JPH0651465A - Formation of color photograph element and color picture - Google Patents

Abstract

PURPOSE: To provide a color photographic material capable of forming an improved color image. CONSTITUTION: This color photographic material comprises a support for holding at least one kind of photographic silver halide emulsion layer and a combination of at least 2 kinds of separate couplers (A) and (B), and the coupler (A) can form a compound to be washed out from the photographic element at the time of reaction with an oxidized developing agent in photographic processing and it can release a development inhibitor or a timing group containing the development inhibitor, and the coupler (B) can form a compound to be washed out at the time of reaction with the oxidized developing agent in the photographic processing and it can release a photographic development inhibitor at once without any time retarding.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention comprises a combination of couplers which contains at least two couplers capable of forming wash dyes in the photographic material during photographic processing to form improved images. Photographic material and photographic processing.

[0002]

BACKGROUND OF THE INVENTION In the photographic art, various methods of releasing photographic development inhibitors (INH) from compounds such as couplers have been recognized in photographic materials and processing.
For example, US Pat. No. 4,248,962 describes compounds that release photographically useful groups by intramolecular nucleophilic substitution reactions in photographic materials. Other examples of means for releasing photographically useful groups are described, for example, in U.S. Pat. Nos. 4,409,323 and 4,861,701. These compounds, especially couplers, capable of releasing a photographically useful group have some control over the diffusion rate and diffusion distance of the photographically useful group, as well as the timing and rate of release.

Part of the compound that remains in the photographic material after releasing the photographically useful group (PUG), especially the development inhibitor group, and is formed in the material by reaction with the oxidized color developing agent. Dyes often impart undesirable properties to photographic materials during or after photographic processing. For example, dyes formed from couplers upon release of photographically useful groups often adversely affect the desired image. One solution to this has been to provide the coupler matrix with a coupler having a water-solubilizing group to allow dye formation from the coupler washed out of the photographic element during photographic processing. Such couplers are described, for example, in U.S. Pat. Nos. 4,482,629 and 5,026,628.

[0004]

A combination of a photographic material and a coupler in a photographic process which allows the removal of wash-out dye formed from the coupler during photographic processing while at the same time allowing improved image formation. There is a need to provide. Within a photographic material that allows the removal of undesired dyes formed from the compound during photographic processing, while at the same time allowing a high degree of control to generate and accept an interimage effect with silver development inhibitor groups. There remains a need to enable imaging elements. Furthermore, such coupler combinations should not require significant modification of the development inhibitor group, and such groups should not be released so as to adversely affect the ultimate end use of the group. The need to not exist exists with the added variables.

[0005]

The present invention provides these advantages with a color photographic element comprising a support having at least one photographic silver halide emulsion layer and a combination of at least two separate couplers. to enable. At least one of said couplers is capable of forming a compound which, upon reaction with an oxidized developer, is washed out of the photographic element during photographic processing and is capable of releasing a photographic development inhibitor group. It is a coupler (A). Also, at least one of the couplers is capable of releasing a coupling-off group upon reaction with an oxidized developer, which in turn releases a timing group and a photographic development inhibitor group. Are such couplers (B) which are capable of releasing a photographic development inhibitor group in the absence of a timing group. The combination of such couplers is intended to enable improved finishing of color photographic elements and interlayer effects in processing, such as the interlayer effect between the green and red sensitive layers of color photographic elements. Especially useful. With such a combination of couplers, for example, color saturation, image sensitometric curve shape, and image acutance can be better controlled.

The coupler (A) is capable of forming a compound, preferably a dye, that upon reaction with an oxidized developer, especially an oxidized color developer, is washed out of the photographic element during photographic processing, It can also be any coupler capable of releasing a photographic development inhibitor group. The coupler (A) can be represented by, for example, the following formula.

[0007]

[Chemical 2]

In the above formula, SOL is a water-solubilizing group. SO
L is known in the photographic art and is described in, for example, US Pat.
5,026,628. The water solubilizing group is a carboxylic group, a sulfo group and a hydroxyl group, which form a salt, as described in U.S. Pat. No. 4,482,629 (incorporated herein by reference). Hydrophilicity sufficient to impart good alkali solubility to the dye formed by the coupling reaction between the oxidized product of the color developing agent and the coupler (A). Is a group showing. Preferred SOL groups, -CONH _2, -
CONHCH _3, include -CO ₂ H and -OH.

COUP is a coupler moiety, such as a cyan, magenta or yellow dye-forming coupler moiety. REL is a releasing group known in the photographic art, preferably containing photographic ballast groups, as described in US Pat. No. 5,026,628. n and p are each independently 0 or 1. INH is a releasable development inhibitor group, also known in the photographic art. Typical development inhibitor groups include, for example, U.S. Patent Application Nos. 4,782,012, 4,477,563, 4,886,736.
Nos. 4,912,024 and 5,026,628, which are incorporated herein by reference for their disclosure, include compounds having a heterocyclic ring. Preferred development inhibitor groups include mercaptotetrazole, mercaptooxadiazole, mercaptothiadiazole and benzotriazole.

The coupler (B) is capable of releasing a coupling-off group when it reacts with an oxidized developer, which in turn produces a timing group and a photographic development inhibitor known in the photographic art. It can be any coupler capable of releasing a photographic group or a photographic development inhibitor group in the absence of a timing group. The coupler (B) can be represented by the following formula.

[0011]

[Chemical 3]

In the above formula, SOL is the water-solubilizing group described above. COUP is a coupler moiety as described above, for example a cyan, magenta or yellow dye-forming coupler moiety, with the remainder of the molecule attached at the coupling position. TIME is known in the photographic art as a releasable timing group capable of timely releasing INH during photographic processing, such as those described in US Pat. Nos. 4,409,323 and 4,248,962. It is a timed group. y and m are 0, 1 or 2.

Preferably, the color photographic element comprises a support having at least one photographic silver halide emulsion layer and a combination of at least two separate couplers (A) and (B), the coupler (A) is capable of forming a compound which, upon reaction with an oxidized developer, is washed out of the photographic element during photographic processing and is capable of releasing a photographic development inhibitor or a photographic development inhibitor. Can provide a timed release of said photographic development inhibitor, and coupler (B) can react with oxidized developer during photographic processing. Can form a compound that is washed out of the photographic element,
And capable of releasing the photographic development inhibitor with no time delay, couplers (A) and (B) are represented by the formula:

[0014]

[Chemical 4]

(In the above formula, SOL is a water-solubilizing group;
COUP is a coupler moiety; TIME is a timing group; REL is a releasing group containing a photographic ballast group; n and p are each independently 0 or 1;
INH is a releasable development inhibitor group; and y is 1 or 2.).

As used herein, the term "solubilizing group (SOL)"
Means any water-solubilizing group that allows the dye formed from the coupler described above to be washed out of the photographic element during photographic processing. Such solubilizing groups are preferably amide or carboxy groups such as CONH ₂ or CONHCH ₃ as described above. The coupler moiety can have one or more solubilizing groups. The type and number of water solubilizing groups on the coupler should not render the coupler in the photographic element mobile prior to exposure or processing. If desired, the REL and TIME groups may contain a water solubilizing group.

As used herein, the term "REL group" refers to any releasing group known in the photographic art that is attached to the coupling position of the coupler moiety and is capable of being released upon oxidative coupling of the coupler. Means This REL
The group is not a timed group that can release the development inhibitor moiety during photographic processing with any significant delay. The REL group preferably comprises a photographic ballast group.

