylsulfamoyl, N,N-dialkylsulfamoyl group, N-arylsulfamoyl group, N-alkyl-N-arylsulfamoyl group, N,N-diarylsulfamoyl group), cyano group , hydroxy group,
Represents any one of a mercapto group, a halogen atom, and a sulfo group.

In the formula, R6 is a hydrogen atom or a straight or branched alkyl group having 1 to 32, preferably 2 carbon atoms;
Represents an alkenyl group, a cyclic alkyl group, an aralkyl group, or a cyclic alkenyl group (17), which may have the substituents listed for R5 above.

Further, R6 may represent an aryl group or a heterocyclic group, and these may have the substituents listed for R5 above.

R6 is a cyan group, an alkoxy group, an aryloxy group, a halogen atom, a carboxy group, an alkoxycarbonyl group, an aryloxycarbonyl-4t- group, an acyloxy group, a sulfo group, a sulfamoyl group, a carbamoyl group, an acylamino group, a diacylamino group. group, ureido group, urethane group, sulfonamide group, arylsulfonyl group, alkylsulfonyl group, arylthio group,
It may also represent an alkylthio group, alkylamino group, dialkylamino group, anilino group, N-arylanilino group, N-alkylanilino group, N-acylanilino group, hydroxy group or mercapto group.

R7, R8, and R9 each represent a group used in a normal da equivalent type phenol or an α-naphthol coupler. Specifically, R7 represents a hydrogen atom, a halogen atom, an alkoxycarbonylamino group, or an aliphatic hydrocarbon residue. group, N-arylureido group, acylamino group,
' 12 or -8-R12 (where R12 is an aliphatic hydrocarbon residue), and when one or more R7 exists in the same molecule, the one or more R7 may be different groups, Aliphatic hydrocarbon residues include those having substituents.

Further, when these substituents include an aryl group, the aryl group may have the substituents listed for R5 above.

Examples of R8 and R9 include groups selected from aliphatic hydrocarbon residues, aryl groups and heterocyclic residues, or one of these may be a hydrogen atom,
These groups also include those having substituents. Further, R8 and R9 may jointly form a nitrogen-containing heterocyclic nucleus.

The aliphatic hydrocarbon residues may be either saturated or unsaturated, and may be straight-chain, branched, or
Any ring-shaped one may be used. Preferred are alkyl groups (e.g., methyl, ethyl, propyl, isopropyl, butyl, t-butyl, isobutyl, dodecyl, octadecyl, cyclobutyl, cyclohexyl, etc.) and alkenyl groups (e.g., allyl, octenyl, etc.). .

Aryl groups include phenyl groups, naphthyl groups, etc.
In addition, examples of heterocyclic residues include pyridinyl, kyl/IJyl,
Typical examples of chenyl and bi are lysyl, imidazolyl and the like. Substituents introduced into these aliphatic hydrocarbon residues, aryl groups, and heterocyclic residues include halogen atoms, nitro, hydroxy, carboxyl, amino, substituted amino, sulfo, alkyl, alkenyl, aryl, peterocycle, alkoxy, Aryloxy, arylthio, arylthio, acylamino, carbamoyl, ester,
Examples include groups such as acyl, acyloxy, sulfonamide, sulfamoyl, sulfonyl, and morpholino.

l represents an integer from / to g, q represents an integer from 7 to 3, and p represents an integer from / to j.

RIO is an arylcarbonyl group, an alkanoyl group having 2 to 3 carbon atoms, preferably co-, 2.2 carbon atoms, an arylcarbamoyl group, an alkanecarbamoyl group having 2 to 3.2 carbon atoms, preferably λ to 2.2 carbon atoms; /~3.2 preferably/
-2,2 alkoxycarbonyl group or aryloxycarbonyl group, which may have a substituent, such as an alkoxy group, alkoxycarbonyl group, acyloxy 9-mino group, or alkylsulfamoyl group □ , an alkylsulfonamide group, an alkylsuccinimide group, a halogen atom, a nitro group, a carboxyl group, a nitrile group, an alkyl group, or an aryl group.

R11 is an arylcarbonyl group, an alkanoyl group with 2 to 32 carbon atoms, preferably -2.2, an arylcarbamoyl group, an alkanecarbamoyl group with 2 to 32 carbon atoms, preferably -2, and 7 to 3 carbon atoms. .2 Preferably/~
JJ alkoxycarbonyl group or aryloxycarbonyl group, carbon number 7 to -? , 2 1 or ~ 22
alkanesulfonyl group, arylsulfonyl group, aryl group, negative or di-membered heterocyclic group (hetero atom is selected from nitrogen atom, oxygen atom, sulfur atom, such as triglyl group, imidazolyl group, phthalimide group,
represents a succinimide group, furyl group, pyridyl group or benzotriazolyl group 7)), and these represent R
It may have the substituents mentioned in IO.

