JPH0823673B2 - Silver halide photographic element - Google Patents

Description

FIELD OF THE INVENTION This invention relates to silver halide photographic elements containing bleach accelerator releasing couplers.

[Conventional technology]

Photographic materials useful in forming dye images by methods involving a bleaching step are known and used in the market. Such materials and methods are described, for example, in The Theory of
the Photographic Process , 4th edition, edited by TH James, 4
62-463 and 335-361. The use of bleach accelerator releasing couplers in such photographic materials is described in Research Disclosure , 1973, Item No. 11449. The bleach accelerator releasing coupler, also known as BARC, contained a heterocyclic group as the bleach accelerator moiety that was released during processing of the photographic element. These bleach accelerator releasing couplers cause an undesired degree of adverse development effects.

Couplers having a thioether group in the coupling position are known in the field of photography. Examples of such couplers are, for example, U.S. Pat.Nos. 3,227,554 and 4,293,691.
No. specification. These compounds are useful as development inhibitor releasing (DIR) couplers. Almost all of the couplers referred to as development inhibitor releasing couplers have thioether groups and are oil soluble to help hold the coupler in one position in the hydrophilic emulsion layer of the photographic material. Such couplers typically have a palast group for this purpose. They do not require a balance between strong affinity for silver and water solubility, as is the case with bleach accelerator compounds.

[Problems to be solved by the invention]

The percentage of silver bleached and the bleaching rate of silver in dye-forming silver halide photographic elements containing dye-forming couplers are not as good as desired for exposure and processing. Couplers that have a thioether group in the coupling position and are oil soluble (typically as a result of the presence of ballast groups) do not produce a sufficiently strong affinity for silver and water soluble ballast.

[Means for solving problems]

The present invention, bleaching accelerator-releasing couplers, the _{formula: - (TIME) n -SR 1} -R 2 ( wherein TIME represents a timing group, n represents 0 or 1, R ₁ is a bond group, preferably Is an alkylene group having 1 to 8 carbon atoms or (Wherein L ′ represents an alkylene group having 1 to 8 carbon atoms or a phenylene group), and R ₂ represents a water-solubilizing group, preferably a carboxy group, or a precursor thereof. Solving the above problems by providing a silver halide photographic element containing a silver halide photographic emulsion layer and a bleach accelerator releasing coupler which comprises a coupler moiety (group) having a specific bleach accelerator moiety (group). However, it allows the desired bleaching of silver in such photographic materials when exposed and processed.

The releasable bleach accelerator group is present at a position on the compound that has a group capable of releasing the bleach accelerator group at a point during processing of the photographic element that allows the bleaching process to be accelerated. The bleach accelerator releasing compound is preferably a coupler having a bleach accelerator group at the coupling position. The coupler may be, but need not necessarily be a dye-forming coupler.

A method of developing an exposed silver halide photographic element as described above, wherein the method comprises a silver bleaching step, the bleaching step comprising:
Bleaching is improved when carried out in the presence of a bleach accelerator releasing compound, preferably a bleach accelerator group released from a bleach accelerator releasing coupler as described above.

As used herein, the term "coupler" refers to any compound containing a coupler group and a bleach accelerator group (TIME) _n -SR ₁ -R ₂ . The term coupler group as used herein is
The part of the compound other than the bleach accelerator group shall be referred to.

By varying the specific R ₁ group that binds the sulfur atom and the water solubilizing group R ₂ , such as water solubility, diffusivity, silver affinity, silver ion complex solubility, silver developing effect and other sensitometric effects. The parameters can be adjusted. Since these parameters can be adjusted by modifying R ₁ , these parameters need not be considered important in choosing a particular coupler group and a particular water-solubilizing group, and the choice of such groups and The particular photographic elements and methods are free.

Upon processing, the bleach accelerator fragment is released as a unit at the appropriate time. That is, -SR ₁ -R ₂ is released as a unit. The rate and total time of diffusion of the bleach accelerator fragment in the photographic element must be such that it can promote bleaching in the appropriate layers of the photographic element during processing.
If a timing group is present, this group is also a unit-
Releases SR _1- R ₂ . The choice of R ₁ and R ₂ can also affect the rate and total time of release of the bleach accelerator group from the rest of the compound, preferably the rest of the coupler. It is necessary that the bleach accelerator groups do not adversely affect processing steps and photographic elements. Optimal R ₁
A sufficiently water-soluble bleaching accelerator is selected by selecting R and R ₂ groups to minimize the development inhibiting effect of the bleaching accelerator group and improve the activity of the bleaching accelerator. This helps distinguish between compounds that are useful development inhibitor releasing compounds and compounds that are useful bleach accelerator releasing compounds.

