JPS61201247A - Silver halide photographic element - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention]

FIELD OF INDUSTRIAL APPLICATION This invention relates to silver halide photographic elements containing bleach accelerator releasing couplers. BACKGROUND OF THE INVENTION Photographic materials useful for forming dye images by processes involving bleaching steps are known and used on the market. Such materials and methods are described, for example, in The Theor
y of the Photography%c Pro
cest. 4th edition, edited by T, H, James@, 4.62-463
and pages 335-361. The use of bleach accelerator-releasing couplers in such photographic materials is described in Re, search Disclosure, 19
3rd year, listed in Item shop 11449. Bleach accelerator releasing couplers, also known as BARC, contained a heterocyclic group as the bleach accelerator moiety which was released during processing of the photographic element. These bleach accelerator releasing couplers cause an undesirable degree of adverse development effects. Couplers having a thioether group in the pulling position are known in the field of photography. Examples of such couplers are, for example, U.S. Pat.
, 293,691. These compounds are useful as development inhibitor releasing (DIR) couplers. Almost all of the couplers, referred to as development inhibitor-releasing photogras, have a thioether group and are oil-soluble to help hold the coupler in one position in the hydrophilic emulsion layer of the photographic material. Vc'/i
:ing. Such couplers typically have a ballast 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. [Problem to be Solved by the Invention] The bleaching rate of the bleached silver halide dye in a dye-forming silver halide photographic element containing a dye-forming force sciller is as low as desired for exposure and processing. Forces that have a thioether group in the coupling position and are oil-soluble (typically as a result of the presence of a ballast group) yield a sufficiently strong affinity for silver and a water-solubility balance. [Means for solving the problem] The present invention provides a bleach accelerator-releasing coupler having the formula: % [where TIME represents a timing group, n represents 0 or l, and R, a bonding group, preferably an alkylene group having 1 to 8 carbon atoms or -N 7 II (L') (wherein L' represents an alkylene group having 1 to 8 carbon atoms or a phenylene group), and R2 is a halogenated steel photographic emulsion layer comprising a coupler moiety (group) having a releasable bleach accelerator moiety (4) representing a water-solubilizing group, preferably a carboxy group, or a precursor thereof; The foregoing problems are overcome by providing silver halide photographic elements containing bleach accelerator releasing couplers which, upon exposure and processing, enable the desired bleaching of such photographic materials. The releasable bleach accelerator group is present at a position on the compound having a group capable of releasing the bleach accelerator group at a point during processing of the photographic element to enable acceleration of the bleaching process. Bleach Accelerator Releasing Compound is preferably a coupler having a bleach accelerator group in the coupling position. The coupler may be a dye-forming sciller, but need not necessarily be a dye-forming sciller. A method of developing exposed silver halide photographic elements comprising a silver bleaching step, wherein the bleaching step comprises a bleach accelerator releasing compound, preferably a bleach accelerator releasing coupler such as those described above. Bleaching is improved when carried out in the presence of an agent group.As used herein, the term "coupler" refers to a silica group and a bleach accelerator group (TI]14E)n-S-R, -R2
Represents all compounds containing The term coupler, as used herein, refers to the portion of the compound other than the bleach accelerator group. A specific R that binds the sulfur atom and the water-solubilizing group R2. The groups can be varied to adjust cabarameters such as water solubility, diffusivity, sensitivity, ion complex solubility, kinetic development effects, and other sensitometric effects. Since these parameters can be adjusted by modifying R, these/parent parameters need not be of great importance when choosing a particular coupler group and a particular water-solubilizing group;
The selection of such groups and specific photographic elements and methods include:
Be free. During processing, the bleach accelerator fragments are released as units at appropriate times. That is, they are released as -S-R, -R2 companies- units. The rate and total time of diffusion of the bleach accelerator fragments in the photographic element should be such that they can promote bleaching in the appropriate layers of the photographic element during processing. If a timing group is present, this group also releases -S-R, -R2 as a -unit. The selection of R1 and R2 can also influence the rate and total time of release of the bleach accelerator group from the remainder of the compound, preferably the remainder of the coupler. It is necessary that the bleach accelerator group do not adversely affect the processing process and the photographic element. Optimal selection of R1 and R2 groups selects a bleach accelerator that is sufficiently water soluble to minimize the development inhibiting effects of the bleach accelerator groups and to improve the activity of the bleach accelerator. this is,