As stated above, the general formula (1)Ko-! θ-, when Cp has a diffusion-resistant group, a diffusion-resistant colored or colorless compound is formed after a coupling reaction with the oxidized product of an aromatic primary amine developing agent, and Cp has a non-diffusion-resistant group. When the compound has a diffusible group, the compound formed by the coupling reaction has a diffusivity corresponding to the non-diffusion resistant group of Cp. ! Furthermore, if Cp has an alkali solubilizing group, the compound formed by the coupling reaction will be eluted from the film.

The coupler represented by the general formula (1) of the present invention also includes cases where it is a polymer. That is, it is derived from a monomeric coupler represented by the following general formula (1), and the general formula (X■)
A polymer having a repeating unit represented by, or
It is a copolymer with seven or more non-color-forming monomers containing at least seven ethylene groups that do not have the ability to couple with the oxidized product of an aromatic primary amine developing agent. Here, one or more monomer couplers may be simultaneously polymerized.

General formula (XVI) CH2=C+A2+f-+A3+f-+A15Q General formula (X■) -fcH2-C-)- In the formula, R is a hydrogen atom, a lower alkyl group having 7 to 5 carbon atoms,
or represents a chlorine atom, A1 is -CONH-2-NH
CON) I-1-NHCOO-1-coo-1-so2
-1-co-1-NHCO-1-8O2NH-2-NH
8O2-1-OCO-1-OCONH-1-NH- or -0-, A2 represents -CONH- or -COO-, A3 is an unsubstituted or substituted alkylene group having 7 to 70 carbon atoms, aralkylene group or an unsubstituted or substituted arylene group, and the alkylene group may be linear or branched.

(Examples of alkylene groups include methylene, methylmethylene, dimethylmethylene, dimethylene, trimethylene, tetramethylene, hantamethylene, hexamethylene, and decylmethylene; examples of aralkylene groups include benzylidene; examples of arylene groups include phenylene and naphthylene) Q#' i represents a compound residue represented by the general formula (summer), and may be bonded C2 at any site of Cp T I ME or Dye.

'Xj% and k represent θ straddle/, but fsjs
and k cannot be θ at the same time.

Examples of substituents for the alkylene group, aralkylene group, or arylene group represented by A3 include aryl group (e.g. phenyl group), nitro group, hydroxyl group, cyan group, sulfo group, alkoxy group (e.g. methoxy group), aryloxy group ( For example, phenoxy group), acyloxy group (for example, acetoxy group), acylamino group (for example, acetylamino group), sulfonamide group (for example, methanesulfonamide group), sulfamoyl group IJ, methylsulfamoyl=! 3- group), halogen atoms (e.g. fluorine, chlorine, bromine, etc.)
, a carboxy group, a carbamoyl group (eg, methylcarbamoyl group), an alkoxycarbonyl group (eg, methoxycarbonyl group), and a sulfonyl group (eg, methylsulfonyl group). When there are λ or more substituents, they may be the same or different.

Next, non-color-forming ethylene-like monomers that do not couple with the oxidation products of aromatic-grade amine developers include acrylic acid, α-chloroacrylic acid, α-alkyl acrylic acid, and these acrylic acids, α -chloroacrylic acid, α
Examples include -alkylacrylic acids and esters or amides derived from these acrylic acids, methylenebisacrylamide, vinyl esters, acrylonitrile, aromatic vinyl compounds, maleic acid derivatives, vinylpyridines, and the like. More than one kind of non-color-forming ethylenically unsaturated monomers can be used at the same time.

The above coupler addition layer of the present invention is a photosensitive halo j4t- It is a silver germide-containing layer or a layer adjacent thereto.

When adding the coupler to a photosensitive silver halide-containing layer, the amount added is based on 7 mol of silver halide contained in that layer, and when adding it to an adjacent layer, the amount is based on the amount of halogen contained in the adjacent layer. It is preferably 0.007 to 1 mol per mol of silveride. Particularly preferably 0.00t~θ,! It is in the molar range.

Preferred specific examples of the couplers represented by formula (r) in the present invention are shown below, but the invention is not limited thereto.

An example of a coupler in which the bond between TIME (when n≧l) or Cp (when n=θ) and X in general formula (1) is cleaved to restore the yellow dye! Ma- -t Y-goo j 7- Y-/ -! l- 1J open kIa62-ZU4Z:)/ (1/)Y-/! - to l - 1e1ifl'a62-i? U42b'/ (1dJ Komori 11 flash aJ day s Q Ql) Giant Ipe Σ 9% -H Kai ME 伽-Q λ 1-.