Preferred photographic couplers having releasable bleach accelerator groups have the formula: [In the formula, COUP represents a coupler group, m represents 1 to 8, R ₃
And R ₄ each independently represent hydrogen or an alkyl group having 1 to 4 carbon atoms, The total number of carbon atoms therein is 1 to 8]. The alkyl group is a linear or branched alkyl group, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-
It includes a butyl group and a t-butyl group.

The coupler group can be any group that reacts with the oxidized color developing agent to allow release of the bleach accelerator group. The coupler group is a coupler group useful for a conventional dye-forming coupler which produces a dye when reacted with an oxidized color developing agent, as well as a coupler group which produces a colorless product when reacted with an oxidized color developing agent. including.

The coupler group may or may not have an oil-soluble group. It may be a monomer or may form part of a dimeric, oligomeric or polymeric coupler, in which case more than one bleach accelerator group may be included in the coupler. Each coupling position can release a bleach accelerator group.

Depending on the particular coupler group, the particular color developing agent and the type of treatment, the reaction product of the coupler group with the oxidized color developing agent is (1) colored and non-diffusible, in which case Stays where it is formed; (2) is chromogenic and diffusive, in which case it can be removed during processing or moved to a different location; or (3) It is colorless and diffuse or non-diffuse, in which case the reaction products do not contribute to the image density. In the cases of (2) and (3), the reaction product initially develops color and / or is non-diffusible, but it may be converted into a colorless and / or diffusible product during the course of the treatment.

The bleach accelerator group is attached at the coupling position of the coupler group which can replace the bleach accelerator group when the coupler reacts with the oxidized color developing agent.

In such bleach accelerator releasing organic compounds, preferably bleach accelerator releasing couplers, the bleach accelerator group may be attached to the rest of the organic compound via a timing group (TIME). TIME in the above structural formula
Is a group that allows the timed release of -SR ₁ -R ₂ from COUP. The timing mechanism may be any timing mechanism useful for releasing a photographically useful group from a coupler group. For example, the timing mechanism may be, for example, U.S. Pat.
It may be as described in 09,323.

Release of the bleach accelerator group may involve a single reaction or a continuous reaction. For example, to release a bleach accelerator group,
Two or more consecutive reactions must occur within the TIME group. As another example, the TIME group can have two bleach accelerator groups attached at different positions on the TIME group, and from the coupler group
When the TIME group is released, two reactions occur in succession,
Allows continuous release of two bleach accelerator groups. Another example is the release of a second coupler group containing another timing group to which a photographically useful group is attached, the TIME group being released after reaction of the second coupler group with an oxidized color developing agent. Is the reaction in.

The TIME group controls one or more of the reaction rate between COUP and the oxidized color developer, the diffusion rate of -TIME-SR ₁ -R ₂ and the release rate of -SR ₁ and R _{2 when} released from COUP. Such groups and substituents may be included. The TIME group may contain additional substituents, such as those photographically useful that remain attached to the timing group and may be independently released. The TIME group may include a ballast group. Representative TI
ME groups are described in US Pat. Nos. 4,248,962 and 4,409,323.

R ₂ may optionally be a precursor group for a water solubilizing group. For example, R ₂ may be an ester group that forms a water-solubilized carboxylic acid group when hydrolyzed.

When the R ₁ group represents a bonding group composed of an alkylene group having 1 to 8 carbon atoms, the R ₂ group represents a water-solubilizing group or a precursor thereof as listed below, and the R ₁ group represents when representing the tetrazole group of the structural formula, in particular represents a water solubilising groups or precursor thereof as listed _{below: -COOH -COOCH 3 -COOC 2 H 5} -NHSO 2 CH 3 -NHCOOCH 3 -NHCOOC 2 H ₅ -SO ₃ H -OH -SO ₂ NH ₂ -NR ₅ R ₆ [wherein R ₅ represents H or an alkyl group having 1 to 4 carbon atoms, R ₆ represents an alkyl group having 1 to 4 carbon atoms,
At least one of R ₅ and R ₆ is an alkyl group, and R ₅ and
The total number of carbon atoms in R ₆ is 8 or less].

