JPH0619091A - Improved multilayer color photographic element - Google Patents

Abstract

PURPOSE: To improve speed and fog by forming a green-sensitive layer contg. a pyrazolotriazole dye forming coupler and a dye-contg. yellow filter layer. CONSTITUTION: This multilayered color photographic element has at least one green-sensitive silver halide emulsion layer and a yellow filter layer adjacent to the green-sensitive layer as a unit and the green-sensitive layer contains a pyrazolotriazole dye forming coupler represented by one of the formulae and a dye-contg. yellow filter layer. In the formulae, R is a 1-6C org. group selected from among methyl, ethyl, methoxy, acetamido and phenyl, COG is a group releasable by coupling, each of R1 -R3 is H, alkyl, phenyl, N or O, at least one of R1 -R3 is H, R2 may be methyl or unsubstd. phenyl and R3 may be a tri- or di-substd. nitrogen group.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION This invention carries at least one green-sensitive silver halide emulsion layer having an active magenta dye-forming coupler and an adjacent yellow filter layer containing a dye for filtering blue light. It relates to a photographic light-sensitive material comprising a support and having improved speed and fog level.

[0002]

Color photographic light-sensitive materials comprising a plurality of layers containing photographic couplers are well known. Typical photographic light-sensitive materials are U.S. Pat. Nos. 4,145,219, 4,724,198, 4,184,876, 4,186,016 and 4,724. , 198.

[0003]

Conventional photographic light-sensitive materials present problems with exposure reciprocity, speed, retained silver, color reproduction and neutral gray scale, skin tone reproduction, and image composition or granularity. .

[0004]

Various methods have been recognized in the photographic art for overcoming these problems. Thus, for example, granularity can be improved, but often at the expense of other properties, such as speed. Alternatively, skin tone tone reproduction can be improved, but the neutral gray scale is adversely affected. Furthermore, when active couplers, such as certain magenta dye-forming couplers, are used in photographic elements containing fine silver in the adjacent interlayers, undesired physical levels that produce unacceptably high levels of fog. You will experience development. Conventional solutions to this problem have involved the use of few active couplers, such as magenta dye-forming couplers, however this gives a slower film speed.
Therefore, there is a great demand for a photographic light-sensitive material capable of improving these properties without seriously adversely affecting them.

For example, active couplers, referred to as magenta image dye-forming couplers, are less exposed at equal doses when coated in the same format with equal molar loadings and exposed and processed in substantially the same manner. Includes couplers that provide higher gammas and higher densities than active couplers.

[0006]

DETAILED DESCRIPTION OF THE INVENTION For high fog, the present invention is an improved multi-layer color photographic element having a reduced level of fog which comprises a support coated on its side with a photographic silver halide emulsion layer. Wherein the layer comprises at least one green-sensitive silver halide emulsion layer and a unit of a yellow filter layer adjacent to said green-sensitive layer, wherein the green-sensitive layer is a pyrazolotriazole dye-forming coupler [coupler is of the formula

[0007]

[Chemical 4]

(Wherein R is an organic group having 1 to 6 carbon atoms, R is selected from methyl, ethyl, methoxy, acetamide and phenyl, and COG is a coupling leaving group. , R ₁ , R ₂ and R ₃ are selected from hydrogen, alkyl, phenyl, nitrogen and oxygen, and 1 in the above formula
Or less R ₁ , R ₂ and R ₃ are hydrogen)
This problem is solved by providing an element comprising a yellow filter layer comprising a dye as well.

Further, R₂Is a methyl or unsubstituted phenyl group
More selectable, and R₃Is a trisubstituted nitrogen group and a disubstituted
It may be substituted oxygen. Furthermore, at least one
R₁, R ₂, R₃Is one carboxylic acid and sulfamide
It may contain solubilized ballast groups containing groups.

Such a pyrazolone dye-forming coupler is represented by the following formula, for example.

[0011]

[Chemical 5]

In addition, the multilayer color photographic element comprises a support coated on its side with photographic silver halide emulsion layers, the layers being the second or intermediate greens more sensitive than the third green-sensitive layer. It comprises units of at least three green sensitive silver halide emulsion layers having a first green sensitive layer which is more sensitive than the sensitive layers, the green sensitive layers are adjacent and the units contain a masking coupler. The first green sensitive layer comprises at least one magenta image dye-forming coupler (A), a timed (tim).
ed) comprising development inhibitor releasing couplers and preferably non-timed development inhibitor releasing couplers. The second layer is
It comprises at least one first magenta image dye-forming coupler, (A), preferably at least one second magenta image dye-forming coupler, a development inhibitor releasing coupler and preferably a cyan dye-forming coupler.
The third layer is at least one magenta image dye-forming coupler, which is also a bleach accelerator releasing coupler,
Comprising. In addition, the third layer contains a development inhibitor releasing coupler.

A typical photographic element according to the present invention typically comprises the following layers in that order:

[0014]

[Table 1]

The overcoat layer may comprise components known in the photographic art for overcoat layers including UV absorbers, matting agents and surfactants and the like. Also, UV layers containing similar materials can be used. UV useful for this layer and antihalation layer
The absorbing dyes are represented by the following formula.

[0016]

[Chemical 6]

This layer can contain, for example, dyes that can also help adjust the photographic speed of the element. Such a dye can be a green filter dye. Suitable green filter dyes have the formula:

[0018]

[Chemical 7]

Suitable red filter dyes have the formula:

[0020]

[Chemical 8]

Other dyes that can be used include efflux dyes of the type discussed herein and filter dyes that are decolorized during photographic processing steps.