-1p- In the present invention, the coupler represented by general formula (1) is
All compounds can be synthesized by a direct substitution method between the dye moiety and the coupler core, and more specific synthesis examples of the compounds of the present invention are shown below.

Synthesis of dyes N-methylethanolamine (,2,2,og1θ.

3 mol) triethylamine (7 g 1 θ, 2 mol) is dissolved in T)iF (ro Oml) and stirred at room temperature. A THF solution (3θomll) of the compound /(/, 29 g, 0°3 mol) was added dropwise thereto.

After the addition, the mixture was stirred at room temperature for 3 hours, and the crystals formed were filtered. When the mother liquor is distilled off under reduced pressure, an oily substance is obtained (/jj
g). Add at least 6 liters of oil without refining.

The reaction mixture is warmed to 20°C and stirred for 10 minutes, then cooled to 100C.

A DMAC solution (200 ml) containing 3 qqg (0.32 mol) of the compound was added dropwise thereto.

Stir at 100~/j0C for 3 hours, add water, and
Adjust H to g, t (dilute hydrochloric acid).

The reaction mixture was extracted repeatedly with ethyl acetate, and the organic layer was washed with water and dried over Na2SO4. The organic solvent was distilled off under reduced pressure, and the obtained oil was recrystallized twice from ethyl acetate/hexane to obtain 2/g of the desired compound y.

Synthesis of Y-/ (<togo, 1 mol) acetonitrile θOm
I will fight against l. In it, triethylamine/jg (
θ, 1 mol) and stir.

After stirring for 1 hour at a system temperature of tθ0C, the reaction mixture was poured into 00ml of diluted hydrochloric acid (291). The aqueous layer was extracted with ethyl acetate, and the organic layer was washed with water and dried over Na2SO4.

The solid obtained by distilling off the organic solvent under reduced pressure was recrystallized twice from ethyl acetate/acetonitrile to obtain 2 g of the desired Y-/ as yellow crystals.

In the photographic emulsion layer of the photographic light-sensitive material used in the present invention, any silver halide such as silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, and silver chloride may be used. The silver halide is silver iodobromide or silver iodochlorobromide containing up to about 30 mole percent silver iodide. Particularly preferred is about 2 mol%.
silver iodobromide containing up to about 25 mole percent silver iodide.

The silver halide grains in the photographic emulsion may be so-called regular grains having a regular crystal structure such as a cube, octahedron, or dodecahedron, or may have an irregular crystal shape such as a spherical shape. It may be one with crystal defects such as twin planes or a composite form thereof.

The grain size of the silver halide may be fine grains of about 0.1 micron or less, large grains with a projected area diameter of about 10 microns, monodisperse emulsion with a narrow distribution, or polydisperse with a wide distribution. An emulsion may also be used.

The silver halide photographic emulsion that can be used in the present invention can be produced by a known method.
RD), No. 17643 (December 1978), 22
-23 pages% 'T e Emulsion 3fi (EIIluls
ion preparation and types)
” and SNo. 18716 (November 1979),
This ends by following the method described on page 648.

The photographic emulsion used in the present invention is described in "Physics and Chemistry of Photography" published by Grass 7, published by Paul Montell (P.

1afkides, Cbimie et Phys
ique PhotographiquePaul H
ontely 1967), Duffint, "Photographic Emulsion Chemistry", 7th Edition, published by Cal Press (G, F, Duffint)
Pl+oto-graphic Emu! 5ion
Chemistry (Focal Press, 1
966), "Manufacture and Coating of Photographic Emulsions" by Zelikman et al.
7 Published by Oichi Cal Press (V, L, Zelikman
etal, Making and Coat
ing Pl+otographic Emul-
sion, Focal Press, 1964
), etc.). That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt with the soluble halogen salt may be any one-sided mixing method, simultaneous mixing method, or a combination thereof. It is also possible to use a method (so-called back-mixing method) in which good single grains are formed under an excess of silver ions. As one type of simultaneous mixing method, a method of keeping I) All in the liquid phase in which silver halide is produced, ie, a so-called Chondrald double jet method, can also be used. According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained.

Two or more types of silver halide emulsions formed separately may be mixed and used.

The halogenated 1 emulsion consisting of the above regular grains is
I) Obtained by controlling Ag and pH during particle formation. For more information, please refer to 7 otograpic science and engineering (PI+otogripl).
+ic 5science and Engineering
ng) Volume 6, pp. 159-165 (1962); Journal of 7 Otographic Science (Jour
nal ofPhotographic 5cienc
e)t Vol. 12, pp. 242-251 (1964), U.S. Patent No. 3,655,394 and British Patent No. 1,41
No. 3,748.