The term "TIME group" herein refers to any timed group known in the photographic art capable of timed release of development inhibitor groups during photographic processing of said photographic element. Means Examples of time groups include, for example, U.S. Patent Applications Nos. 4,409,323, 4,248,962 and 5,02.
The thing described in the specification of 6,628 is mentioned.

TIME, as referred to herein, is the release delay as measured by half-life and can extend, but not exceed, the normal time required for development of photographic elements. That is, in the present invention, at least half of the coupling-off INH must be released at the end of the development period. The release delay of INH is usually about 5 seconds or more, preferably in the range of 5 to 600 seconds, and typically in the range of 10 to 100 seconds. This measurement is most often performed at a pH of 10 or 14.
Can be carried out in an aqueous solution of

In the present invention, the REL, or release, of the timed group in the development of the photographic element is without substantial delay. Release of the timing group (as measured by half-life) can occur with a half-life of usually less than 5 seconds, preferably within 2-3 seconds, and typically less than 1 second. As mentioned above,
Half-life can almost always be measured in aqueous solutions with a pH of 10 or 14.

"Aqueous solution having a pH of 10" means Tr at 23 ° C.
Contains 3% iton X-100 (a nonionic surfactant commercially available from Aldrich Chemical Company (Milwaukee, WI),
It means an aqueous solution whose pH is adjusted to 10 with a phosphate buffer.

"Aqueous solution having a pH of 14" means 45% acetonitrile and 55% 0.1N potassium hydroxide at 23 ° C.
% Means an aqueous solution containing.

[0023]

The preferred coupler (A) is represented by the following formula.

[0024]

[Chemical 5]

In the above formula, R ^1a is hydrogen and has 1 to 3 carbon atoms.
Alkyl groups, or alkyl or aryl groups containing at least one solubilizing group as described above; R ^2a , R ^3a and R ^4a are each independently hydrogen,
R ^5a is a substituted or unsubstituted alkyl or aryl, or a substituent that does not adversely affect the performance washed out of the photographic element of the dye formed upon reaction with an oxidized developer and the release of INH; , Methyl, or-
_{NO 2, Cl, -NHSO 2 R} , -SO 2 NHR, -O
CH ₃ , -NHCOR or -CONHR (in the formula, R
Can be a substituted or unsubstituted alkyl or aryl containing 1 to 10 carbon atoms, and IN
(Which does not adversely affect the release of H)); at least one of R ^2a , R ^3a and R ^4a is a photographic ballast group; s is 0 or 1; INH is a releasable development inhibitor group, also mercaptotetrazole, mercaptooxadiazole,
It can be selected from mercaptothiadiazole or benzotriazole inhibitor groups.

Another preferred coupler (A) has the formula:

[0027]

[Chemical 6]

Wherein R ^1b and R ^2b can be substituted or unsubstituted alkyl or aryl containing at least one solubilizing group as described above; R ^3b , R ^4b and R ^5b are , Each independently, hydrogen, substituted or unsubstituted alkyl or aryl, or a substituent that does not adversely affect the release of INH; at least one of R ^3b , R ^4b and R ^5b is a photographic ballast group. S is 0 or 1; and INH is the development inhibitor group described above.

The term "alkyl or aryl containing from 1 to 10 carbon atoms" herein refers to a dye formed which is to be washed out of the photographic element during processing and which can contain, for example, water solubilizing groups. Means a group allowing sufficient water solubility in

Further preferred couplers (A) capable of forming washout dyes can be represented by the formula:

[0031]

[Chemical 7]

In the above formula, R^6aIs hydrogen, 1 to 3 carbon atoms
Containing an alkyl group or a solubilizing group as described above
At least one substituted or unsubstituted alkyl containing
Can be aryl; R^7aOr R
^12aIs hydrogen, methyl, or -NO₂ , Cl, -NH
SO₂ R ^15a, -SO₂ NHR^15a, -OCH₃ , -N
HCOR^15aOr-CONHR^15aSubstituents such as
Can be, where R^15aHas 1 to 10 carbon atoms
Substituted or unsubstituted alkyl or aryl containing
Can adversely affect the release of INH
No, for example -NO₂ , Cl, -OCH₃ , -CONHC
H₃ , NHCOCH₃ , SO₂ NHCH₃ And R^8a
Is hydrogen, methyl, or -NO₂ , Cl, -NHSO
₂ R^16a, -SO ₂ NHR^16a, -OCH₃ , -NHC
OR^16aOr -CONHR^16aIs a substituent such as
Yes, but R^16aContains 1 to 40 carbon atoms
Substituted or unsubstituted alkyl or aryl.
Can be done; R^9aOr R^10aIs hydrogen, methyl, carbon
A substituted alkyl or aryl containing 1 to 40 children
Can be; s can be 0 or 1; R
^13aOr R^14aIs hydrogen, methyl, 1 to 10 carbon atoms
Substituted or unsubstituted alkyl or aryl containing
Can be reel; R^8a, R^9a, R^10aAnd R
^11aAt least one of which is a photographic ballast;
INH is a releasable development inhibitor group as described above.
is there.

The first part of the coupling-off group, which is attached directly to the coupling position of the coupler, is intramolecularly capable of being replaced by a quinone-methide group or other such group which is released by the elimination reaction. It is recognized that it may contain carbamate-type groups which are liberated by the cyclization reaction.

The preferred coupler (B) is represented by the following formula.

[0035]

[Chemical 8]

Wherein R ^1a can be hydrogen, alkyl containing 1 to 3 carbon atoms, or alkyl or aryl containing at least one solubilizing group as described above; R ^2a , R ^3a and R ^4a are each independently hydrogen, substituted or unsubstituted alkyl or aryl,
Or a substituent that does not adversely affect the release of INH; R ^5a is hydrogen, methyl, or —NO ₂ , Cl, —
_{NHSO 2 R, -SO 2 NHR,} -OCH 3, -NHC
OR or -CONHR (In the formula, R is carbon atom 1 to 1)
0 or a substituted or unsubstituted alkyl or aryl, and may be a substituent such as (which does not adversely affect the release of INH);
At least one of R ^2a , R ^3a and R ^4a is a photographic ballast group; s is 0 or 1; and INH
Is a releasable development inhibitor group and can be selected from mercaptotetrazole, mercaptooxadiazole, mercaptothiadiazole or benzotriazole inhibitor groups.

Another preferred coupler (B) has the formula:

[0038]

[Chemical 9]

Wherein R ^1b and R ^2b can be substituted or unsubstituted alkyl containing at least one solubilizing group as described above; R ^3b , R ^4b and R ^5b are each Independently hydrogen, substituted or unsubstituted alkyl or aryl, or a substituent that does not adversely affect the release of INH; at least one of R ^3b , R ^4b and R ^5b is a photographic ballast group; s Is 0 or 1; and INH is the development inhibitor group described above.