Image Dye- Forming Couplers The image dye-forming couplers in the blue-, green- and red-sensitive layers described are the photographic arts for such layers to form yellow, magenta and cyan dye images. It can be any of the image dye-forming couplers known in the art. Such couplers include coupler moieties (C) as known and described in the art.
OUP). Combinations of image dye-forming couplers may be useful in the photographic silver halide emulsion layers described.

Couplers that are yellow dye-forming couplers are typically acylacetamides, such as benzoylacetanilides and pivalylacetanilides. Such couplers are described in US Pat.
No. 5,057, No. 2,407,210, No. 3,2
65,506, 2,298,443, and 3,
048,194, 4,022,620, 4,443,536 and 3,447,928, and "Farbkuppler: Eine Literatuerbersich.
t ”, Agfa Mitteilungen Publishing, Band III, 112-126
It is described in representative patents and publications such as page (1961).

Couplers that are cyan image dye-forming couplers (C) are typically phenols or naphthols, such as those described in the photographic literature for producing cyan dyes upon oxidative coupling. It is like

Specific examples of such couplers (C) which produce cyan dyes are typically found in US Pat.
No. 2,162, No. 3,772,002, No. 4,5
26,864, 4,500,635, 4,
254,212, 4,296,200, 4,457,559, 2,895,826, 3,002,936, 3,002,836,
No. 3,034,892, No. 2,474,293
No. 2,423,730, No. 2,367,53
No. 1, No. 3,041,236, No. 4,443,5
No. 36, No. 4,124, 396, No. 4,775,
No. 616, No. 3,779,763 and No. 4,33.
No. 3,999 and "Farbkuppler: Eine Litera
tuerbersicht ", Agfa Mitteilungen Publishing, Band III,
The phenols and naphthols described in representative patents and publications such as pages 156-175 (1961).

Coupler (A) for producing magenta dyes
Are typically pyrazolones, pyrazolotriazoles and benzimidazoles, and such couplers are disclosed in US Pat. Nos. 2,600,788, 2,369,489, and 2,343,703, 2,311,082, 3,824,250,
No. 3,615,502, No. 4,076,533
Issue No. 3,152,896, No. 3,519,42
No. 9, No. 3,062,653, No. 2,908,5
No. 73, No. 4,540, 654, No. 4,443.
No. 536, No. 3,935, 015, No. 3,45
No. 1,820, No. 4,080,211 and No. 4,2
No. 15,195, No. 4,518,687, and No. 4,612,278 and European Patent No. 2
84,239, 284,240, 240,
Nos. 852 and 177,765 and "Farb
kuppler: Eine Literatuerbersicht '', Agfa Mitteilung
En patent publications, Band III, pages 126-156 (1961).

The photographic element can be processed to form a developed image on an exposed color photographic element by developing the element with a color developing solution.

In the high speed yellow photographic element, the high blue sensitive layer or high speed yellow layer is
Contains a timed development inhibitor releasing coupler (DIR). The high sensitivity yellow layer is a coupler deficient layer. Preferably the layer is free of image dye-forming couplers. Coupler deficient, as used herein, refers to the state of the layer in which there is less dye-forming coupler than is theoretically possible to react with all the oxidized developing agent produced at maximum exposure. Couplers other than image dye-forming couplers can be present in this layer and such couplers include, for example, the timed developing couplers or non-timed DIR couplers and color correcting couplers described above. These other couplers are typically used at densities known in the photographic art and are typically capable of producing yellow dyes that do not exceed about 3% of the total yellow record density.

Suitable timed DIR couplers for use in the fast yellow layer include substituents

[0030]

[Chemical 9]

(Wherein X is alkylene having 1 to 3 carbon atoms, R is alkyl having 1 to 4 carbon atoms, and the sum of the carbon atoms of X and R is A mercaptotetrazole development inhibitor capable of releasing a DIR coupler (E). Typically the DIR couplers are pivalylacetanilide couplers such as those described in US Pat. No. 4,782,012, the contents of which are incorporated herein by reference.

The timed DIR coupler can be any timed DIR coupler useful in the photographic art that will release a timed development inhibitor. That is, a development inhibitor-releasing coupler containing at least one timing group (T) capable of temporally controlling the release of a development inhibitor group is at least one timing group known in the photographic art. Can be any development inhibitor releasing coupler containing Development inhibitor releasing couplers containing at least one timing group are represented by the formula:

[0033]

[Chemical 10]

Where COUP is a coupler moiety, typically a cyan, magenta or yellow dye-forming coupler moiety as described, and T and T ¹ are separate timing groups, typically a timing group. U.S. Pat. No. 4,248,
962 and 4,409,232 (the contents of which are incorporated herein by reference), n is 0 or 1, and Q ¹ Is a releasable development inhibitor group known in the photographic art. Q ¹ can be selected from the INH groups as described.

Preferred couplers of this type are described in US Pat. No. 4,248,962. Preferred timed DIR couplers of this type are of the formula:

[0036]

[Chemical 11]

[0037]

[Chemical 12]

More suitable timed DIR couplers have the formula:

[0039]

[Chemical 13]

[0040]

[Chemical 14]

Color from the fast yellow layer results primarily from the migration of the oxidized developer produced in the fast yellow layer to the adjacent slow yellow layer and reaction to produce a yellow dye. .