A typical monodisperse emulsion is an emulsion in which silver halide grains have an average grain diameter of greater than about 0.1 micron, and at least about 95% by weight of the silver halide grains are within ±40% of the average grain diameter. The average grain diameter is between about 0.25 and 2 microns, and at least 95% by weight or at least about 95% by volume of the silver halide grains have an average grain diameter of ±20 microns.
% can be used in the present invention. A method for producing such an emulsion is described in U.S. Pat. No. 3.5.74,6.
No. 28, No. 3,655,394 and British Patent No. 1
, No. 413,748. Also, JP-A-48
-8600, 51-39027, 51-830
No. 97, No. 53-137133, No. 54-48521
No. 54-99419, No. 5 B-37635,
Monodisperse emulsions such as those described in Japanese Patent No. 58-49938 can also be preferably used in the present invention.

Tabular grains having aspect ratios of about 5 or more can also be used in the present invention. The tabular grains are ff)7'It
, 7 Autographic Science and Engineering (Cutoff, PhotographicS
science ancl Engineering),
Volume 14, pp. 24B-257 (1970); U.S. Pat. It can be easily prepared by the method described in No. 2t1.12.157. When tabular grains are used, there are advantages such as improved color sensitization efficiency by sensitizing dyes, improved graininess, and increased sharpness, as disclosed in the above-cited U.S. Pat. No. 4,434,226. It is detailed in the issue etc.

The crystal structure of these emulsion grains may be uniform, or may have a layered structure with different halogen compositions inside and outside.
No. 46, U.S. Patent No. 3,505.068, U.S. Patent No. 4,44
No. 4,877 and Japanese Patent Application No. 58-248469. *In addition, silver halides of different compositions may be bonded by epitaxial bonding, or may be bonded with compounds other than silver halide, such as silver oxide or lead oxide.These emulsion grains , U.S. Patent No. 4,094,684, U.S. Patent No. 4,142,900,
No. 4,459,353, British Patent No. 2゜038.79
No. 2, U.S. Patent No. 4,349,622, U.S. Patent No. 4,395
, No. 478, No. 4,433,501, No. 4,463,
No. 087, No. 3,656,962, No. 3,852,0
No. 67, JP-A-59-162540, etc.

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

The emulsion of the present invention is usually used which has been subjected to physical ripening, chemical ripening and spectral sensitization. Additives used in such processes are Research Disclosure No. 17.
643 and No. 18716, and the relevant parts are summarized in the table below.

Known photographic additives that can be used in the present invention are also described in the above two research studies and disclosures, and the descriptions are shown in the table below.

Additive f! Class 41 RD17643 RD18
7161 Chemical sensitizers Page 23 Page 648 Right column 2 Sensitivity enhancers Same as above 3 Spectral sensitizers, Pages 23-24 Page 648 Right column - Super sensitizers
Page 649 Right column 4 Brightener Page 24 5 Antifoggant Page 24-25 Page 649 Right column and stabilizer 6 Light absorber, 7 Pages 25-26 649 Right column - Ilter dye 650 Left column Ultraviolet absorber Anti-fogging agent Agent page 25 right column page 650 left to right column 8
Dye image stabilizer page 25 9 Hardener page 26 Page 651 Left column 10 Bingu Page 26 Same as above 11 Plasticizer, lubricant Page 27 850 Right column 12 Coating aid, Table 26~
Page 27 Same as above Surface activator 13 Static prevention Page 27 Same as above Stop agent Various color couplers can be used in the present invention.
RD) No. 17643, ■-C-G. As dye-forming couplers, couplers that give the three primary colors (i.e., yellow, agenta, and cyan) in subtractive color development are important.Specific examples of diffusion-resistant, 4-equivalent or 2-equivalent couplers are mentioned above.
In addition to the couplers described in the patents D17643, ■-C and D, the following can be preferably used in the present invention.

A representative example of the yellow coupler that can be used in the present invention is a hydrophobic acylacetamide coupler having a ballast group. A specific example is U.S. Pat.
US Pat. , No. 408.194, No. 3,447,92
No. 8, No. 3.933,501 and No. 4,022
, 620, Japanese Patent Publication No. 5B-10739, U.S. Patent No. 4,401,752, U.S. Patent No. 4,326,024,
RD18053 (1979 47'i), UK Patent No. 1
, No. 425,020, West German Application No. 2,219.91
No. 7, No. 2,261,361, No. 2.329,5
Typical examples include the nitrogen atom separation type yellow couplers described in No. 87 and No. 2,433,812. α-pivaloylacetanilide couplers have excellent color fastness, particularly light fastness, while α-benzoylacetanilide couplers provide high color density.