The term "alkyl or aryl containing from 1 to 10 carbon atoms" herein refers to a formed dye which is to be washed out of the photographic element during processing and which can contain, for example, water solubilizing groups. Means a group allowing sufficient water solubility in

Further preferred couplers (B) capable of forming washout dyes can be represented by the formula:

[0042]

[Chemical 10]

In the above equation, R^6aIs hydrogen, 1 to 3 carbon atoms
Containing an alkyl group or a solubilizing group as described above
At least one substituted or unsubstituted alkyl containing
Can be aryl; R^7aOr R
^12aIs hydrogen, methyl, or -NO₂ , Cl, -NH
SO₂ R ^15a, -SO₂ NHR^15a, -OCH₃ , -N
HCOR^15aOr-CONHR^15aSubstituents such as
Can be, where R^15aHas 1 to 10 carbon atoms
Substituted or unsubstituted alkyl or aryl containing
Can adversely affect the release of INH
No; R^8aIs hydrogen, methyl, or -NO₂ , Cl, −
NHSO₂ R^16a, -SO ₂ NHR^16a, -OCH₃ ,
-NHCOR^16aOr-CONHR^16aSuch as
Can be a substituent, provided that R is^16aIs 1 to 40 carbon atoms
Substituted or unsubstituted alkyl or aryl containing
Can be le; R^9a, R^10aOr R^11aIs water
Substituted alkyls containing elemental, methyl and 1 to 40 carbon atoms
Can be either aryl or aryl; s is 0 or 1
Can be; R^8a, R^9a, R^10aAnd R^11aOut of
At least one of which is a photographic ballast; R^13aOr
R^14aContains hydrogen, methyl, 1 to 10 carbon atoms
A substituted or unsubstituted alkyl or aryl
INH can be released as described above.
It is a development inhibitor group.

The first part of the coupling-off group, which is directly attached to the coupling position of the coupler, is intramolecularly capable of being replaced by a quinone-methide group or other such group which is released by the elimination reaction. It is recognized that it may contain carbamate-type groups which are liberated by the cyclization reaction.

Another preferred coupler (B) has the formula:

[0046]

[Chemical 11]

In the above formula, R ^6b and R ^7b are carbon atoms 1 to 1
Selected from substituted or unsubstituted alkyl or aryl containing 0; R ^8b is hydrogen, methyl, —NO ₂ ,
^{_{Cl, -NHSO 2 R 15a, -SO}} 2 NHR 15a, -O
CH _3, selected from -NHCOR ^15a and -CONHR ^15a, also R ^15a are not adversely affect the release of the alkyl or the aryl and INH substituted or unsubstituted containing from 1 to 40 carbon atoms; R ^9b And R
^10b is selected from hydrogen, methyl, substituted or unsubstituted alkyl or aryl containing 1 to 40 carbon atoms; R ^11b is methyl, substituted alkyl or aryl containing 1 to 40 carbon atoms Can be done; s is 0
Or 1; at least one of R ^8b , R ^9b , R ^10b and R ^11b is a photographic ballast; and INH
Is a development inhibitor group.

Preferred examples of the coupler (A) are described below.

[0049]

[Chemical 12]

[0050]

[Chemical 13]

[0051]

[Chemical 14]

[0052]

[Chemical 15]

[0053]

[Chemical 16]

[0054]

[Chemical 17]

[0055]

[Chemical 18]

[0056]

[Chemical 19]

[0057]

[Chemical 20]

[0058]

[Chemical 21]

[0059]

[Chemical formula 22]

[0060]

[Chemical formula 23]

Preferred examples of the coupler (B) are described below.

[0062]

[Chemical formula 24]

[0063]

[Chemical 25]

[0064]

[Chemical formula 26]

[0065]

[Chemical 27]

[0066]

[Chemical 28]

[0067]

[Chemical 29]

[0068]

[Chemical 30]

[0069]

[Chemical 31]

[0070]

[Chemical 32]

[0071]

[Chemical 33]

[0072]

[Chemical 34]

Although the above compounds are shown with a nitro group, it will be appreciated that other electron withdrawing groups can be used, for example sulfones, nitriles and halogens such as chlorine.

A preferred embodiment of the present invention is at least one red-sensitive photographic silver halide emulsion layer comprising at least one cyan image dye-forming coupler; at least one magenta image dye-forming coupler, eg pyrazolone, pyrazolone. At least one green-sensitive photographic silver halide emulsion layer comprising a zolotriazole or a polymeric magenta image dye-forming coupler, and a combination of couplers (A) and (B) described above; and at least one yellow image dye A color photographic element comprising a support having at least one blue sensitive photographic silver halide emulsion layer comprising the resulting coupler. The combination of couplers (A) and (B) in at least one magenta image dye-forming layer is particularly useful in allowing the advantageous interlayer effect to provide improved color images.

The proportions and densities of couplers (A) and (B) in the photographic elements described are such as the desired image, the particular silver halide emulsion in the element, the photographic processing, the strength of the development inhibitor, the element. It may vary depending on factors such as other components of the. The ratio of coupler (A) to coupler (B) is
It can be in the range of 0.1-20, preferably 0.3-15, and typically 0.3-10.

The hue of the color image in the layer containing the couplers (A) and (B) depends on the couplers (A) and (B).
The hue of the dye formed from may be the same or different. For example, couplers (A) and (B)
Can produce a cyan colored dye in a layer comprising an image dye-forming coupler that forms a magenta dye image. Couplers (A) and (B) do not form a permanent dye and therefore can be used in contact with any dye forming element or in combination therewith.

Ballast groups, as used herein, are known in the photographic art. The photographic ballast groups described are organic groups sized and shaped to impart sufficient bulk to a molecule so that the molecule in the photographic element is not substantially diffusible from the layer in which it is coated. Is. Representative ballast groups include substituted or unsubstituted alkyl, typically containing 8 to 40 carbon atoms,
Aryl, ester, carbonamide, carbamoyl,
Includes sulfonamide, sulfamoyl, sulfone, sulfoxide and alkoxy groups.

As used herein, the terms "coupler" and "coupler compound" refer to an entire compound containing a coupling-off group containing INH and a coupler moiety. The term "coupler moiety" refers to the moiety of a compound other than the coupling-off group.

The coupler moiety (COUP) can be any moiety that reacts with the oxidized color developer to cleave the bond between the coupling-off group and the coupler moiety.
The coupler moiety in the present specification includes a coupler moiety used in a conventional color forming coupler which produces a colorless product upon reaction with an oxidized color developing agent, and coloring by reaction with an oxidized color developing agent. A coupler moiety is included that gives rise to the product. Both types of coupler moieties are well known to those skilled in the photographic art.

The coupler moiety may or may not be ballasted, provided that the dye formed upon oxidative coupling of the unballasted coupler needs to be washed out of the photographic element. The coupler moiety may be a monomer or part of a dimer, oligomer or polymer coupler.

The photographic element can also comprise a coupler capable of releasing another photographic reagent or dye. The photographic reagents herein, upon release,
Moieties that further react with components in the photographic element, such as development inhibitors, development accelerators, bleach inhibitors, bleach accelerators, couplers (eg competitive couplers, dye-forming couplers or development inhibitor releasing couplers [DIR couplers. ], Dye precursors, dyes, developers (for example, competitive developers, dye-forming developers or silver halide developers), silver complexing agents, fixing agents, image toners, stabilizers, hardeners, tanning agents. , Fog agents, UV absorbers, antifoggants, nucleating agents, chemical or spectral sensitizers or desensitizers.

INH may be present as a preformed species in the coupling-off group or in blocked form or as a precursor. INH may be a particularly preformed development inhibitor, or the development inhibitory action may be blocked.

Listed below are patents and publications that describe representative COUP groups useful in the present invention.