Another coupler class which is a development inhibitor releasing coupler as described is, for example, US Pat.
No. 48,962, No. 3,227,554, No. 3,
Those described in 384,657, 3,615,506, 3,617,291 and 3,733,201 and British Patent 1,450,479. Includes. Preferred development inhibitors are heterocyclic compounds such as mercaptotetrazole, mercaptotriazole, mercaptooxadiazoles, selenotetrazole, mercaptobenzothiazoles, selenobenzothiazoles, mercaptobenzoxazoles, selenobenzoxazole. , Mercaptobenzimidazoles, selenobenzimidazoles, benzotriazoles, benzodiazoles and 1,2,4-triazoles, tetrazoles and imidazoles.

Low Speed Yellow Layer In the photographic element the low blue sensitive layer or low speed yellow layer contains a yellow image dye-forming coupler. Such yellow image dye-forming coupler can be any yellow dye-forming coupler useful in the photographic art.

Couplers that are yellow image dye-forming couplers are typically acylacetamides, such as benzoylacetanilides and pivalylacetanilides, such as photographic arts that produce yellow dyes upon oxidative coupling. It is described in the literature.

Typically, the yellow dye-forming coupler in the slow yellow layer is a pivalyl acetanilide coupler containing a hydantoin coupling-off group.
Such a coupler is specifically represented by the following formula.

[0046]

[Chemical 15]

Wherein R ² is chlorine, bromine or alkoxy, R ³ is a ballast group such as a sulfonamide or carboxamide ballast group and Z is a coupling leaving group, preferably US Pat. Hydantoin coupling-off groups as described in US Pat. No. 4,022,620, the contents of which are incorporated herein by reference.

Yellow dye-forming couplers suitable for the slow yellow or blue sensitive layer are of the formula:

[0049]

[Chemical 16]

[0050]

[Chemical 17] Preferred yellow dye-forming couplers for the slow yellow layer are shown below.

[0051]

[Chemical 18]

The timed or non-timed DIR couplers described for the fast yellow layer may also be used in the slow yellow layer.

In the intermediate layer photographic element a yellow filter layer is provided between the slow yellow and fast magenta. This layer is Carey Le
a Silver (CLS), bleach-accelerating silver salts, any oxidized developing agent scavenger known in the photographic art, such as those described in US Pat. No. 4,923,787. , And dyes that can improve image sharpness or dyes that adjust the photographic speed of the element. A preferred oxidized developer scavenger is of the formula:

[0054]

[Chemical 19]

Other oxidized developer scavengers useful in the present invention include those of the formula:

[0056]

[Chemical 20]

When fine silver, such as Carey Lea silver, is used in the yellow filter layer, then preferably in the photographic element in which the interlayer contains a yellow filter and a bleach accelerator releasing coupler (BARC). Offered between different layers. Preferably, when bleach accelerating silver salt (BASS) is used in the yellow filter, then it is preferred to provide an intermediate layer to isolate the BASS containing layer from the rest of the film. This intermediate layer may contain the oxidized developer scavenger.
Further, the intermediate layer may be continuous with the yellow filter layer and may be disposed on both sides of the yellow filter layer. Representative bleach-accelerating silver salts are disclosed in US Pat.
65,965, 4,923,784 and 4,163,669. The bleach accelerating silver salts can comprise salts of mercaptoproprionic acid.

The BARC and BASS compounds may be used in combination in the element. Another typical bleach-accelerating silver salt used in the intermediate layer is of the structure shown below.

[0059]

[Chemical 21]

Instead of using fine silver in the yellow filter layer, filter dyes may be used. If filter dyes are used, then the intermediate layer continuous or adjacent to the yellow filter layer may be omitted.
The oxidized developer scavenger may be used in the yellow filter layer with the filter dye. Specific examples of filter dyes, such as effluxing or decolorizing dyes useful in the present invention, are found in US Pat. No. 4,923,78.
No. 8 (which is incorporated herein by reference). Such a filter dye is represented by the following formula.

[0061]

[Chemical formula 22]

In the above formula, R is a substituted or unsubstituted alkyl or aryl, X is an electron-withdrawing group, and R'is a substituted or unsubstituted aryl or a substituted or unsubstituted aromatic group. A heterocyclic nucleus, and L, L '
And L ″ are each independently a substituted or unsubstituted methine group.

Preferred alkyl groups are straight chain alkyls,
For example, it includes branched chain alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, decyl and dodecyl, for example, alkyl having 1 to 20 carbon atoms including isopropyl, isobutyl and t-butyl.
These alkyl groups have numerous known substituents, for example:
It can be substituted with any of sulfo, sulfato, sulfonamide, amide, amino, carboxyl, halogen, alkoxy, hydroxy, phenyl and the like. These substituents can be placed virtually anywhere on the alkyl group. The possible substituents are not limited to those exemplified and one skilled in the art can readily select from the numerous substituted alkyl groups that will provide useful compounds according to the formula.

Preferred aryl groups for R include optionally substituted aryl having 6 to 10 carbon atoms (eg phenyl, naphthyl). Useful substituents for aryl groups are the substituents known for any of the numerous aryl groups, such as sulfo, sulfato, sulfonamide (eg, butanesulfonamide), amide, amino, carboxyl, halogen, alkoxy, hydroxy. , Acyl, phenyl, alkyl and the like.

The filter dyes may be used in combination with fine silver. It will be appreciated that permanent yellow filter dyes can be used in place of CLS or efflux filter dyes. Such permanent dyes are represented by the following formula, for example.

[0066]

[Chemical formula 23]

Microcrystalline dyes useful in the present invention are represented by the formula:

[0068]

[Chemical formula 24]

High Sensitive Magenta Layer The highest green sensitive layer or high sensitivity magenta layer is a magenta image dye-forming coupler (A), a timed development inhibitor releasing coupler (DIR), preferably a non-timed DIR coupler and preferably a masking coupler. Comprising.