Magenta couplers useful in the present invention include hydrophobic ingzolone- or cyanoacetyl-based couplers, preferably 5-pyrazolone- and pyrazoloazole-based couplers, which have a ballast group. The 5-pyrazolone coupler is preferably a color in which the 3-position is substituted with an arylamino group or an acylamino group from the viewpoint of the hue and color density of the coloring dye.
, No. 311.082, No. 2,343,703, No. 2,600,788, No. 2,908,573, No. 3,062,653, No. 3,152,896 and No. 3,936,015, etc.

Particularly preferred as the leaving group for the two-equivalent 5-pyrazolone coupler are the nitrogen atom leaving group described in U.S. Pat. No. 4,310,619 or the arylthio group described in U.S. Pat. No. 4,351.897. Also European Patent No. 73
, No. 636, the 5-pyrazolone coupler having a ballast group can provide high color density. As a pyrazoloazole coupler, U.S. Patent No. 3,061,432
pyrazolobenzimidazoles described in US Pat. No. 3,725,067, preferably pyrazolo[
5,1-cl[1,2,4]) lyazoles, pyrazolotetrazoles and Research Disclosure 242 described in Research Disclosure 24220 (June 1984) and JP-A-6.0-33552
30 (June 1984) and JP-A-60-43659
The imidazo[1,2
-bl pyrazoles are preferred, U.S. Pat. No. 4,540
．． Pyrazolo [Ls-bl[i, 2°4
1 triazole is particularly preferred.

Cyan couplers that can be used in the present invention include hydrophobic, diffusion-resistant, 7-thol and phenolic couplers, such as the naphthol couplers described in U.S. Pat. 4,052,
No. 212, No. 4,146.396, No. 4,228
Typical examples include two-equivalent 7-toll couplers of the oxygen atom dissociation type described in No. 233 and No. 4,296,200. Further, specific examples of phenolic couplers are given in U.S. Patent Nos. 2,369,929 and 2,80.
1.171, 2.77.2, 162, 2.
No. 895,826, etc.

Couplers capable of forming humidity and temperature-fast cyan dyes are preferably used in the present invention, exemplified by the ethyl phenolic nucleus meta-position described in U.S. Pat. No. 3,772,002. Phenolic cyan coupler with alkyl group or more, US patent @2,7
No. 72,162, No. 3,758,308, No. 4,
No. 126,396, No. 4,334,011, No. 4
, No. 327,173, West German Patent Publication Route 3,329,72
9 and European Patent No. 121,365, etc.,
U.S. Patent No. 3,446,622, U.S. Patent No. 4,333,9
No. 99, No. 4,451,559 and No. 4゜42
These include phenolic couplers having a phenylureido group at the 2-position and a 7-syl amino group at the 5-position, as described in No. 7.767. European Patent No. 161,626
The cyan coupler described in No. A, in which the 5-position of the 7-tole is substituted with a sulfonamide group, an amide group, etc., also has excellent fastness of the colored image and can be preferably used in the present invention.

In order to correct unnecessary absorption of chromophores, it is preferable to use a colored coupler in combination with a color photosensitive material for photographing to perform masking, as disclosed in U.S. Pat. The yellow-tinted magenta couplers described in U.S. Pat. No. 4,004,929, U.S. Pat.
Typical examples include the magenta-colored cyan coupler described in No. 6,368. Other colored couplers are described in the above-mentioned RD17643, items ① to G.

Granularity can be improved by using a coupler button in which the coloring dye has an appropriate diffusibility. Such a coupler is
U.S. Patent No. 4,366,237 and British Patent No. 2,
No. 125,570 contains examples of magenta couplers, and European Patent No. 96,570 and West German Application No. 3,2
No. 34,533 describes specific examples of yellow, magenta or cyan couplers. .

The dye-forming couplers and specialty couplers described above may form dimers or more polymers; typical examples of polymerized dye-forming couplers are described in U.S. Pat. No. 3,451,82.
No. 0 and No. 4,080,211. A specific example of a polymerized magenta coupler is described in the British patent $
No. 2,102,173 and U.S. Patent No. 4,367,2
It is described in No. 82.

Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. The DIR coupler releasing the development inhibitor is the aforementioned RD17643,
The patent couplers listed in Sections .-F. are useful.