The following are examples of useful R ₁ groups: —CH ₂ — —CH ₂ CH ₂ — —CH ₂ CH ₂ CH ₂ — ‐CH ₂ CH ₂ CH ₂ CH ₂ ‐ ‐CH ₂ CH ₂ OCH ₂ CH ₂ ‐ [Wherein L'represents an alkylene group having 1 to 8 carbon atoms or a phenylene group], for example, Or Listed below are patent specifications and publications that describe representative COUP groups useful in the present invention: In these structures, does the unsaturated bond in each COUP group represent the point of attachment to the TIME group? , Or the absence of a TIME group indicates the point of attachment to the bleach accelerator group. The vertical unsaturated bond in the TIME group is
The point of attachment of COUP is shown and the horizontal unsaturated bond at TIME is the point of attachment of the bleach accelerator group.

I.COUP A. Useful couplers that form cyan dyes when reacted with oxidized color developing agents are described in U.S. Pat.
No. 2,895,826, No. 3,002,836, No. 3,034,892
No. 2,474,293, 2,423,730, 2,367,53
Nos. 3,041,236 and 4,666,999 are representative patent specifications.

Such couplers form cyan dyes when reacted with an oxidized color developing agent, and have phenols having a releasable bleach accelerator group bonded at the coupling position, that is, at the 4-position of the coupler group. It is preferably a naphthol. The structure of the preferred cyan dye-forming coupler group is
It is as follows: [Wherein R ₈ , R ₉ ′, R ₁₀ , R ₁₁ and R ₁₂ each independently represents a ballast group, and R ₇ and R ₉ are each at least one halogen atom, for example, chlorine or fluorine, an alkyl group,
For example, an alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, a propyl group, or a butyl group, or an alkoxy group, such as an alkoxy group having 1 to 4 carbon atoms, such as a methoxy group, an ethoxy group, a propoxy group, and butoxy group. Represents a group].

Examples of such cyan dye-forming couplers are shown below.

B. Examples of couplers that form magenta dyes when reacted with oxidized color developing agents are described, for example, in U.S. Pat.
No. 8, No. 2,369,489, No. 2,343,703, No. 2,311,0
No. 82, No. 3,152,896, No. 3,519,429, No. 3,062,
They are described in representative patent specifications such as 653 and 2,908,573.

Such magenta dye-forming couplers are preferably pyrazolones and pyrazolotriazoles that form magenta dyes when reacted with an oxidized color developer. The structures of preferred magenta dye-forming couplers are shown below: [Wherein R ₁₄ , R ₁₆ and R ₁₇ are each independently an aryl group,
An alkyl group, for example, an alkyl group having 1 to 30 carbon atoms, R ₁₃ , R ₁₅ and R ₁₈ are each independently a ballast group, or a phenyl group or a substituted phenyl group, for example, a 2,4,6-trihalophenyl group, For example, it represents a 2,4,6-trichlorophenyl group].

Examples of such magenta dye-forming couplers are shown below: C. A coupler that forms a yellow dye when reacted with an oxidized color developing agent is, for example, U.S. Patent Nos. 2,875,057, 2,407,210, 3,265,506, and 2,298,443,
No. 3,048,194 and No. 3,447,928.

Such yellow dye-forming couplers are preferably acylamides such as benzoylacetanilides and pivalylacetanilides.

Examples of such yellow dye forming couplers are shown below: [Wherein R ₂₁ , R ₂₃ and R ₂₅ each independently represent a ballast group, and R ₁₉ , R ₂₀ , R ₂₂ and R ₂₄ each independently represent hydrogen or one or more halogens such as chlorine or fluorine, an alkyl group. Represents an alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, a propyl group and a butyl group, an alkoxy group, for example, an alkoxy group having 1 to 20 carbon atoms, or a ballast group].

Examples of such yellow dye-forming couplers are given below: D. Couplers which form colorless products or which do not sufficiently absorb electromagnetic radiation in the visible spectral range are described, for example, in GB 861,138, U.S. Pat.
Representative patent specifications such as 3,632,345, 3,928,041, 3,958,993 and 3,961,959 are described. Such couplers are preferably cyclic carbonyl group-containing compounds that form colorless products when reacted with oxidized color developing agents.