The magenta image dye-forming coupler (A) can be any image-forming coupler dye that is useful in the photographic art. A typical magenta image dye-forming coupler is pyrazolotriazole. Suitable couplers for forming magenta dyes include those of the formula:

[0071]

[Chemical 25]

[0072]

[Chemical formula 26]

[0073]

[Chemical 27]

[0074]

[Chemical 28]

Preferred magenta image dye-forming couplers have the formula:

[0076]

[Chemical 29]

Suitable timed DIR couplers comprise DIR couplers (E) capable of releasing the mercaptotetrazole development inhibitors described for the fast yellow layer.

The masking coupler can be any masking coupler suitable for use in photographic elements. The masking coupler is preferably represented by the following formula.

[0079]

[Chemical 30]

The masking coupler can be placed in any of the three magenta imaging layers. The non-timed DIR coupler (B) used in the fast magenta layer can be any non-timed DIR coupler known in the photographic art. Specific examples of such non-timed DIR couplers are disclosed in US Pat. No. 3,227,554, which is incorporated herein by reference. Preferred non-timed DIR couplers (B) are represented by the following formula.

[0081]

[Chemical 31]

Medium-Sensitivity Magenta Layer The medium-sensitivity magenta or intermediate green-sensitive layer is at least 1
One first magenta image dye-forming coupler, and preferably at least one second magenta image dye-forming coupler, preferably a non-timed DIR coupler and preferably a cyan dye image-forming coupler (C).

The fast magenta image dye-forming coupler can be the coupler (A) discussed in the fast magenta layer. The second magenta image dye-forming coupler can be any image-forming coupler dye useful in the photographic art, and is a magenta image dye-forming coupler (A) as discussed in the fast magenta layer. Can be included.

A typical magenta image dye-forming coupler is pyrazolotriazole. A preferred second image dye-forming coupler is coupler (34). Coupler (14) is another preferred second magenta image dye-forming coupler.

Suitable non-timed DIR couplers useful in the medium magenta layer are those described for the fast magenta layer and can be, for example, the preferred coupler (B).

The cyan image dye-forming coupler (C) described is any cyan image dye-forming agent known in the photographic art that has its use in magenta recording, referred to herein as a color-correcting coupler. It can be a sex coupler. Cyan image dye-forming couplers are typically phenol or naphthol couplers as described in representative patents and publications as previously described herein. Preferred cyan image dye-forming couplers (C) for the medium-speed magenta layer are represented by the following formula.

[0087]

[Chemical 32]

[0088]

[Chemical 33]

The coupler (21) may be used in the medium-speed magenta layer.

The slow magenta layer The slow magenta layer contains at least one magenta image dye-forming coupler which is preferably a bleach accelerator releasing coupler (BARC). The slow magenta layer also contains a development inhibitor releasing coupler (DIR), preferably a non-timed DIR.

The bleach accelerator releasing coupler can be any bleach accelerator releasing coupler known in the photographic art. Also, combinations of such couplers are useful. Bleach accelerator releasing couplers can be represented by the formula:

[0092]

[Chemical 34]

Where COUP is a coupler moiety, as described, typically a cyan, magenta or yellow dye-forming coupler moiety, and T ² is a timing group known in the photographic art, typically Are timing groups described in U.S. Pat. Nos. 4,248,962 and 4,409,323 (the contents of which are incorporated herein by reference), m
Is 0 or 1, R ³ is an alkylene group, in particular a branched or straight chain alkylene group containing 1 to 8 carbon atoms, and R ⁴ is a water-soluble group, preferably It is a carboxy group.

Typical bleach accelerator releasing couplers are described, for example, in EP 193,389, the contents of which are incorporated herein by reference. Suitable bleach accelerator releasing couplers have the formula:

[0095]

[Chemical 35]

Preferred bleach accelerator releasing couplers have the formula:

[0097]

[Chemical 36]

A combination of bleach accelerating couplers may be used and the bleach accelerating couplers may be used in another imaging layer including the magenta imaging layer. The DIR coupler for the slow magenta layer can be a coupler similar to the coupler (B) used for the fast magenta or medium magenta layer.

An intermediate layer may be added between the high-sensitivity and medium-sensitivity or the medium-sensitivity and low-sensitivity magenta layers. The cyan dye-forming coupler (C) may be used in the low-speed magenta layer and the medium-speed magenta layer.

Intermediate Layer The intermediate layer between the slow magenta and fast cyan layers can contain oxidized developer scavengers or dyes added to adjust the photographic speed or density of the film. Preferred oxidized developer scavengers are those described for the yellow filter layer. The dyes may be similar to those for the UV layer, and further dyes useful in this layer may include coupler (11).

High Speed Cyan Layer The high speed cyan or highest red sensitive layer comprises a cyan image dye forming coupler (C), a first non-timed DIR coupler, preferably a second non-timed DIR coupler, a masking coupler and a yellow image dye forming. Contains a sex-correcting coupler.

Cyan image dye-forming couplers (C) useful in the fast cyan layer are those described for the mid magenta layer. Preferred cyan image dye-forming couplers are
The coupler is the same as the coupler (C) preferable for the medium-speed magenta layer.

The first and second non-timed DIR couplers in the fast cyan or highest red sensitive layer can be any development inhibitor releasing coupler known in the photographic art. Typical DIR couplers are, for example, US Pat. Nos. 3,227,554 and 3,384,65.
No. 7, No. 3,615, 506, No. 3,617, 2
91 and 3,733,201 and British Patent 1,450,479. Preferably, such DIR couplers do not contain groups that timed or retard the release of development inhibitor groups upon oxidative coupling. DIR couplers are typically represented by the formula:

[0104]

[Chemical 37]

In the above formula, COUP is the coupler moiety and INH is the releasable development inhibitor group attached to the coupler moiety at the coupling position. The coupler moiety COUP can be any coupler moiety capable of releasing an INH group upon oxidative coupling.