Preferred in combination with the present invention is JP-A-57-
Developer deactivated type represented by No. 151944; U.S. Patent No. 4,248,962 and JP-A-154234
Timing type represented by No. 1987-39653
Particularly preferred are JP-A-57-151944, JP-A-58-217.932, JP-A-59-75474, JP-A-59-82214,
Developer deactivation type DIR couplers described in No. 59-82214 and No. 59-90438, etc. and Japanese Patent Application No. 1973
This is a reactive DIR coupler described in No. 9-39653 and the like.

In the light-sensitive material of the present invention, a coupler that releases a nucleating agent, a development accelerator, or a precursor thereof in an image form during development can be used. Specific examples of such compounds are given in British Patent Nos. 2w097t14.0 and 2,131.
, No. 188. Particularly preferred are couplers that release a nucleating agent that has an adsorption effect on silver halide.
8 and 59-170840.

Suitable supports for use in the present invention include, for example, the R
D, No. 17643, page 28 and same, No. 187
16, from the right column on page 647 to the left column on page 648.

The color photographic material according to the present invention includes the above-mentioned RD, N
o, 17643, pp. 2.8-29 and same, No. 18
Development processing can be carried out by the usual methods described in 651 left column to right column of 716.

The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. Aminophenol compounds are also useful as color developing agents, but p-7
Enylenecyamine-based compounds are preferably used, and typical examples include 3-methyl-4-7minor-N, N-yethylaniline, and 3-methyl-4-amino-N-ethyl-N-.
β-Hydroxylethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N
-β-no)xyethylaniline and their sulfates,
Examples include hydrochloride and p-)luenesulfonate. These diamines are generally more stable in their salt form than in their free state, and are therefore preferably used.

The color developer may contain pH buffering agents such as alkali metal carbonates, borates or phosphates, development inhibitors or capri-inhibitors such as bromides, iodides, benzimidazoles, benzothiazoles or mercapto compounds. Generally, it contains agents such as agents.

In addition, if necessary, preservatives such as hydroxylamine or sulfites, organic solvents such as triethanolamine and diethylene glycol, development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts, and amines, and dyes may be added. forming coupler, competition coupler,
Nucleating agents such as sodium boron hydride, auxiliary developers such as 1-phenyl-3-pyrazolidone, viscosity-imparting agents, amide/polycarboxylic acids, aminopolyphosphonic acids,
Various chelating agents such as alkylphosphonic acids and phosphonocarboxylic acids, antioxidants described in West German Patent Application (OL S) No. 2,622,950, and the like may be added to the color developer.

In the development process for reversal color photosensitive materials, black and white development is usually performed followed by color development. This black and white developer contains dihydroxybenzene Q such as hydroquinone, 1-phenyl-
3-pyrazolidones such as 3-pyrazolidone or N-
Known black and white developers such as aminophenols such as methyl-p-7 minophenol can be used alone or in combination.

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

The bleaching process may be performed simultaneously with the fixing process, or may be performed separately. In order to further speed up the processing,
A bleach-fixing treatment may be used after bleaching. Examples of bleaching agents include compounds of polyvalent metals such as iron ([1), cobalt (■), chromium (Vl), and copper (II)], peracids, and quinone. 7 Typical bleaching agents include erythyanide; dichromate; iron (II), nitrone compounds, etc.
I) or Kobal) (III), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid,
complex salts of aminopolycarboxylic acids such as nitrilotriacetic acid, 1゜3-diamino-2-propatoltetraacetic acid, or organic acids such as citric acid, tartaric acid, malic acid; persulfates;
Manganate; nitroso-7 ale, etc. can be used. Of these, iron ethylenecyaminetetraacetate (III
) salt, diethylenetriaminepentaacetic acid iron (lI[) salt and persulfate are preferred from the viewpoint of rapid processing and environmental pollution.
Furthermore, the ethylenediaminetetraacetic acid iron(II) complex salt is particularly useful in both stand-alone bleach solutions and bleach-fix solutions.

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

Specific examples of useful bleach accelerators are described in U.S. Pat. No. 3.893.858, German Pat.
, No. 290,812, No. 2,059,988, JP-A No. 53-32736, No. 53-57831, No. 37418, No. 53-65
No. 732, No. 53-72623, No. 53-95630
No. 53-95631, No. 53-104232,
No. 53-124424, No. 53-141623, No. 53-28426, Research Disclosure N
Compounds having a mercapto group or disulfide group as described in Japanese Patent Publication No. 17129 (July 1978); Thiazolidine derivatives as described in JP-A-50-140129; Japanese Patent Publication No. 45-8506, JP-A-52 -20
No. 832, No. 53-32735, US Patent @ 3,70
Thiourea derivatives described in No. 6.561; West German patent @1,
127.715, iodide described in JP-A-58-16235; West German Patent No. 966.410, JP-A No. 2,748.
Polyethylene oxides described in No. 430;
Polyamine compound described in JP-A-49-42434, JP-A-49-59644, JP-A-5
No. 3-94927, No. 54-35727, No. 55-2
Compounds described in No. 6506 and No. 5B-163940 and iodine and bromine ions can also be used. Among them, compounds having a mercapto group or a disulfide group are preferable from the viewpoint of a large promoting effect, and in particular, compounds having a mercapto group or a disulfide group are preferred, and are particularly preferred in US Pat.
No. 858, West German Patent No. 1,290,812, JP-A-5
The compounds described in U.S. Pat. No. 3-95630 are preferred, and the compounds described in U.S. Pat. These bleach accelerators are particularly effective when bleach-fixing.