It helps distinguish between compounds that are useful image inhibitor releasing compounds and compounds that are useful bleach accelerator releasing compounds. Preferred photographic couplers having releasable bleach accelerator groups have the formula: COUP Fi coupler group, m represents 1 to 8, and R and R4 are each independently hydrogen or carbon -4 alkyl group, and the total number of carbon atoms in (C)m R4 is 1 to 8. The alkyl group is a straight-chain or branched alkyl group, such as a methyl group, an ethyl group, an n-gelobyl group, an i-gelobyl group,
Contains n-butyl and t-butyl groups. The coupler group may be any group that reacts with oxidized color developer to allow release of bleach accelerator groups. Coupler groups are useful in conventional dye-forming color pigments that produce dyes when reacted with oxidized color developers, as well as coupler groups that produce colorless products when reacted with oxidized color developers. Contains one unit. The coupler group may have or be free of oil-soluble groups. It may be a monomer or 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 developer, and the type of processing, the reaction product of the coupler group and the oxidized color developer may be (1) colored, non-diffusive, and in this case; teeth,
(2) is colored and diffusible, in which case it can be removed during processing or moved to a different location from the place where it was formed; or (3)
) colorless, diffusible or non-diffusible, in which case:
Reaction products do not contribute to image density. (2) and (3)
In this case, the reaction product is initially colored and/or non-diffusible, but may transform into a colorless and/or diffusible product during the course of the treatment. A bleach accelerator group is attached at each coupling position of the coupler group that can displace the bleach accelerator group when the coupler and oxidized color developer react. In bleach accelerator-releasing organic compounds, preferably bleach accelerator-releasing couplers, as described above, the bleach accelerator group may be linked to the remainder of the organic compound via a timing group (TIME). T in the above structural formula
IME adjusts the time from COUP to -S-R, -R2
It is a group that allows the release of The timing mechanism may be any timing mechanism useful for releasing a photographically useful group from a Kagler group. For example, the timing mechanism is described in, for example, U.S. Pat.
248,962 or 4,409,323. Release of the bleach accelerator group may involve one reaction or may involve a series of reactions. For example, T
Two or more consecutive reactions must occur within the I group. As another example, a TIME group connects two bleach accelerator groups to TIME
It can be attached to different positions on the substrate, and when the TIME group is released from one coupler group, two reactions occur in succession, allowing for the sequential release of two bleach accelerator groups. Another example is to release a second coupler group containing another timing group to which a photographically useful group is attached, and the TIME released after the second coupler group reacts with an oxidized color developer. It is basically a reaction. The TIME group determines the rate of reaction between COUP and the oxidized color developer, and when released from COUP -TIME-S-R
It may contain groups and substituents that can adjust one or more of the diffusion rate of 1-R2 and the rate of release of -8-R and R2. The TIME group may contain additional substituents, such as photographically useful additional groups that remain attached to the timing group and can be released independently. The TIME group may include a ballast group. Representative TIME groups are described in US Pat. No. 4,248,962 and US Pat. No. 4,409,323. R2 may optionally be a precursor group for a water-solubilizing group. For example, R211 may be an ester group that upon hydrolysis forms a water-solubilized carginic acid group. The following R2 groups are examples of useful water-solubilizing groups and their precursor groups: COOH -COOCH3 -COOC2H5 -NHSO2CH3 -N■cOOcH3 NHC00C2■5 o3H OH f-N O\l -SO2NH2 NR5R6 [wherein 85 represents ■ or an alkyl group having 1 to 4 carbon atoms, R6 represents an alkyl group having 1 to 4 carbon atoms, at least one of R5 and R6 is an alkyl group, and the total number of carbon atoms in R5 and R6 is 8 or less]. The following are examples of useful R2 groups: C2 - CH2CH2- -CH2CH2CH2- -CH2CH2C1{2CH2- -CH2CH-CH2CH2 2H5 -CH2CH20CH2CH2 -N 1t, 1% (L)- [wherein L' represents an alkylene group or a phenylene group having 1 to 8 carbon atoms], for example -N 1t II CH2CH2 or N //II Next, patent specifications and publications describing representative COUP groups useful in the present invention In their structures, indicate the unsaturated bond in each COUP group, the point of attachment to the TIME group, or, if the TIME group is present, the point of attachment to the bleach accelerator group. shows. The vertical unsaturated bond in the TIME group indicates the point of attachment of the coup, and the horizontal unsaturated bond in the TIME group indicates the point of attachment of the bleach accelerator group. 1, COITP A, a useful coupler that forms a cyan dye when reacted with an oxidized color developer is disclosed in U.S. Pat.