The coupler moiety (COUP) is, for example, a cyan, magenta or yellow forming coupler known in the photographic art. COUP can be ballasted with ballast groups known in the photographic art. Also, CO
UP may be a monomer, or it may be a dimer,
It may be part of an oligomeric or polymeric coupler, in which case one or more inhibitor groups may be included in the DIR coupler.

The releasable development inhibitor group (INH) can be any development inhibitor group known in the photographic art. Specific INH groups are mercaptotetrazoles,
Selenotetrazoles, mercaptobenzothiazoles, selenobenzothiazoles, mercaptobenzimidazoles, selenobenzimidazoles, mercaptobenzoxazoles, selenobenzoxazoles,
Mercaptooxadiazoles, mercaptothiadiazoles, benzotriazoles and benzodiazoles. Preferred inhibitor groups are mercaptotetrazoles and benzotriazoles. Particularly preferred inhibitor groups are described, for example, in US Pat. Nos. 4,477,563 and 4,782,012. CO
Preferred DIR couplers within the UP-INH range are coupler (37) and

[0108]

[Chemical 38]

The timed DIR couplers that may be used in this layer have couplers (24), (27) and (28) and the structure of the following formula.

[0110]

[Chemical Formula 39]

The second non-timed DIR coupler that may be used in the fast cyan layer has the structure:

[0112]

[Chemical 40]

A further second non-timed DIR coupler which may be used in the fast cyan layer has the structure of coupler (37). The masking coupler in the highest red sensitive layer is typically a cyan dye-forming masking coupler, such as
It is a naphthol cyan dye-forming masking coupler. Preferred cyan dye-forming masking couplers for the cyan dye-forming layer of photographic elements are of the formula:

[0114]

[Chemical 41]

The yellow image dye-forming coupler can be any such coupler useful in the photographic art for which its use exists in cyan recording, often referred to as a color-correcting coupler. Couplers that are yellow dye-forming couplers are typically acylacetamides, such as benzoylacetanilides and pivalylacetanilides as described. Such couplers are described in representative patents and publications such as those mentioned above.

Preferably the yellow dye forming coupler is a pivalyl acetanilide which comprises a phenoxy coupling leaving group. Such yellow dye-forming couplers have a structure similar to that used in the slow yellow layer, and the preferred coupler is coupler (6).
Is.

Low Sensitive Cyan Layer The slow cyan or low red sensitive layer comprises a cyan image dye forming coupler (C), a timed DIR coupler or a development inhibitor anchimeric releasing coupler (DIAR), a non-timed DIR coupler. , And a yellow image dye-forming corrective coupler.

The cyan image dye-forming coupler can be a coupler similar to the cyan image dye-forming coupler (C) used in the fast cyan layer. Also, the yellow image dye-forming corrective coupler can be a coupler similar to the yellow image dye-forming coupler used in the fast cyan layer.

Specific development inhibitor releasing couplers containing at least one timing group (T) capable of timely controlling the release of the development inhibitor group preferably have the structure of coupler (5). The non-timed DIR coupler is
It can be the same as for the fast cyan layer.

Intermediate Layer An intermediate layer is provided between the slow cyan layer and the antihalation layer. The intermediate layer can contain oxidized developer scavenger. Preferred oxidized developer scavengers are those described for the yellow filter layer. This interlayer solves the problem of fog enhancement caused by the interaction of the bleach accelerator releasing coupler with silver in the antihalation layer. Thus, providing this intermediate layer between any BARC-containing layer and the antihalation layer in the element to separate the antihalation layer from the layer containing the dye-forming coupler may be achieved, for example, by the desired acutance. It favors the use of BARC for good silver bleaching, while maintaining the same, without increasing fog or Dmin for the antihalation layer.

Antihalation Layer The antihalation layer is a very fine gray or black silver filament or colloidal silver such as CLS, and preferably UV absorbing dyes, gelatin as well as colored dyes for providing concentration to the film, such as eg. Coupler (1
1) can be included.

Although antihalation layers have been described with respect to silver, other materials can be used in place of or with silver. That is, instead of using fine silver in the antihalation layer, filter dyes such as efflux dyes or decolorizing dyes of the type discussed herein may be used. When filter dyes are used in the antihalation layer, the intermediate layer adjacent to the antihalation layer may be omitted. Oxidized developer scavenger may be removed from the antihalation layer if filter dyes are used. Specific examples of dyes that may be used in the antihalation layer are described in the aforementioned US Pat. No. 4,923,788.

The bleach-accelerating silver salts described for the yellow filter layer may be used in the antihalation layer with finely divided silver. When a bleach-accelerating silver salt is used in the antihalation layer, it is preferred to use an interlayer on the antihalation layer as described to minimize fog or Dmin.

[0124] In the following discussion of suitable materials for use in the emulsions such and elements such present invention, references in Research Disclosure (Research Disclosure), 1989 December
Mon, Item 308119, Kenneth Mason Publications Publishing, Lt
d., Dudley Annex, 12a North Street, Emsworth, Hampshire
P010 7DQ, ENGLAND, the contents of which are incorporated herein by reference. This publication will be identified hereafter by the term "Research Disclosure".