Examples of the fixing agent include thiosulfates, thiocyanates, thioureas of 1,000-onythyl compounds, and large amounts of iodides, but 1,000-sulfuric acid sulfate is commonly used. Preservatives for bleach-fixing solutions and fixing solutions are preferably sulfites, bisulfites, or carbonyl bisulfite adducts.

After the bleach-fixing treatment or the fixing treatment, washing treatment and stabilization treatment are usually performed. In the water washing process and stabilization process, various known compounds may be added for the purpose of preventing precipitation and saving water. For example, in order to prevent precipitation, inorganic phosphoric acid, aminopolycarboxylic acid, organic amino Hard water softeners such as polyphosphonic acids and organic phosphoric acids, disinfectants and anti-pyre agents that prevent the growth of various bacteria, algae, and mold, metal salts such as magnesium salts, aluminum salts, and bismuth salts, and dry load and The weight can be reduced by adding surfactants and various hardening agents as necessary to prevent unevenness. Or Wester 7 Autograph Science and Engineering Magazine (L, E, We
stSPhot, Sci.

Eng-), Volume 6, 344-359 Beno (1965
) etc. may be added, and the addition of chelating agents and anti-piping agents is particularly effective.

In the washing process, two or more tanks are generally used for countercurrent washing to save water. Furthermore, instead of the water washing process,
A multi-stage countercurrent stabilization process as described in No. 8543 may be implemented.In the case of a 0-unit process, 2 to 9 countercurrent baths are required.In the 0-unit stabilization bath, the above-mentioned addition In addition to the agent, various compounds are added for the purpose of stabilizing the image.For example, the membrane p
Various buffering agents (e.g. borate, metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide) for adjusting H (e.g. pH 3-9) 17um, ammonia Typical examples include water, monocarboxylic acid, dicarboxylic acid, polycarboxylic acid, etc.) and aldehydes such as formalin. In addition, chelating agents (inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphoric acid, organic phosphonic acid, ami/polyphosphonic acid, phosphonocarboxylic acid, etc.), fungicides (benzisothiazolinone, isothiazolone, 4- Various additives such as thiazoline (benzimiguzole, halogenated phenol, sul7anilamide, benzotriazole, etc.), surfactants, optical brighteners, hardeners, etc. may be used, and compounds for the same or different purposes may be used. Two or more types may be used in combination.

In addition, ammonium chloride,
It is preferable to add various ammonium salts such as ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, and ammonium thiosulfate.

Furthermore, in the case of color sensitive materials for photography, the normally performed post-fixing (washing-stabilization) process can be replaced with the above-mentioned stabilization process and water-washing process (water-saving process). At this time, if the magenta coupler is 2 equivalents, the formalin in the stable solution may be removed.

The washing and stabilization processing time of the present invention varies depending on the type of sensitive material and processing conditions, but is usually 20 seconds to 10 minutes, preferably 20 seconds to 5 minutes.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up processing. In order to incorporate a color developing agent, it is preferable to use various precursors of the color developing agent.

For example, indoaniline compounds described in US Pat. No. 3,342,597, US Pat. No. 3,342,599, Research Disclosure No. 14850 and US Pat. No. 1515.
Including Schiff base type compounds described in No. 9, Fuldol compounds described in U.S. Pat. No. 13924, metal salt complexes described in U.S. Pat. Showa 56-6235
No. 56-16133, No. 56-59232, No. 56-67842, No. 56-83734, No. 56-
No. 83735, No. 56-83736, No. 56-897
No. 35, No. 56-81837, No. 56-54430, No. 56-106241, No. 56-107236,
Examples include various salt-type precursors described in Japanese Patent No. 57-97531 and Japanese Patent No. 57-83565.