The structures of representative couplers that form colorless products are shown below: [In the formula, R ₂₆ , R ₂₇ , R ₂₈ , R ₂₉ and R ₃₀ each independently represent a ballast group, and m represents 1 or 2].

Examples of such couplers which can form colorless or nearly colorless products are given below: Other colorless couplers such as oxazolinones, such as the following are also useful: (In the formula, R ₃₀ is --CH ₂ --COOH --CH ₂ CH ₂ --COOH --CH ₂ CH ₂ CH ₂ --COOH --CH ₂ CH ₂ CH ₂ CH ₂ --COOH --CH ₂ CH ₂ OH --CH ₂ CH ₂ SO ₃ H ‐CH ₂ CH ₂ SO ₂ NH ₂ ‐CH ₂ CH ₂ CH ₂ SO ₂ NH ₂ E. couplers that form a black dye when reacted with an oxidized color developing agent include, for example, U.S. Pat.Nos. 1,939,231, 2,181,944, 2,333,106, and 4,429,035,
No. 4,439,518, No. 4,254,213, No. 4,387,158
No. 4,126,461 and No. 4,200,466.

Such couplers include resorcinols or black dyes that form black products when reacted with oxidized color developing agents.
It is preferably m-aminophenol. The structures of preferred couplers capable of forming black dyes are shown below: [Wherein R ₃₁ and R ₃₂ are each independently an alkyl group such as an alkyl having 3 to 20 carbon atoms, a phenyl group or a hydroxy group, a halogen such as chlorine or bromine, an amino group,
An alkyl group, for example, an alkyl group having 1 to 20 carbon atoms, or an alkoxy group, for example, a phenyl group substituted with an alkoxy group having 1 to 20 carbon atoms, R ₃₃ and R ₃₄ each independently represent hydrogen or an alkyl group. , For example 1 to 1 carbon atoms
20 alkyl groups, alkenyl groups, such as C1-C20 alkenyl groups, or aryl groups, such as C6-C6
Represents an aryl group of 20 and R ₃₅ is one or more halogen, such as chlorine or bromine, an alkyl group, for example, an alkyl group having 1 to 20 carbon atoms, an alkoxy group, for example, an alkoxy group having 1 to 20 carbon atoms, or Represents other monovalent organic groups that do not adversely affect dye formation or the release of bleach accelerator groups].

Examples of such couplers capable of forming black dyes are given below: The useful TIME group allows the release of the bleach accelerator group at a suitable point during processing, that is, at a point that may facilitate bleaching of the photographic element. Examples of such TIME groups are: A. Acyclic TIME groups: [In the formula, n represents 1 to 4, R ₃₆ represents hydrogen, an alkyl group, for example, an alkyl group having 1 to 20 carbon atoms, or an aryl group, for example, an aryl group having 6 to 20 carbon atoms, preferably an unsubstituted phenyl group or a substituted phenyl group] .

B. Aromatic TIME group: [In the formula, n represents 0 or 1, R ₃₇ represents an alkyl group such as an alkyl group having 1 to 20 carbon atoms, or an aryl group such as an aryl group having 6 to 20 carbon atoms, such as a phenyl group, and X represents hydrogen, a cyano group, or fluorine. , Chlorine, bromine, iodine, nitro group, alkyl group,
For example, an alkyl group having 1 to 20 carbon atoms, preferably a methyl group, an ethyl group, a propyl group or a butyl group, or an aryl group, for example, an aryl group having 6 to 20 carbon atoms, preferably an unsubstituted phenyl group or a substituted phenyl group. Represents].

The bleach accelerator releasing coupler can be used in combination with a colorless coupler or a color forming coupler and added to a silver halide emulsion together with a dye image forming coupler, or an auxiliary layer,
For example, it can be added in the form of an independent emulsion in the intermediate layer and / or the undercoat layer. The bleach accelerator releasing compound is useful alone or in combination with two or more bleach accelerator releasing compounds.

Bleach accelerator releasing couplers can be incorporated into the photographic element such that when exposed photographic element is developed it is in reactive association with the oxidized color developing agent. The coupler compound incorporated into the photographic processing solution should have a molecular size and structure such that the compound diffuses through the photographic layer with the processing solution. When incorporated in a photographic element, the coupler compound should generally be non-diffusible. That is, these compounds should have a molecular size and structure such that they do not diffuse or migrate significantly from the layer being coated.