The silver halide emulsions used in the elements of this invention can be negative working. Suitable emulsions and their method of preparation are described in Research Disclosure Sections I and II and the publications cited therein. Vehicles suitable for the emulsion layer and other layers of the element of the invention are described in Research Disclosure Section IX and the publications cited therein.

In general, in addition to the above couplers, the elements of this invention include further couplers as described in Research Disclosure Section VII, paragraphs D, E, F and G and the publications described therein. Can be included. These couplers are based on Research Disclosure
It can be incorporated into the elements and emulsions described in Section VII, paragraph C and the publications described therein.

The photographic elements or their individual layers of the present invention may include optical brighteners (see Research Disclosure Section V), antifoggants and stabilizers (see Research Disclosure Section VI), Anti-staining agents and image dye stabilizers (Research Disclosure V
Section II, paragraphs I and J), Light-absorbing and scattering materials (see Research Disclosure Section VIII)
, Hardeners (see Research Disclosure Section IX), plasticizers and lubricants (see Research Disclosure Section XII), antistatic agents (see Research Disclosure Section XIII), matting agents (Research・
Disclosure Section XVI), development modifiers (see Research Disclosure Section XXI), surfactants and coating aids.

Photographic elements can be coated on a variety of supports described in Research Disclosure Section XVII and references cited therein.

Photographic elements are exposed to actinic radiation, typically in the visible spectral region to form a latent image, as described in Research Disclosure Section XVIII, and then to Research Disclosure Section XIX. It can be processed as described in 1. to form a visible dye image. Processing methods for forming a visible dye image include 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 developing agent then reacts with the coupler to provide the dye.

With negative working silver halide, the processing step described above gives a negative image. Development is followed by bleaching, fixing or bleach-fixing steps to remove traditional silver and silver halide, washing and drying steps.

[0131]

EXAMPLE I Three color photographic films were prepared using traditional surfactants,
Prepared as follows using antifoggants and the indicated materials. After providing a developable image, the Kodak C-41 process (British Journal of Photog
Processing according to raphic, pages 196-198 (1988) gave excellent results, eg improved color, sharpness, granularity and neutral scale. All silver halide emulsions were treated with 4-hydroxy-6-methyl-1,
Stabilized with 1.75 gm of 3,3a, 7-tetraazaindene. All silver halide emulsions were sensitized with the appropriate red, green and blue spectral sensitizing dyes.

Support mg / m ² mg / ft ² Layer 1 Halation 215 20 Black colloidal silver prevention layer 91 8.5 UV absorbing dye coupler (1) 91 8.5 UV absorbing dye coupler (2) 14.3 13 Blue filter dye (11 ) 2422 225 Gelatin

Layer 2 Intermediate layer 54 5.0 D-Ox scavenging coupler (3) 861 80.0 Gelatin

Layer 3 Lowest Red Sensitive Layer 915 85 Red sensitized silver iodobromide emulsion (4.5% iodide, tabular grains having an average grain size of 1.1 micron and an average grain thickness of 0.1 micron) 1238 115 red Sensitized silver iodobromide emulsion (Cubic grains having 0.5% iodide and average edge length of 0.21 micron) 603 56 Cyan dye-forming image coupler (4) 36 3.3 Cyan dye-forming development inhibitor releasing type ( DIR) coupler (5) 86 8.0 yellow dye-forming image coupler (6) 3078 286 gelatin

Layer 4 Highest Red Sensitive Layer 1291 120 Red sensitized silver iodobromide emulsion (3% iodide, octahedral grains having an average grain size of 0.90 micron) 54 5.0 Cyan dye-forming image coupler (4) 32.3 3 Cyan dye forming masking coupler (7) 50 4.6 Cyan dye forming DIR coupler (9) 11 1.0 Yellow dye forming image coupler (6) 2368 220 Gelatin 4.3 0.4 Cyan dye forming DIR coupler (8)

Layer 5 Intermediate layer 129 12 Oxidized developing agent scavenging coupler (3) 861 80 Gelatin 11 1 Green filter dye (10) 49 4 Blue filter dye (11)

Layer 6 Lowest green-sensitive layer 124 15 Green sensitized silver iodobromide emulsion (3% iodide, flat plate-like grains having an average grain size of 0.8 micron and an average grain thickness of 0.1 micron) 592 55.0 Green Sensitized silver iodobromide emulsion (tabular grains having 0.5% iodide, average grain size 0.5 micron and average grain thickness 0.1 micron) 161 15.0 Magenta dye releasing bleach accelerating fragment-forming image coupler (12) 12 1.1 Magenta dye forming DIR coupler (13) 1507 140 Gelatin

Layer 7 Intermediate Green Sensitive Layer 969 90.0 Green sensitized silver iodobromide emulsion (3% iodide, flat grain having an average grain size of 0.8 micron and an average grain thickness of 0.1 micron) 75.0 7.0 Magenta Dye-forming image coupler (14) 54.0 5.0 Magenta dye-forming image coupler (15) 9.0 0.8 Magenta dye-forming DIR coupler (13) 11.0 1.0 Cyan dye-forming image coupler (4) 1238 115.0 Gelatin

Layer 8 Highest green-sensitive layer 753.0 70.0 Green sensitized silver iodobromide emulsion (6% iodide, flat plate-like grains having an average grain size of 1.0 micron and an average grain thickness of 0.1 micron) 22.0 2.0 Magenta Dye-forming image coupler (15) 13.0 1.2 Magenta dye-forming DIR coupler (13) 65.0 6.0 Magenta dye-forming development masking coupler (16) 26.0 2.4 Yellow dye-forming DIR coupler (17) 969 90.0 Gelatin