The silver halide color photosensitive material of the present invention may contain various 1-phenyl-
3-pyrazolidones may be incorporated. Typical compounds are JP-A Nos. 56-64339, 57-144547, 57-211147, 58-50532, 58-50536, 5B-50533, 5B-
No. 50534, No. 5B-50535 and No. 58-1
It is described in No. 15438, etc.

Various treatment liquids in the present invention are used at 10°C to 50°C. A temperature of 33°C to 38°C is standard, but higher temperatures may be used to accelerate processing and shorten processing time, or lower temperatures may be used to improve image quality and stability of the processing solution. be able to. Further, in order to save silver on the photosensitive material, a treatment using cobalt intensification or hydrogen peroxide intensification as described in West German Patent No. 2,226,770 or US Pat. No. 3,674,499 may be carried out.

A heater, a temperature sensor, a liquid level sensor, a circulation pump, a filter, a floating pig, a squishy, etc. may be provided in each of the processing baths as necessary.

Further, during continuous processing, a constant finish can be obtained by using a replenisher for each processing solution to prevent fluctuations in the solution composition. The amount of light can be reduced to half or less than the standard replenishment amount to reduce costs.

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

Incidentally, the structural formulas of compounds other than those of the present invention used in the examples are summarized at the end of the examples.

Example/In order to evaluate the effectiveness of the compound of the present invention, Sample 10/ was prepared by coating the emulsion layer shown below on a transparent cellulose triacetate film support provided with an undercoat layer.

Sample 10/ (emulsion layer) Negative silver iodobromide emulsion (iodide steel y morch, average grain size 0.1=p) o, 3 years old g/m2 Yellow coupler (Cp-/) o, ttg/m2 high Boiling point organic solvent 0-/ θ, j t g/m2 Gelatin J, d g/m2 (housing layer) Gelatin / , 3 g/m2
4t-dichloro-hydroxy-8-triazine sodium salt tomg/m2 (sample 1
02~/θ4t) Yellow coupler Cp-/ of sample 10/ is changed to Cp-co, C
Sample 10 except that p-3 and Cp-a were replaced by equimolar amounts.
Samples 70.2 to 10 da were prepared in the same manner as in /.

(Samples 101 and 10) Samples/θ except that the yellow coupler Cp-/ of sample 10/ was replaced with compounds Y-/ and Y-1 of the present invention in equimolar amounts.
Samples /l)j, /θ were prepared in the same manner as /.

These samples were subjected to sensitometric exposure and color development as shown below, and the yellow density of the resulting processed samples was measured. The results of photographic properties are shown in Table 1.

Development processing was performed using jtoc as described below.

Color development 3 minutes and 10 seconds Bleach white for minutes 30 seconds Water washing minutes/θ seconds Fixed arrival time - 0 seconds Water washing 3 minutes/seconds Stable 7 minutes Oj seconds The composition of the treatment liquid used in each step was as follows.

Color developer diethylenetriaminepentaacetic acid /, θg/-hydroxyethylidene-/, /-diphosphonic acid 2.0g Sodium sulfite, og Potassium carbonate
3theta,og potassium bromide
/, 41g potassium iodide
/, 3 mg hydroxylamine sulfate
2.41gy-(N-ethyl-N-β-hydroxyethylamino) monocomethylaniline sulfate 4t, jg Add water /・oppH10,θ Bleach solution Ethylenediaminetetraacetic acid ferric ammonium salt 100. θg Ethylenediaminetetraacetic acid disodium salt 7060g Ammonium bromide /! O1θg Ammonium nitrate 70.0g Add water
/, 01 pH B, O Fixer ethylenediaminetetraacetic acid disodium salt /, 0 g Sodium sulfite g, θg Ammonium thiosulfate aqueous solution (70%) /7j, 0 m Add g water to 11 Sodium bisulfite g,
/, 01tpH, 10/- Stabilizing solution *Rules: y (<to%) a, oml
Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization / θ) 0.7 g with water It can be seen that the sensitivity is high, the maximum density is high, and the color development is extremely high.

Due to this high color development, the amount of coupler used can be reduced, thinner layers can be achieved, and improvement in sharpness in photographic performance can be expected.

Cp-/ Cp-,2 −／　θdar

Claims (1)

[Claims] It has a dye moiety whose maximum absorption wavelength is shifted to the short wavelength side by a bond that is cleaved directly or via a timing group by a coupling reaction with an oxidized form of a developing agent, and as a result of this reaction, A compound having a dye moiety having a maximum absorption wavelength (hereinafter referred to as compound A) can be produced, and the hue of the compound A can be fixed on the long wavelength side, or/and the compound A can be immobilized in a photographic layer. A silver halide conventional color photographic light-sensitive material containing a coupler having a diluent group in the dye moiety.