The photographic element incorporating the coupler can be a simple element consisting of one silver halide emulsion layer or it can be a multilayer multicolor element. The coupler compounds of this invention are incorporated into a silver halide emulsion layer or another layer, e.g., an adjacent layer which is in reactive association with an oxidized color developing agent having developed silver halide in the emulsion layer. Can be mixed. The silver halide emulsion layer contains other photographic coupler compounds,
For example, development inhibitor releasing (DIR) couplers, color forming couplers and color forming masking couplers may be included or combined therewith. These other photographic coupler compounds are capable of forming dyes of the same or different colors and hues as the bleach accelerator releasing compound. In addition, the silver halide emulsion layers may contain magenta normally contained in such layers.

A typical multilayer multicolor photographic element according to this invention comprises a support and thereon a red-sensitive silver halide emulsion unit having a cyan dye image-forming material associated therewith, a green-sensitive silver halide emulsion having a magenta dye image-forming material associated therewith. It comprises a blue-sensitive silver halide emulsion unit in which an emulsion unit and a yellow dye image-forming material are combined, at least one of which is associated with a bleach accelerator releasing compound as described above. Each silver halide emulsion unit consists of one or more layers, and the various units and layers may be arranged in different positions from each other. Typical arrangements are U.S. Pat.Nos. 3,227,554, 3,620,747 and
No. 3,843,369 and British Patent No. 923,045. The coupler compound may be incorporated in or combined with one or more layers or units of the element. The layers and units affected by the bleach accelerator group can be adjusted by providing scavenger layers in appropriate locations on the element that limit the effect of the bleach accelerator group to the desired layer or unit.

The light-sensitive silver halide emulsion contains coarse, normal or fine silver halide crystals or a mixture thereof, and is composed of silver chloride, silver bromide, silver bromoiodide, silver chlorobromide, silver chloroiodide, chloroiodobromide. It may contain silver halide such as silver halide and mixtures thereof. The emulsion may be a negative working or direct positive working emulsion. These can form a latent image mainly on the surface of the silver halide grain or can form a latent image mainly inside the silver halide grain. They can be sensitized chemically and spectrally. The emulsion is typically a gelatin emulsion, although other hydrocolloids can be used in the conventional manner. For example, Research Disclosure , 1983
January, 2013, tabular grain silver halide photographic emulsions described in Item No. 22534 and U.S. Pat. No. 4,434,226
Particularly useful.

When the coupler group is a dye-forming coupler, it reacts with oxidized developer in the same or adjacent layers,
It is possible to form dyes of the same or different color or hue as those obtained from the first coupler. When the coupler group is a competing coupler, it can react with oxidized color developer in the same or adjacent layers to reduce dye density.

Typical concentrations of bleach accelerator releasing compounds in photographic elements are
It is in the range of about 50 to about 500 mg / m ² .

Particularly useful photographic elements in accordance with this invention are dye-forming photographic elements having a layer structure known to be useful in forming multicolor images in the subtractive process. Any or all of each color record may be present in the form of a two or three layer structure.

The method of forming a dye image in a photographic element as described above comprises
Includes conventional color processing including bleaching steps. The bleaching process is
It is preferably performed separately from fixing. The bleaching composition contains a known bleaching agent. An example of a typical method is Research Disclos
ure , December 1978, Item No.17643 and “Modern Photogra
phic Processing ", Grant Haist, Volume 2, 569-587 (John Wiley and Sons, New York, 1979).
It is described in. Processing of dye-forming photographic elements in accordance with the present invention typically includes color developing, bleaching and fixing steps. The bleaching step and fixing step can be combined into one step if desired. Other processing steps useful in this method include a precure step, a neutralization step, a first development step (black and white development), a stabilization step and a water wash step. The processing steps are typically carried out in the temperature range of 18-60 ° C.