Layer 9 Intermediate layer 75.0 7.0 D-Ox scavenging coupler (3) 194.0 18.0 Developer bleachable yellow filter Dye (18) 861.0 80.0 Gelatin

Layer 10 Lowest blue-sensitive layer 215.0 20.0 Blue-sensitized silver iodobromide emulsion (octahedral grains having an iodide content of 6% and an average grain size of 0.65 micron) 129.0 12.0 Blue-sensitized silver iodobromide emulsion (iodine) 25% 24.0 Blue sensitized silver iodobromide emulsion (octahedral grains with iodide 5%, average grain size 0.23 micron) 11.0 97.0 Yellow dye Producing Image Coupler (19) 1420 132.0 Gelatin

Layer 11 Highest blue-sensitive layer 377.0 35.0 Blue-sensitized silver iodobromide emulsion (octahedral grains having an iodide content of 6% and an average grain size of 1.0 micron) 11.0 1.0 Yellow dye-forming DIR coupler (17) 1076 100.0 gelatin

Layer 12 First protective layer 215.0 20.0 Non-sensitized silver bromide Lippmann emulsion (0.04 micron) 108.0 10.0 UV absorbing dye (1) 129.0 12.0 UV absorbing dye (2) 753.0 70.0 Tricresyl phosphate 1345 125.0 Gelatin 40 0.4 Green absorbing dye (10) 20 0.2 Red absorbing dye (20)

Layer 13 Second protective layer 44.0 4.1 Matt polyvinyltoluene beads 883.0 82.0 Gelatin

Example II To demonstrate the improvement in fog reduction using an intermediate layer with a fine silver layer, such as an antihalation layer, three color photographic films were tested with traditional surfactants, antifoggants. Prepared as follows using the agents and the indicated materials. After providing a developable image, the element is
odak) C-41 process (British Journal of Photographi
c, 196-198 (1988)).

Support mg / m ² mg / ft ² Layer 1 Halation 183 17 Black colloidal silver prevention layer 91 8.5 UV absorbing dye coupler (1) 2422 225 Gelatin 140 13 Blue absorbing dye (11)

Layer 2 Intermediate layer 161 15 D-Ox scavenging coupler (3) 861 80.0 Gelatin

Layer 3 Lowest Red Sensitive Layer 570 53 Red-sensitized silver iodobromide emulsion (4.5% iodide, tabular grains having an average grain size of 1.1 μm and an average grain thickness of 0.1 μm) 2013 187 red Sensitized silver iodobromide emulsion (0.5% iodide, cubic grains having an average edge length of 0.21 micron) 54 5.0 Cyan dye-forming DIR coupler (8) 430 40 Cyan dye-forming image coupler (4) 97 9.0 Cyan dye-forming coupler releasing bleach-accelerating fragments (21) 2691 250 Gelatin

Layer 4 Highest red-sensitive layer 1291 120 Red-sensitized silver iodobromide emulsion (3% iodide, octahedral grains having an average grain size of 0.90 micron) 38 3.5 Cyan dye-forming DIR coupler (9) 4 0.4 Cyan dye forming DIR coupler (8) 32 3.0 Cyan dye forming masking coupler (7) 102 9.5 Cyan dye forming image coupler (4) 2368 220 Gelatin

Layer 5 Intermediate Layer 43 4 Oxidized developing agent scavenging coupler (3) 861 80 Gelatin green filter dye (10) Blue filter dye (11)

Layer 6 Lowest Green Sensitive Layer 926 86 Green sensitized silver iodobromide emulsion (3% iodide, flat particle having an average particle diameter of 0.8 micron and an average particle thickness of 0.1 micron) 538 50 green Sensitized silver iodobromide emulsion (tabular grains with 0.5% iodide, average grain size 0.5 micron and average grain thickness 0.1 micron) 22 2 Magenta dye-forming masking coupler (22) 4.3 0.4 Magenta dye Forming DIR coupler (13) 2422 225 gelatin 678 63 magenta dye forming image coupler (14)

Layer 7 Highest green-sensitive layer 1345 125 Green sensitized silver iodobromide emulsion (6% iodide, flat plate-like grains having an average grain size of 1.0 micron and an average grain thickness of 0.1 micron) 113 10.5 Magenta Dye-forming image coupler (15) 4.3 0.4 Magenta dye-forming DIR coupler (13) 43 4.0 Magenta dye-forming masking coupler (22) 73 7.0 Yellow dye-forming DIR coupler (17) 1722 160 Gelatin

Layer 8 Intermediate layer 75.0 7.0 D-Ox scavenging coupler (3) 194.0 18.0 Developer bleachable yellow filter Dye (18) 861.0 80.0 Gelatin

Layer 9 Minimum blue-sensitive layer 280 26 Blue-sensitized silver iodobromide emulsion (octahedral grains having an iodide content of 6% and an average grain size of 0.65 micron) 387 36 Blue-sensitized silver iodobromide emulsion (iodine 5%, octahedron particles having an average particle size of 0.40 micron) 1238 115 Yellow dye-forming image coupler (19) 1420 132.0 Gelatin

Layer 10 Highest blue-sensitive layer 430 40 Blue-sensitized silver iodobromide emulsion (6% iodide, octahedral grains having an average grain size of 0.90 micron) 24 2.2 Yellow dye-forming DIR coupler (17) 1076 100.0 Gelatin 54 5 Yellow dye-forming image coupler (19)

Layer 11 First protective layer 215.0 20.0 Non-sensitized silver bromide Lippmann emulsion (0.04 micron) 108.0 10.0 UV absorbing dye (1) 10.8 10.0 UV absorbing dye (2) 108 100 Tricresyl phosphate 1345 125.0 Gelatin

Layer 12 Second protective layer 44.0 4.1 Matt polyvinyltoluene beads 883.0 82.0 Gelatin

The following tests were performed to demonstrate the benefits of the interlayer using the layer construction of Example II.