No. 2,162, No. 2,895,826, No. 3.0
No. 02,836, No. 3,034,892, No. 2.
4 F No. 4,293, No. 2.423. Fu No. 30,
It is described in representative patent specifications such as JP 2,367,531, JP 3,041,236 and JP 4,666,999. Such couplers form cyan dyes when reacted with oxidized color developer, and the coupling site, i.e.
Preferred are phenols and naphthols having a releasable bleach accelerator group attached to the 41-position of the coupler group. The structure of the preferred cyan dye-forming puller group is as follows: OH. +CONHR,2 [wherein R8, R, I, R,. , R, and R1□ each independently serve as a palust group, and R7 and R each contain at least one halogen atom, such as fluoride or fluorine, an alkyl group, such as an alkyl group having 1 to 4 carbon atoms, For example, it represents 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 zolopoxy group and a butoxy group]. Examples of such cyan color forming couplers are shown below. SCH2CH2COOH 1]ゝπOne dishNHC, 2H25 12ゝW'Rice)-Five leprosy C12H25 E! CM2CH2COOH C5H11″″! Fortune c,! Examples of couplers that form magenta dyes when reacted with oxidized color developers are e.g. U.S. Pat.
00. F No. 88, No. 2.369.489, No. 2
, 343. F No. 03, No. 2,311.082, No. 3,152.896, No. 3,519.429,
It is described in representative patent specifications such as JP-A No. 3,062,653 and JP-A No. 2,908.5-3. Preferably, such magenta dye-forming colorants are pyrazolones and pyrazolotriazoles that form magenta dyes when reacted with oxidized color developers. The structure of a preferred magenta dye-forming power sciller is shown below: R111, R15 and R1B each independently represent a palust group, or a phenyl group or a substituted phenyl group, such as 2.4.rho) 10 phenyl groups, e.g. 2
．． 4.64 represents a dichlorophenyl group]. The N of such a magenta dye-forming power sciller is shown below: //X'FN-N ■了1iJ7FCH2). CH. 8CH2CH2COOH (274). C, Kapler, Inc., which forms a yellow dye when reacted with an oxidized color developer, e.g., U.S. Patent No. 2.8 F 5
, No. 057, No. 2,407,210, No. 3.26
No. 5,506, No. 2,298,443, No. 3.0
No. 48,194 and No. 3.442, No. 928 are representative patent specifications. -・-' Such a yellow pigment-forming compound, +47#i, acyl, -1-:, amide, such as penzoylacetic acid 1. Preferably, there are compounds such as methane, trichloride, and piparyl acetanilide. Examples of yellow pigment-forming turnips such as ξ
Shown on the digit: -ji ji1;-1J seichi -1\\'-pe 1) -, knee, ; , :i) 5, L13-, - "22・-' 飄 [in the formula"2. :,,! -z:s, ^-B25 represents a group (independently), and "19, R20, I!2
□ and R, each of the two sides independently hydrogen or 1 or more fluorine, such as chlorine or fluorine, an alkyl group, such as alkyl group having 1 to 40 carbon atoms, such as a methyl group,
Ethyl group, propyl group and butyl group,
For example, it represents a tokoxy group or a 9-last group with 1 to 20 carbon atoms]. 9 examples of such yellow pigment-forming fogs are listed below: , So, NHCH3 SCH2CH2COOn CH-f-CNH-? Cufflers that form products that do not sufficiently absorb electromagnetic radiation within are disclosed, for example in British Patent No. 861,138;