A. Couplers that produce cyan dyes upon reaction with oxidized color developer are described in the following representative patents and publications: US Patent Application No. 2,772,1
No. 62; No. 2,895,826; No. 3,002,836; No. 3,0
No. 34,892; No. 2,474,293; No. 2,423,730; No.
2,367,531; 3,041,236 and 4,333,999, and Agfa Mitteilungen, Band III, pp. 156.
-175 (1961) published "Farbkuppler-eine Lite
raturubersicht ". Preferably, such couplers are phenols and naphthols that produce cyan dyes upon reaction with oxidized color developer.

B. Couplers that form magenta dyes upon reaction with oxidized color developer are described in the following representative patents and publications: US Patent Application No. 2,60
No. 0,788; No. 2,369,489; No. 2,343,703; No.
No. 2,311,082; No. 3,152,896; No. 3,519,429;
Nos. 3,062,653 and 2,908,573, and
"Farbkuppler-eine Literaturubersich" published in Agfa Mitteilungen, Band III, pp. 126-156 (1961).
t ". Preferably, such couplers are pyrazolones and pyrazolotriazoles which upon reaction with an oxidized color developing agent produce a magenta dye.

C. Couplers that produce yellow dyes upon reaction with oxidized color developer are described in the following representative patents and publications: US Patent Application No. 2,87
No. 5,057; No. 2,407,210; No. 3,265,506; No.
2,298,443; 3,048,194 and 3,447,928, and Agfa Mitteilungen, Band III, pp. 112.
-126 (1961) published "Farbkuppler-eine Lite
raturubersicht ". Preferably, such yellow dye-forming couplers are acylacetamide, such as benzoylacetamide and pivaloylacetamide.

D. Couplers that produce colorless products on reaction with oxidized color developer are described in the following representative patents: British Patent 861,138; U.S. Patent Application No. 3,632,345; 3,928,041; 3,958,993 and 3,961,959.

INH can be any releasable development inhibitor group. Typical INH groups are described, for example, in U.S. Patent Application Nos. 4,477,563, 4,782,012 and 4,88.
6,736, 4,912,024, 4,959,299 and 5,026,628. The disclosures of these are incorporated herein by reference.
Preferred development inhibitor groups are heterocyclic inhibitor groups, including, for example, mercaptotetrazole, mercaptooxadiazole, mercaptothiadiazole and benzotriazole. Structural formula A-1 described below
~ A-8 represent typical releasable development inhibitor groups.

[0089]

[Chemical 35]

[0090]

[Chemical 36]

In the above formula, R_b, R_e, R_hAnd R_iIs each
Independently of each other, hydrogen, substituted or unsubstituted with 1 to 8 carbon atoms
Substituted alkyl such as methyl, ethyl, propyl, buty
, 1-ethylpentyl, 2-ethoxyethyl, substituted fluorine
Phenyl, unsubstituted phenyl; substituted with 6 to 10 carbon atoms
Or unsubstituted phenyl; alkylthio, such as methyl,
Ethyl, propyl, butyl or octylthio; or
Alkyl ester such as -CO₂ CH₃ , -CO₂ C
₂ H_Five , -CO₂ C₃ H₇ , -CO₂ C_Four H₉ , -CH
₂ CO₂ CH₃ , -CH₂ CO₂ C₂ H_Five , -CH₂ C
O₂ C₃ H₇ , -CH₂ CO₂ C_Four H₉ , -CH₂ CH
₂ CO₂ CH₃ , -CH₂ CH₂ CO₂ C ₂ H_Five , -C
H₂ CH₂ CO₂ C₃ H₇ And -CH₂ CH₂ CO₂ C
_Four H₉ Or an aryl ester such as -CO₂ 
R_j, -CH₂ CO₂ R_j, -CH₂ CH₂ CO₂ R_j
(R_jIs substituted or unsubstituted phenyl); R
_c, R_d, R_fAnd R_gIs R_b, R_e, R_hAnd R_i
As described above, or each is independent
With one or more halogen, such as chloro, fluoro or
Is bromo; carboxyl, ester or other substitution
Groups, for example -NHCOCH₃ , -SO₂ OCH₃ , -O
CH₂ CH₂ SO₂ CH₃ , -OCOCH₂ CH₃ ,-
NHCOCH₃ Or a nitro group.

The photographic couplers of this invention can be incorporated into photographic elements by means and methods known in the photographic art. In the photographic element before exposure and processing, the photographic coupler must be sized and shaped so that it does not diffuse through the photographic layers.

The photographic elements of this invention can be processed by conventional techniques in which the color coupler and color developer are incorporated in separate processing solutions or compositions, or in the element.

The photographic elements in which the compounds of this invention are incorporated can be simple elements comprising a support and a single silver halide emulsion layer, or they can be multilayer or multicolor elements. Good. The compounds according to the invention can be incorporated in at least one silver halide emulsion layer and / or in at least one further layer, for example an adjacent layer, in which the silver halide developed in the emulsion layer is oxidized. It will react with the color developing agent. The silver halide emulsion layer may contain or be combined with other photographic coupler compounds such as dye-forming couplers, colored masking couplers and / or competing couplers. These other photographic couplers are capable of forming dyes of the same or different colors and hues as the photographic couplers of this invention. In addition, the silver halide emulsion layers and other layers of the photographic element may contain addenda conventionally contained in such layers.

Each silver halide emulsion unit can consist of one or more layers, and the various units and layers can be arranged differently with respect to each other.

The light-sensitive silver halide emulsion may contain coarse-grained, ordered-grained or fine-grained silver halide crystals or mixtures thereof, and also silver chloride, silver bromide, silver bromoiodide, silver chlorobromide. , Silver chloroiodide, silver chlorobromoiodide, and mixtures thereof. The emulsion may be a negative type or a direct positive type. The emulsion may form a latent image mainly on the surface of the silver halide grains or may form mainly on the inside of the silver halide grains. The emulsion may be chemically or spectrally sensitized. The emulsion is typically a gelatin emulsion, but other hydrophilic colloids are also useful. Especially preferred is the combination of T-grains and conventional emulsions. A combination of T-grains and conventional emulsions of high cubic nature is highly preferred. Research Disclosure , January 1983,
Tabular grain photosensitive silver halide as described in Item No. 22534 and U.S. Pat. No. 4,434,226 are particularly useful.

The support can be any support used in photographic elements. Typical supports include cellulose nitrate films, cellulose acetate films, polyvinyl acetal films, polyethylene terephthalate films, polycarbonate films and related films or resin materials as well as glass, paper, metals and the like. Typically, a flexible support such as a polymer film or paper support is used. The paper support may be acetylated and may also be baryta and / or α-.
It may be coated with olefin polymers, especially polymers of α-olefins containing 2 to 10 carbon atoms, such as polyethylene, polypropylene, ethylene-butene copolymers and the like.

The photographic couplers described can be used in photographic elements as well as photographic couplers which release development inhibitor groups. However, because of the improved ability to control INH release, the couplers of the present invention allow for improved or more selective effects.

The couplers described which release development inhibitors are:
It may be incorporated or reactively combined in one or more silver halide emulsion units in color photographic elements. When the silver halide emulsion unit is composed of two or more layers, one or more of such layers may contain the couplers described, and emulsions of the same spectral sensitivity may be separated by relative sensitivity. It is preferable to use. The layer can contain other photographic couplers conventionally used in the art. In the following discussion of suitable materials for use in the emulsions and elements of the present invention, Re
search Disclosure , December 1978, Item 17643 (Indust
rial Opportunities Ltd., Homewell Havent, Hampshir
e P09 1EF, UK), the disclosure of which is incorporated herein. This publication is referred to as the term "Research Disclosure".
Will be referred to hereafter.