Bleach accelerator releasing compounds are prepared by organic synthetic procedures known in the art of synthesizing organic compounds. For example, the coupler group could be reacted with a bleach accelerator in a suitable solvent. The following describes a representative method for making bleach accelerator releasing couplers: Synthesis Example A: This example relates to the synthesis of the following bleach accelerator releasing couplers: The following compound (coupler component) in 500 ml of dimethylformamide (solvent): A solution of 20 g (33 mmol), 1- (2-carboxyethyl) tetrazoline-5-thione (bleaching accelerator component) 5.8 g (33 mmol) and potassium carbonate (K ₂ CO ₃ ) 14 g was heated at 80 ° C for 2 hours. To do. The resulting composition is then cooled and placed in ice cold dilute hydrochloric acid. The resulting product is isolated and purified. this is,
Extraction and then purification by silica gel chromatography and recrystallization from acetonitrile gives a nearly colorless product. This product is identified by elemental analysis as the desired bleach accelerator releasing coupler.

Synthesis Example B: This example relates to the synthesis of the following bleach accelerator releasing coupler: Coupler component: To a solution of 5.6 g (8 mmol) (prepared by the procedure described in US Pat. No. 4,248,962) in 25 ml of anhydrous pyridine the formula: 1.1 g (8 mmol) of 2-dimethylaminoethanethiol hydrochloride represented by are added. Stir the mixture overnight,
Then put in water. Then extract the resulting product,
Purify. The desired product is isolated by extraction with ethyl acetate, triturated with ligroin and dried to give the desired bleach accelerator releasing coupler, mp 130-131 ° C. It is identified by spectroscopic and elemental analysis.

Synthesis Example C: This example relates to the synthesis of a bleach accelerator releasing coupler.

Coupler components in 75 ml of tetrahydrofuran stirred under nitrogen gas: Tetramethylguanidine 1.4 in 5 g (9.9 mmol) solution
g (9.9 mmol) and then 1.1 ml of ethyl acrylate (9.9
Mmol). After 30 minutes, 50 ml of methanol and 1.
Add 10 ml of 25N sodium hydroxide solution and add 1 to the resulting composition.
Stir for 5 minutes. The mixture is then placed in ice cold dilute hydrochloric acid.
The desired product is extracted and purified. For example, after extraction of the desired product with diethyl ether and crystallization, the desired bleach accelerator releasing coupler is obtained, which has a melting point of 139.
It is a colorless solid at ˜141 ° C. In addition, the product is identified by elemental analysis and spectroscopic analysis.

Synthesis Example D: This example relates to the synthesis of a bleach accelerator releasing coupler: Compound in 75 ml of dimethylformamide: 20 g (70 mmol) and 3-mercaptopropionic acid (HSC
To a stirred solution of 7.4 g (70 mmol) H ₂ CH ₂ COOH, 3.85 ml bromine in 25 ml dimethylformamide are added dropwise. After stirring overnight, the mixture is placed in water. The only product (P-
2): Is isolated by filtration. Then P-2 in 200 ml glacial acetic acid
11 g of zinc is added to a solution of 5.6 g (13.7 mmol) and stirred for 30 minutes before filtration. Then a compound designated P-3: 6.9 g (13.7 mmol) are added to the filtrate, stirred for 1 hour and the mixture is poured into water. The resulting product, isolated by extraction, is then dissolved in methanol / tetrahydrofuran (equal volume), hydrolyzed with 50% sodium hydroxide solution and acidified with excess cold dilute hydrochloric acid. The desired bleach accelerator releasing coupler is then extracted and purified by silica gel chromatography. The bleach accelerator releasing coupler has a melting point of 120-122 ° C and is identified by elemental analysis. Elemental analysis reveals the presence of one molecule of water of hydration.

〔Example〕

 The following examples further illustrate the present invention.

Example 1 This example illustrates a multilayer color photographic element containing a bleach accelerator releasing coupler according to the invention.

A multilayer color photographic element shown as sample a was prepared by coating the following layers in the order listed on a cellulose triacetate film support (coating concentration shown in mg / m ² , silver halide as silver concentration). Layer 1 (bottom layer) low-sensitivity cyan layer-low-sensitivity red sensitized silver bromoiodide tabular grain gelatin emulsion (1615
mg / m ² ), gelatin (2153 mg / m ² ). This layer is also C-1
Cyan image dye-forming coupler (603 mg / m ² ): And C-3 shown below as a color forming coupler (65 mg / m ² ) and D-1 as a development inhibitor releasing coupler (43 mg / m ² ).
m ² ): including.