[0159]

[Table 2]

* Low-sensitivity cyan layer ** Halation-prevention layer *** Low-sensitivity magenta layer

When the slow cyan layer contains a bleach accelerator releasing coupler (BARC), the addition of an interlayer between the antihalation layer (AHU) and the slow cyan layer significantly reduces the red Dmin. It can be seen from Table I.

Example III To illustrate the improvement in red Dmin when a photographic element was prepared with a bleach-accelerating silver salt (BASS) according to the present invention, a photographic element having the layer construction shown in Example II was prepared. Manufactured.

[0163]

[Table 3]

As can be seen from Table II, some examples (5-
In 7), the element was prepared without the bleach accelerator releasing coupler and without an interlayer to isolate the fine silver containing antihalation layer. Table II shows that the standardized red Dmin is zero (0).

In the second example (5-4) bleach accelerator releasing couplers were used in the slow cyan (SC) layer to make elements. However, no interlayer was used between the antihalation layer and the rest of the element. It can be seen that the standardized red Dmin increases to 0.054.

In a third example (5-8), a silver salt of mercaptoproprionic acid (AgSCH ₂ CH ₂ COOH) was used in the antihalation layer and an intermediate layer between the antihalation layer and the rest of the element. Not used. The standardized red Dmin increased to 0.093.

In the fourth example (4-2), no bleach accelerating releasing coupler was used in the element and an interlayer was used between the antihalation layer and the rest of the element. The standardized red Dmin was zero (0).

Finally, in this example (4-4), a silver salt of mercaptoproprionic acid was used in the antihalation layer and an intermediate layer was placed between the antihalation layer and the rest of the element. The amount of standardized red Dmin was reduced to a level of 0.009.

Thus, when using a bleach-accelerating silver salt in an antihalation layer containing fine silver, the interlayer provided between the antihalation layer and the rest of the element surprisingly produces a significant red Dmin. Has the effect of reducing.

Example IV This example was prepared to demonstrate the advantage of reduced fog when an interlayer is provided between the fine silver containing filter layer and the bleach accelerator releasing coupler. Except that fine silver was used in the yellow filter layer, intermediate layers were provided above and below the fine silver layer, and bleach accelerator releasing couplers were provided in the slow yellow high speed magenta and medium speed magenta. As shown, the photographic elements used were substantially similar to Example I.

[0171]

[Table 4]

The data provided in Table III show the results of incorporating a fine silver layer (CLS layer) with an intermediate layer below and / or above the CLS layer.

[0173]

[Table 5]

* Standardization ** Low sensitivity yellow *** High sensitivity magenta *** Medium sensitivity magenta

From Table III, BARC for film elements containing colloidal silver (CLS) in the non-imaging layer.
It is noted that the addition of compounds resulted in a significant Dmin increase in the layer containing the dye-forming couplers adjacent to the CLS layer. Adding an intermediate layer to separate the CLS layer from the layer containing the dye-forming couplers,
The Dmin produced by using BARC compounds in the presence of the CLS layer was significantly reduced.

Example V The following coatings were made using the photographic element of Example I to illustrate the reduction of fog in a photographic element with an active magenta coupler, such as coupler (15).
Coating 1 was similar to Example I. Fine silver (CLS) was used in the yellow filter layers of Coatings 2 and 3 instead of dye coupler (18). Further, a coupler (14) and a low activity coupler were used instead of the coupler (15) as follows.

[0177]

[Table 6]

From Table IV, there is a loss of green speed in Coatings 2 and 3 and the dye (1
It is observed that using 8) and coupler (15) increases the green speed (Coating 1). Furthermore, coating film 2
And 3 had enhanced green minimum density (fog) compared to the coatings of this invention.

Although the present invention has been described in detail with particular reference to those particular embodiments, it will be understood that variations and modifications are possible within the spirit and scope of the invention.

[0180]

The photographic elements of this invention significantly reduce fog.

Claims (2)

[Claims] 1. An improved multi-layer color photographic element with reduced fog levels comprising a support coated on its surface with a photographic silver halide emulsion layer, the layer comprising at least one green layer. The green-sensitive layer comprises a unit of a yellow filter layer adjacent to the light-sensitive silver halide emulsion layer and the green-sensitive layer, wherein the green-sensitive layer is (a) a pyrazolotriazole dye-forming coupler [the coupler is represented by the following formula: (In the above formula, R is an organic group having 1 to 6 carbon atoms, and R is
Selected from methyl, ethyl, methoxy, acetamide and phenyl, COG is a coupling leaving group, R ₁ , R ₂ and R ₃ are selected from hydrogen, alkyl, phenyl, nitrogen and oxygen, and in the above formula No more than one R ₁ ,
R ₂ and R ₃ are hydrogen))
And (b) a yellow filter layer comprising a dye, and 2. An improved multi-layer color photographic element having a reduced level of fog comprising a support coated on its side with a photographic silver halide emulsion layer, the layer comprising at least one green layer. The improvement includes a unit of a sensitive silver halide emulsion layer and a yellow filter layer adjacent to the green sensitive layer, and (a) a magenta dye-forming coupler in the green sensitive layer (the coupler is represented by the following formula: , And (b) the following formula: An element comprising a yellow filter layer comprising a microcrystalline dye represented by.