Photographic elements are Research Disclosure Sectio
It can be applied to the various support surfaces described in n XVII and the references cited therein.

Photographic elements are Research Disclosure Sectio
n XVIII, exposure to actinic radiation, typically actinic radiation in the visible region of the spectrum to form a latent image, followed by treatment as described in Research Disclosure Section XIX. A visible dye image can be formed. Processing to form a visible dye image includes the step of contacting the element with a color developing agent to reduce developable silver halide and oxidize the color developing agent. The oxidized color developer in turn reacts with the coupler to form a dye.

Preferred color developers useful in the present invention are p
-Phenylenediamines. Especially preferred are 4-amino-N, N-diethylaniline hydrochloride; 4
-Amino-3-methyl-N, N-diethylaniline hydrochloride; 4-amino-3-methyl-N-ethyl-N-β-
(Methanesulfonamide) ethylaniline sulfate hydrate; 4-amino-3-methyl-N-ethyl-N-β
-Hydroxyethylaniline sulfate; 4-amino-3-β- (methanesulfonamide) -ethyl-N, N
-Diethylaniline hydrochloride; and 4-amino-N-ethyl-N- (2-methoxyethyl) -m-toluidinedi-
p-toluenesulfonic acid may be mentioned.

The photographic materials and methods described can be used with photographic silver halide emulsions and addenda known to be useful in the photographic art, such as Research
Disclosure , December 1989, Item 308,119, which is incorporated herein by reference.

The use of negative-working silver halide produces a negative image by the processing steps described above. To obtain a positive (or reversal) image, develop the exposed silver halide by treating it with a non-color developer before this step, but do not produce dye, and then fog it uniformly to expose it unexposed. The silver halide may be made developable. Alternatively, a direct positive emulsion can be used to obtain a positive image.

Development is followed by conventional steps of bleaching, fixing or bleach-fixing steps to remove silver and silver halide, washing steps and drying steps.

The described compounds are described in US Patent Application No. 724,553.
It can be prepared by the reactions and methods known in the art of synthesizing organic compounds, as described in U.S. Pat. The disclosures of these are incorporated herein by reference.

Photographic elements in which the DIR compounds of this invention are incorporated are preferably multilayer, multicolor elements. The DIR compounds of the present invention are capable of releasing development inhibitors and enhancing the effect of intralayer acutance as well as causing interimage in another layer for color correction and acutance of another color record. . In addition to the above effects,
These DIR compounds have their own color record
It is very effective in making a very good receptor for the interlayer interimage effect (IIE). The improved ability to accept this IIE results in significant improvements in acutance and color saturation.

[0108]

The following examples further illustrate the present invention.

Example 1 The following example and data illustrates a color photographic material comprising a combination of couplers as described.

The following layers were coated on a cellulose triacetate film support (coating units are grams / square meter):

[0111] layer 1 and the gelatin {Antihalation layer} 2.691 g / m ^2, black colloidal silver sol containing silver 0.323 g / m ^2.

Layer 2 {Low-sensitivity cyan layer} 1.3 g / m ² of medium-sized tabular emulsion [iodide 3.0 mol%]
² with 1.1 g / m ² small cubic emulsion [iodide 3.5 mol%]
Seeds of red sensitized silver iodobromide grains, 3.0 g / m ² gelatin, 0.87 g / m ² cyan imaging coupler C-1, 0.06
5 g / m ² DIR coupler D-1, 0.01 g / m ² bleach accelerator releasing coupler D-2 and 0.036 g / m ² antifoggant
4-Hydroxy-6-methyl-1,3,3a, 7-tetraazaindene.

Layer 3 {high-sensitivity cyan layer} 0.81 g / m ² of red-sensitized tabular silver iodobromide emulsion [iodide 6.
0 mol%], 0.151 g / m ² cyan dye forming image coupler C-1, 0.065 g / m ² DIR compound D-1, 0.032 g / m ²
D-3, 1.68 g / m ² gelatin and 0.036 g / m ² antifoggant 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene.

Layer 4 { Interlayer} Oxidized developer scavenger N, N- (4-hydroxy-) at 0.054 g / m ^2.
1,3-phenylene) bis [4- (dodecyloxy) benzenesulfonamide] and 1.3 g / m ² gelatin.

[0115]Layer 5 {Low sensitivity magenta layer} 0.54 g / m² Green sensitized tabular silver iodobromide emulsion [Iodide 6.
0 mol%], 0.26 g / m ² Green sensitized tabular emulsion [iodide
1.5 mol%], 0.344 g / m²Magenta dye forming image cap
Ra M-1, 0.075 g / m²DIR compound D-1, 0.108
g / m²Masking coupler M-2, 1.64 g / m² Zelac
And 0.036 g / m²Antifoggant 4-hydroxy-6-meth
Le-1,3,3a, 7-tetraazaindene.

Layer 6 {high-sensitivity magenta layer} 0.754 g / m ² of high-sensitivity emulsion [iodide 3.0 mol%] and 0.53
A blend of two green sensitized tabular silver iodobromide grains with a medium emulsion of 8 g / m ² [iodide 3.0 mol%], 0.151 g / m ² magenta dye forming image coupler M-1, 0.065 g / m ² masking coupler M- ² , 1.40 g / m ² gelatin, DIR couplers listed in Table 1 and 0.036 g / m ² antifoggant
4-Hydroxy-6-methyl-1,3,3a, 7-tetraazaindene.

Layer 7 {yellow filter layer } 0.86 g / m2 gelatin, 0.043 g / m2 Carey Lea silver and
0.054 g / m ² of oxidized developer scavenger N, N- (4-hydroxy-
1,3-phenylene) bis [4- (dodecyloxy) benzenesulfonamide] and 1.3 g / m ² gelatin.

[0118]Layer 8 {Low sensitivity yellow layer} 0.36 g / m² Blue sensitized tabular silver iodobromide emulsion [Iodide 3.
0 mol%], 0.10 g / m ² Blue-sensitized tabular bromoiodide emulsion
[Iodide 3.0 mol%], 1.73 g / m² Gelatin, 0.88
3 g / m²Yellow dye-forming image couplers Y-1 and 0.09
7 g / m²DIR coupler D-4.

Layer 9 {high-sensitivity yellow layer} 0.43 g / m ² of blue-sensitized tabular silver iodobromide emulsion [iodide 3.
0 mol%], 0.807 g / m ² gelatin, 0.513 g / m ² yellow dye-forming image coupler Y-1 and 0.032 g / m ² DI.
R coupler D-4.

Layer 10 {Protective overcoat and UV film
Luther layer} 1.24 g / m ² gelatin, 0.23 g / m ² silver bromide Lippmann emulsion, 0.23 g / m ² UV absorber and total gelatin weight of 1.
8% bis (vinylsulfonyl) methane.

Photographic recording materials were prepared as described. The following modifications were made in Layer 6 (high speed magenta layer):
The coupler combinations listed in Table 1 were used. The results are shown in Table 1 below as working concentrations.

The following examples and data exemplify a color photographic element which comprises a combination of DIR couplers, both forming wash dyes. The results of Example 1 are listed in Table 1 below.