Layer 2: High Speed Cyan Layer-High speed red sensitized silver bromoiodide tabular grain gelatin emulsion prepared as described in U.S. Pat. No. 4,434,226. This layer also contains gelatin (1615mg / m ² ) and C-2.
Cyan image dye-forming coupler (194 mg / m ² ): And a color coupler (16 mg / m ² ) designated as C-3: including.

Layer 3: Intermediate Layer-Gelatin (1292 mg / m ² ) Layer 4: Low Sensitive Magenta Layer-Green Sensitized Silver Bromoiodide Tabular Grain Gelatin Emulsion Prepared as Described in U.S. Pat. No. 4,434,226. . This layer is further provided with a magenta image dye-forming coupler designated Coupler M-1: And color couplers designated M-3: And DIR coupler D-2, a development inhibitor releasing coupler: including.

Layer 5: High Speed Magenta Layer-High speed green sensitized silver bromoiodide tabular grain gelatin emulsion prepared as described in U.S. Pat. No. 4,434,226. This layer is further referred to as M-2 magenta image dye-forming coupler: And color couplers designated M-3: including.

Layer 6: Intermediate Layer-Gelatin Layer 7: Low Speed Yellow Layer-Blue sensitized silver bromoiodide tabular grain gelatin emulsion prepared as described in U.S. Pat. No. 4,434,226 (3-6 moles iodine). %). This layer further comprises a yellow image dye-forming coupler Y-1 and a development inhibitor releasing coupler (DIR coupler): And a gelatin hardening agent.

Layer 8: High Speed Yellow Layer High speed blue sensitized silver bromoiodide gelatin emulsion prepared as described in U.S. Pat. No. 3,320,069 and optionally sulfur and gold sensitized. This layer is further designated as Y-1 yellow image dye-forming coupler: including.

Layer 9: Protective Overcoat Layer-Mixture of UV Absorber and Gelatin Coupler C-2 in Layer 2 in the amounts shown in Table 1 for comparative coupler C-4, and bleach accelerator releasing coupler BARC-. 1,-
Samples b, d, f, and h were manufactured by the same method as the sample a, except that 2 or -3 was used instead. Further, samples c, e, g and i are couplers C- in layer 1 of sample a.
It was similarly prepared by substituting 1 for each of the comparative couplers C-4 and BAR couplers 1, 2 or 3 in the amounts shown in the table. Each of these samples was exposed to white light through a stepwise density step tablet and the British Journal of P
Processed in a color developer of the type described in Hotography Annual, 1979, pp. 204-206. Plot the density for red light against the logarithmic exposure and plot D-min, D-max,
And relative photographic sensitivity ΔS (in logE units at D = fog + 0.1)
Was measured and is shown in Table A. X of the silver remaining after the bleaching process
Table A shows the averages for the two highest exposure steps, measured by line fluorescence measurement.

From the data presented in Table A, the addition of BARC-1, -2 or -3 to the cyan layer of a multilayer element improves the removal of silver which otherwise would be retained and cause problems in color reproduction. I understand that it will be done. When added to the high sensitivity layer at a relatively high concentration, BARC-1 and -2 cause a significant decrease in sensitivity,
With BARC-3, such a decrease is small. When added to the slow layer, all but BARC-2 increase the minimum concentration.

As used herein, Comparative C-4 is the following compound: As used herein, BARC-1 is the following compound: As used herein, BARC-2 is the following compound: As used herein, BARC-3 is the following compound: Example 2 A multilayer coupler-incorporated photographic element was prepared in the same manner as Sample a of Example 1 (the coating amount is shown in mg / m ² ). Control sample j was coated on a film support as follows.

Layer 1 Low-sensitivity cyan layer- (Bottom layer) Red-sensitized silver bromoiodide tabular grain emulsion blend)
(1615), gelatin (2153), cyan image coupler C-1
(603), color coupler C-2 (32) and DIR coupler-D-1
Including (32).

Layer 2: High speed cyan layer-High speed red sensitized silver bromoiodide tabular grain emulsion (1076), gelatin (1615), cyan image coupler C-2 (151) and color coupler C-3 (48) are contained. .

Layer 3: Intermediate Layer-Contains gelatin (1292).

Layer 4: Low-sensitivity magenta layer-green sensitized silver bromoiodide tabular grain emulsion blend (1292), gelatin (1615), magenta image coupler M-1 (646), color coupler M-3 (43) and DIR coupler Including D-2 (13).