[0123]

[Table 1]

1) Green contrast obtained by exposure to green light only 2) Green contrast obtained from exposure to white light 3) Gamma (G of G) / gamma (G of N) 4) Exposure of white light only Red contrast obtained from

The data show that the green interimage effect, measured in gamma ratio, increases with increasing amount of coupler UDIR-1. In addition, the contrast of the red image is the coupler UDIR-1
Decreased as the amount of The reduction in red recording contrast suggests a green overlay effect on red.

Example 2 The following example and data show that acetanilide type DIR couplers which form washout dyes and D which do not form washout dyes.
3 illustrates a color photographic element comprising a combination with an IR coupler.

The procedure described in Example 1 was repeated using coupler UDIR-5 and coupler DIR-1 which are acetanilide couplers. The results are shown in Table 2 below.
Shown in.

[0128]

[Table 2]

This data shows that U in controlling the stacking effect
3 illustrates the effect of the combination of DIR-5 and DIR-1.

Example 3 The following example and data illustrates a color photographic element comprising a combination of two DIR couplers each forming a wash-dye.

Coupler UD at the concentrations listed in Table 3 below.
The procedure described in Example 1 was repeated using IR-1 and UDIR-2.

[0132]

[Table 3]

Example 4 The following example and data illustrates a color photographic element in which both couplers comprise another combination of DIR couplers which form a wash dye.

The procedure described in Example 1 was repeated substituting the DIR couplers listed in Table 4 below in place of the couplers.

[0135]

[Table 4]

Examples 5-8 The following examples and data illustrate color photographic elements comprising other combinations of DIR couplers.

Table 5 below instead of the DIR coupler
The procedure described in Example 1 was repeated using the DIR couplers described in -8. Table 5 is another example in which both DIR couplers form washout dyes. Tables 6-8
Is an example where one DIR coupler forms a wash dye but the second does not.

[0138]

[Table 5]

[0139]

[Table 6]

[0140]

[Table 7]

[0141]

[Table 8]

The structural formulas of the couplers used in the examples are shown below.

[0143]

[Chemical 37]

[0144]

[Chemical 38]

[0145]

[Chemical Formula 39]

[0146]

[Chemical 40]

[0147]

[Chemical 41]

[0148]

[Chemical 42]

[0149]

[Chemical 43]

[0150]

[Chemical 44]

[0151]

[Chemical formula 45]

[0152]

[Chemical formula 46]

[0153]

[Chemical 47]

[0154]

[Chemical 48]

[0155]

[Chemical 49]

[0156]

[Chemical 50]

[0157]

[Chemical 51]

[0158]

[Chemical 52]

[0159]

[Chemical 53]

Further embodiments of the invention are listed below in connection with the claims.

A color photographic element according to claim 1 wherein coupler (A) is a coupler of the formula

[0162]

[Chemical 54]

A color photographic element according to claim 1 wherein coupler (B) has the formula:

[0164]

[Chemical 55]

Color photographic element according to claim 1 wherein coupler (A) has the formula:

[0166]

[Chemical 56]

In the above formula, R ^1a is hydrogen, and has 1 to 3 carbon atoms.
Alkyl groups, alkyls containing at least one solubilizing group, aryls; R ^2a , R ^3a and R
^4a is selected from hydrogen, substituted or unsubstituted alkyl or aryl, and substituents that do not adversely affect the release of INH; R ^5a is hydrogen, methyl, -NO ₂ , C
_{l, -NHSO 2 R, -SO 2} NHR, -OCH 3, -
Selected from NHCOR or —CONHR, where R is a substituted or unsubstituted alkyl or aryl containing 1 to 10 carbon atoms and does not adversely affect the release of INH; R ^2a , R ^3a and At least one of R ^4a is a photographic ballast group; TIME is
Is a timed group; s is 0 or 1; and INH
Is a releasable development inhibitor group.

Color photographic element according to claim 1 wherein coupler (A) has the formula:

[0169]

[Chemical 57]

Wherein R ^1b and R ^2b are selected from substituted or unsubstituted alkyl containing at least one solubilizing group; R ^3b , R ^4b and R ^5b are hydrogen, substituted or unsubstituted Selected from alkyl or aryl and substituents that do not adversely affect the release of INH; at least one of R ^3b , R ^4b and R ^5b is a photographic ballast group; TIME is a timing group; s is , 0 or 1; and INH is a development inhibitor group.

Color photographic element according to claim 1 wherein coupler (A) has the formula:

[0172]

[Chemical 58]

In the above formula, R^6aIs hydrogen, 1 to 3 carbon atoms
Containing alkyl and at least one solubilizing group
Substituted or unsubstituted alkyl or aryl having
Selected from; R^7aOr R^12aIs hydrogen, methyl,-
NO₂ , Cl, -NHSO₂ R^15a, -SO₂ NHR
^15a, -OCH₃ , -NHCOR^15aAnd -CONHR
^15a(R ^15aIs a substitution containing 1 to 10 carbon atoms
Selected from unsubstituted alkyl or aryl,
In addition, it does not adversely affect the release of INH)
R; R^8aIs hydrogen, methyl, -NO₂ , Cl, -NHS
O₂ R^16a, -SO₂ NHR^16a, -OCH₃ , -NH
COR^16aAnd -CONHR^16a(R^16aIs 1 carbon atom
Substituted or unsubstituted alkyl containing ~ 40 or
Is aryl); R^9a, R^10aAnd R
^11aContains hydrogen, methyl, 1 to 40 carbon atoms
Selected from substituted alkyl or aryl; s is 0 or
Can be 1; R^13aAnd R^14aIs hydrogen,
Methyl, substituted or unsubstituted containing 1 to 10 carbon atoms
Selected from substituted alkyl or aryl; R^8a,
R^9a, R^10aAnd R^11aAt least one of them is a photo
Contains ballast; and INH is a releasable development inhibitor.
It is a drug base.

Color photographic element according to claim 1 wherein coupler (B) has the formula:

[0175]

[Chemical 59]

In the above formula, R ^6b and R ^7b are each 1 to 1 carbon atom.
Selected from substituted or unsubstituted alkyl or aryl containing 0; R ^8b is hydrogen, methyl, —NO ₂ ,
^{_{Cl, -NHSO 2 R 15a, -SO}} 2 NHR 15a, -O
CH _3, selected from -NHCOR ^15a and -CONHR ^15a, also R ^15a are not adversely affect the release of the alkyl or the aryl and INH substituted or unsubstituted containing from 1 to 40 carbon atoms; R ^9b And R
^10b is selected from hydrogen, methyl, substituted or unsubstituted alkyl or aryl containing 1 to 40 carbon atoms; R ^11b is methyl, substituted alkyl or aryl containing 1 to 40 carbon atoms Can be done; s is 0
Or 1; at least one of R ^8b , R ^9b , R ^10b and R ^11b contains photographic ballast; and IN
H is a development inhibitor group.

Color photographic element according to claim 1 wherein coupler (B) has the formula:

[0178]

[Chemical 60]

Wherein R ^1a is selected from hydrogen, alkyl containing 1 to 3 carbon atoms, or alkyl or aryl containing at least one solubilizing group;
R ^2a , R ^3a and R ^4a are selected from hydrogen, substituted or unsubstituted alkyl or aryl, and substituents that do not adversely affect the release of INH; R ^5a is hydrogen, methyl, —NO ₂ , Cl, -NHSO ₂ R, -SO ₂ NH
R, -OCH _3, during -NHCOR and -CONHR (wherein, R is selected from substituted or unsubstituted alkyl or aryl containing 1 to 10 carbon atoms, also I
Does not adversely affect the release of NH));
At least one of R ^2a , R ^3a and R ^4a is a photographic ballast group; and INH is a releasable development inhibitor group.

The coupler (A) has the following formula:

[0181]

[Chemical formula 61]

(In the above formula, R ^1a represents hydrogen, carbon atoms 1 to 3)
At least one alkyl containing, or solubilizing group
Selected from alkyl or aryl containing; R
^2a , R ^3a and R ^4a are selected from hydrogen, substituted or unsubstituted alkyl or aryl, and substituents that do not adversely affect the release of INH; R ^5a is hydrogen, methyl,
_{-NO 2, Cl, -NHSO 2 R} , -SO 2 NHR, -
R ^2a selected from OCH ₃ , —NHCOR and —CONHR, where R is a substituted or unsubstituted alkyl or aryl containing 1 to 10 carbon atoms and does not adversely affect the release of INH. , R ^3a and R ^4a
At least one of which is a photographic ballast group; TI
ME is a timing group; s is 0 or 1; and INH is a releasable development inhibitor group) and coupler (B) is of the formula:

[0183]

[Chemical formula 62]

(In the above formula, R ^6b and R ^7b are each a carbon atom of 1 to
Selected from substituted or unsubstituted alkyl or aryl containing 10; R ^8b is hydrogen, methyl, -NO
^{_{2, Cl, -NHSO 2 R 15a}} , -SO 2 NHR 15a,
-OCH _3, is selected from -NHCOR ^15a and -CONHR ^15a, also R ^15a are not adversely affect the release of the alkyl or the aryl and INH substituted or unsubstituted containing from 1 to 40 carbon atoms; R ^9b and R ^10b are selected from hydrogen, methyl, substituted or unsubstituted alkyl or aryl containing 1 to 40 carbon atoms; R ^11b is methyl, substituted alkyl or aryl containing 1 to 40 carbon atoms. Can be; s
Is 0 or 1; at least one of R ^8b , R ^9b , R ^10b and R ^11b contains a photographic ballast; and INH is a development inhibitor group). Color photographic elements.

The coupler (A) has the following formula:

[0186]

[Chemical formula 63]

(In the above formula, R ^1a represents hydrogen or a carbon atom of 1 to 1).
Selected from three alkyl groups, alkyl containing at least one solubilizing group, aryl; R ^2a , R ^3a and R ^4a
Is selected from hydrogen, substituted or unsubstituted alkyl or aryl, and substituents that do not adversely affect the release of INH; R ^5a is hydrogen, methyl, —NO ₂ , Cl,
_{-NHSO 2 R, -SO 2 NHR,} -OCH 3, -NH
COR or -CONHR (In the formula, R is 1 to 1 carbon atom)
Substituted or unsubstituted alkyl or aryl containing 10 and not adversely affecting the release of INH); at least one of R ^2a , R ^3a and R ^4a is a photographic ballast group. TIME is a timing group; s is 0 or 1; and INH is
Is a releasable development inhibitor group) and the coupler (B) is of the formula:

[0188]

[Chemical 64]

(In the above formula, R ^1a represents hydrogen, carbon atoms 1 to 3)
At least one alkyl containing, or solubilizing group
Selected from alkyl or aryl containing; R
^2a , R ^3a and R ^4a are selected from hydrogen, substituted or unsubstituted alkyl or aryl, and substituents that do not adversely affect the release of INH; R ^5a is hydrogen, methyl,
_{-NO 2, Cl, -NHSO 2 R} , -SO 2 NHR, -
OCH _3, (wherein, R represents a carbon atom containing from 1 to 10 selected from substituted or unsubstituted alkyl or aryl, also does not adversely affect the release of the INH) -NHCOR and -CONHR selected from; R ^At least one of ^2a , R ^3a and R ^4a is a photographic ballast group; and INH is a releasable development inhibitor group)
The color photographic element of claim 1 having the formula:

The coupler (A) has the following formula:

[0191]

[Chemical 65]

Wherein R ^1b and R ^2b are selected from substituted or unsubstituted alkyl containing at least one solubilizing group; R ^3b , R ^4b and R ^5b are hydrogen, substituted or unsubstituted R ^3b , R ^4b selected from the alkyl or aryl groups of R ⁴ and substituents that do not adversely affect the release of INH;
And at least one of R ^5b is a photographic ballast group; TIME is a timing group; s is 0 or 1; and INH is a development inhibitor group).
And the coupler (B) has the following formula:

[0193]

[Chemical formula 66]

(In the above formula, R ^6b and R ^7b are each a carbon atom of 1 to
Selected from substituted or unsubstituted alkyl or aryl containing 10; R ^8b is hydrogen, methyl, -NO
^{_{2, Cl, -NHSO 2 R 15a}} , -SO 2 NHR 15a,
-OCH _3, is selected from -NHCOR ^15a and -CONHR ^15a, also R ^15a are not adversely affect the release of the alkyl or the aryl and INH substituted or unsubstituted containing from 1 to 40 carbon atoms; R ^9b and R ^10b are selected from hydrogen, methyl, substituted or unsubstituted alkyl or aryl containing 1 to 40 carbon atoms; R ^11b is methyl, substituted alkyl or aryl containing 1 to 40 carbon atoms. Can be; s
Is 0 or 1; at least one of R ^8b , R ^9b , R ^10b and R ^11b contains a photographic ballast; and INH is a development inhibitor group). Color photographic elements.

The coupler (A) has the following formula:

[0196]

[Chemical formula 67]

Wherein R ^1b and R ^2b are selected from substituted or unsubstituted alkyl containing at least one solubilizing group; R ^3b , R ^4b and R ^5b are hydrogen, substituted or unsubstituted R ^3b , R ^4b selected from the alkyl or aryl groups of R ⁴ and substituents that do not adversely affect the release of INH;
And at least one of R ^5b is a photographic ballast group; TIME is a timing group; s is 0 or 1; and INH is a development inhibitor group).
And the coupler (B) has the following formula:

[0198]

[Chemical 68]

(In the above formula, R ^1a represents hydrogen, carbon atoms 1 to 3)
At least one alkyl containing, or solubilizing group
Selected from alkyl or aryl containing; R
^2a , R ^3a and R ^4a are selected from hydrogen, substituted or unsubstituted alkyl or aryl, and substituents that do not adversely affect the release of INH; R ^5a is hydrogen, methyl,
_{-NO 2, Cl, -NHSO 2 R} , -SO 2 NHR, -
OCH _3, (wherein, R represents a carbon atom containing from 1 to 10 selected from substituted or unsubstituted alkyl or aryl, also does not adversely affect the release of the INH) -NHCOR and -CONHR selected from; R ^At least one of ^2a , R ^3a and R ^4a is a photographic ballast group; and INH is a releasable development inhibitor group)
The color photographic element of claim 1 having the formula:

The coupler (A) has the following formula:

[0201]

[Chemical 69]