Layer 5: High speed magenta layer-High speed green sensitized silver bromoiodide tabular grain emulsion (969), gelatin (1292), magenta image coupler M-2 (108) and color coupler M-3 (46) are contained. .

Layers 6-9: Same as Sample a of Example 1 Sample k was made as Sample j, except the magenta layer was changed as follows.

Layer 4: Coupler M-1 (484, Coupler D-2 (32) and added bleach accelerator releasing coupler BARC-4 (108) Layer 5: Coupler M-2 (54) and added BARC-4 (54) Sample 1 was manufactured in the same manner as sample j except that the cyan layer was changed as follows.

Layer 1: Coupler C-1 (517) and added BARC-3 (86) Layer 2: Coupler C-2 (75) and added BARC-3 (60) As shown in the preparation of samples k and l Sample m was prepared in the same manner as sample j, except that the bleach accelerator releasing coupler was added to the modified cyan and magenta layers 1, 2, 4 and 5.

Photographic results after exposure and processing as in Example 1 are shown in Table B. In the table, R, G and W indicate that the sample was exposed to red light, green light or white light, respectively.

In this example, BARC-4 is the following compound: The following examples can be carried out according to Example 1 except that the bleach accelerator releasing coupler is replaced by the bleach accelerator releasing coupler shown in the examples below.

Example 3 In this example, BARC-5 is the following compound: Example 4 In this example, BARC-6 is the following compound: Example 5 In this example, BARC-7 is the following compound: Effects of the Invention A silver halide photographic element according to the present invention containing a bleach accelerator releasing coupler containing a coupler moiety (group) having a releasable bleach accelerator moiety (group) as described above is exposed and processed. This results in improved silver bleaching.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Robert Hootsugu Romanets New York, USA 14615, Rochester, The Amestown Terrace 263 (72) Inventor Lichyard Peters Zaziewski United States, New York 14620, Rochister, Warner Park 21 (56) References JP-A-51-49725 (JP, A) JP-A-55-135835 (JP, A) JP-A-57-173836 (JP, A)

Claims (2)

[Claims] 1. A silver halide photographic element comprising a silver halide photographic emulsion layer and a bleach accelerator releasing coupler, said bleach accelerator releasing coupler having the formula:-(TIME) _n --S--R. ₁ —R ₂ [wherein TIME represents a timing group, n represents 0 or 1, R ₁ represents a bonding group composed of an alkylene group having 1 to 8 carbon atoms, and R ₂ represents —COOH, — NHSO ₂ CH ₃ , −NHCOOCH
_{3, -NHCOOC 2 H 5, -SO} 3 H, -OH, —SO ₂ NH ₂ and —NR ₅ R ₆ (wherein R ₅ represents H or an alkyl group having 1 to 4 carbon atoms, R ₆ represents an alkyl group having 1 to 4 carbon atoms, R ₅ and
At least one of R ₆ is an alkyl group, and the total number of carbon atoms in R ₅ and R ₆ is 8 or less) and represents a water-solubilizing group selected from the group consisting of A silver halide photographic element containing a coupler portion having a bleach accelerator portion. 2. A silver halide photographic element comprising a silver halide photographic emulsion layer and a bleach accelerator releasing coupler, said bleach accelerator releasing coupler having the formula:-(TIME) _n --S--R. _1- R ₂ [wherein TIME represents a timing group, n represents 0 or 1, and R ₁ represents (In the formula, L'represents an alkylene group having 1 to 8 carbon atoms)
Represents a linking group consisting of, and R ₂ is --COOH, --NHSO ₂ CH
_{3, -NHCOOCH 3, -NHCOOC 2 H} 5, -SO 3 H, -OH, --SO ₂ NH ₂ and --NR ₅ R ₆ (wherein R ₅ is H or 1 to 10 carbon atoms).
4 represents an alkyl group, R ₆ represents an alkyl group having 1 to 4 carbon atoms, at least one of R ₅ and R ₆ is an alkyl group, and the total number of carbon atoms in R ₅ and R ₆ is 8 or less. Which represents a water-solubilizing group selected from the group consisting of the following) or a precursor thereof: a silver halide photographic element containing a coupler moiety having a releasable bleach accelerator moiety.