(In the above formula, R^6aIs hydrogen, carbon atoms 1 to 3
Alkyl containing at least one, and at least one solubilizing group
Substituted or unsubstituted alkyl or aryl containing
Selected from Le; R^7aOr R^12aIs hydrogen, methyl,
-NO₂ , Cl, -NHSO₂ R^15a, -SO₂ NHR
^15a, -OCH₃ , -NHCOR^15aAnd -CONHR
^15a(R ^15aIs a substitution containing 1 to 10 carbon atoms
Selected from unsubstituted alkyl or aryl,
In addition, it does not adversely affect the release of INH)
R; R^8aIs hydrogen, methyl, -NO₂ , Cl, -NHS
O₂ R^16a, -SO₂ NHR^16a, -OCH₃ , -NH
COR^16aAnd -CONHR^16a(R^16aIs 1 carbon atom
Substituted or unsubstituted alkyl containing ~ 40 or
Is aryl); R^9a, R^10aAnd R
^11aContains hydrogen, methyl, 1 to 40 carbon atoms
Selected from substituted alkyl or aryl; s is 0 or
Can be 1; R^13aAnd R^14aIs hydrogen,
Methyl, substituted or unsubstituted containing 1 to 10 carbon atoms
Selected from substituted alkyl or aryl; R^8a,
R^9a, R^10aAnd R^11aAt least one of them is a photo
Contains ballast; and INH is a releasable development inhibitor.
The coupler (B) is represented by
formula:

[0203]

[Chemical 70]

(In the above formula, R ^6b and R ^7b are each a carbon atom of 1 to
Selected from substituted or unsubstituted alkyl or aryl containing 10; R ^8b is hydrogen, methyl, -NO
^{_{2, Cl, -NHSO 2 R 15a}} , -SO 2 NHR 15a,
-OCH _3, is selected from -NHCOR ^15a and -CONHR ^15a, also R ^15a are not adversely affect the release of the alkyl or the aryl and INH substituted or unsubstituted containing from 1 to 40 carbon atoms; R ^9b and R ^10b are selected from hydrogen, methyl, substituted or unsubstituted alkyl or aryl containing 1 to 40 carbon atoms; R ^11b is methyl, substituted alkyl or aryl containing 1 to 40 carbon atoms. Can be; s
Is 0 or 1; at least one of R ^8b , R ^9b , R ^10b and R ^11b contains a photographic ballast; and INH is a development inhibitor group). Color photographic elements.

The coupler (A) has the following formula:

[0206]

[Chemical 71]

(In the above formula, R ^6a represents hydrogen, carbon atoms 1 to 3)
Selected from the group consisting of alkyls containing at least one and substituted or unsubstituted alkyls or aryls containing at least one solubilizing group; R ^7a and R ^12a are hydrogen, methyl,
_{NO 2, Cl, -NHSO 2 R} 15a, -SO 2 NHR
^15a, -OCH _3, -NHCOR ^15a and -CONHR
^15a (R ^{15 a} is selected from alkyl or aryl substituted or unsubstituted containing from 1 to 10 carbon atoms,
It does not adversely affect the release of INH); R ^8a is hydrogen, methyl, —NO ₂ , Cl, —NHS.
_{^{O 2 R 16a, -SO 2 NHR}} 16a, -OCH 3, -NH
COR ^16a and -CONHR ^16a (R ^16a is a carbon atom 1
Is a substituted or unsubstituted alkyl or aryl containing ~ 40); R ^9a , R ^10a and R
^11a is selected from hydrogen, methyl, substituted alkyl or aryl containing 1 to 40 carbon atoms; s can be 0 or 1; R ^13a and R ^14a are hydrogen,
Selected from methyl, substituted or unsubstituted alkyl or aryl containing 1 to 10 carbon atoms; R ^8a ,
At least one of R ^9a , R ^10a and R ^11a contains photographic ballast; and INH is a releasable development inhibitor group) and coupler (B) is of the formula:

[0208]

[Chemical 72]

(In the above formula, R ^1a represents hydrogen, carbon atoms 1 to 3)
At least one alkyl containing, or solubilizing group
Selected from alkyl or aryl containing; R
^2a , R ^3a and R ^4a are selected from hydrogen, substituted or unsubstituted alkyl or aryl, and substituents that do not adversely affect the release of INH; R ^5a is hydrogen, methyl,
_{-NO 2, Cl, -NHSO 2 R} , -SO 2 NHR, -
OCH _3, (wherein, R represents a carbon atom containing from 1 to 10 selected from substituted or unsubstituted alkyl or aryl, also does not adversely affect the release of the INH) -NHCOR and -CONHR selected from; R ^At least one of ^2a , R ^3a and R ^4a is a photographic ballast group; and INH is a releasable development inhibitor group)
The color photographic element of claim 1 having the formula:

The coupler (B) has the following formula:

[0211]

[Chemical formula 73]

The coupler (A) is represented by the following formula:

[0213]

[Chemical 74]

A color photographic element according to claim 1 having the formula:

A color photographic element according to claim 1 wherein the photographic silver halide emulsion layer comprises an image dye-forming coupler.

The coupler according to claim 1, wherein couplers (A) and (B) are naphthol-based or acylacetamide-based couplers and the photographic silver halide emulsion layer comprises at least one magenta image dye-forming coupler. Color photographic element.

A color photographic element according to claim 1 which comprises a support having at least one red-sensitive photographic silver halide emulsion layer comprising at least one cyan image dye-forming coupler. A green-sensitive photographic silver halide emulsion layer comprises at least one magenta image dye-forming coupler and a combination of couplers (A) and (B) as defined in claim 1 and at least one The above color photographic element wherein the blue-sensitive photographic silver halide emulsion layer comprises at least one yellow image dye-forming coupler.

The photographic silver halide emulsion comprises an image dye-forming coupler which allows the formation of an image dye having a first hue, and couplers (A) and (B) are derived from said image dye-forming coupler. A color photographic element according to claim 1 capable of forming a dye having a second hue which is the same as or different from the first hue of the formed dye.

[0219]

The present invention relates to photographic materials and processing,
Provided are combinations of couplers that allow the removal of washout dye formed from the coupler during photographic processing while at the same time allowing improved image formation. Further, the present invention provides
The use of silver development inhibitor groups in photographic materials allows the removal of undesired dyes formed from the compounds during photographic processing, while at the same time creating and accepting interlayer interlayer effects by the highly controlled use of silver development inhibitor groups. To provide an imaging element capable of

 ─────────────────────────────────────────────────── ─── Continued Front Page (72) Inventor Drake Matthew Michino 14580, Webster, Greenpine Lane 9

Claims (2)

[Claims] 1. A color photographic element comprising a support having at least one photographic silver halide emulsion layer and a combination of at least two wash-out couplers (A) and (B) separate from each other. A) is capable of forming a compound which, upon reaction with an oxidized developer, is washed out of the photographic element during photographic processing and is capable of releasing a photographic development inhibitor or a photographic development inhibitor. Capable of releasing a timed group having, the timed group being capable of providing a timed release of said photographic development inhibitor, and also coupler (B)
Is capable of forming a compound which, upon reaction with an oxidized developer, is washed out of the photographic element during photographic processing and is capable of releasing the photographic development inhibitor with no time delay, the coupler (A) and (B) has the following formula: (In the above formula, SOL is a water-solubilizing group; COUP is
Is a coupler moiety; TIME is a timing group; RE
L is a releasing group containing a photographic ballast group; n and p are each independently 0 or 1; INH is a releasable development inhibitor group; and y is 1 or 2) The color photographic element shown by. 2. A method of forming a photographic image comprising the step of developing an exposed photographic silver halide emulsion layer with a color developer in the presence of a combination of at least two separate couplers of claim 1. .