U.S. Patent No. 3,632,345, U.S. Patent No. 3.928,0
No. 41, No. 3,958,993 and No. 3,961
, No. 959, and other representative patent specifications. Such couplers are cyclic carboxyl compounds that form colorless products when reacted with oxidized color developers. Preferably, it is a nyl group-containing compound. The structure of a typical coupler that forms a colorless product is shown below:
each independently represents a palust group, and m represents 1 or 2]. Examples of such couplers that can form colorless or nearly colorless products are shown below:
C〉0 Other colorless couplers, such as the oxasilinones, such as those listed below, are also useful ↓ Melon? CH2CH2C00H [R30 in the formula, -CH2-COOH CH2CH2-COOH CH2CH2CH2-COOH CH2CH2CH2CM2-COOH -CH2CH20H CH2CH2So5H -CH2CH2So2NH2 -CH2CH2CH2SO2 NH2 -CH-COOH CH2CH2-COOH OOH E, black dye when reacted with oxidized color developer Couplers forming
No. 31, No. 2,181,944, No. 2.333,
No. 106, No. 4,429,035, No. 4.439
．． ! No. 118, No. 4,254,213, No. 4.3
No. 87,158, No. 4,126,461, and No. 4,126,461! 4
, 200,466. Such couplers react with oxidized color developers.
．． Preferred are resorcinols or m-aminophenols which form a black product when mixed. The structure of a preferable colorant capable of forming a black pigment is shown below:
For example, an alkyl group having 3 to 2 carbon atoms, a phenyl group or a hydroxy group, a halo such as chlorine or bromine,
Amino group; alkyl group, e.g. alkyl group having 1 to 20 carbon atoms, or alkoxy group, e.g. 1 carbon atom
~2o represents a phenyl group substituted with an alkoxy group,
"ss and R54 each independently represent hydrogen, an alkyl group,
If kept, an alkyl group having 1 to 20 carbon atoms, a γ-arganyl group 111. t represents an alkenyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms; , e.g. C1-C20 alkyl groups, alkoxy groups, e.g. C1-C20 alkoxy groups, or other monovalent organic groups which do not adversely affect the dye formation or the release of bleach accelerator groups. [represents a group]. Examples of such couplers that can form black dyes are shown below: 0■ Cgongu8H! 7 1. TIME Useful TIλIE groups are suitable for release of bleach accelerator groups at appropriate times during processing, i.e., at points that can promote sunrise of the photographic element.
Rub the surface. Examples of such TIλIE groups are shown below as A, an acyclic TI 3.1E group [wherein n represents 1 to 4, R36 is hydrogen, an alkyl group, for example, a carbon atom number of 1 to 20]
an anoryl group or an aryol group, e.g. 6 carbon atoms
represents an anol group, preferably an unsubstituted phenyl group or a substituted phenyl group. Now (CH2)n-N-C- [In the formula, n represents 0 or 1, R, is hydrogen, an alkylated group, e.g., carbon number 1 to 207]
-alkyl or aryl group, e.g. from 6 carbon atoms
20 aryl groups, such as phenyl, X represents hydrogen, cyano, fluorine, chlorine, bromine, iodine, nitro, alkyl, such as chloro, propyl or butyl; It is preferably an unsubstituted phenyl group or a substituted phenyl coupler. The bleach accelerator-releasing compound added to the silver generide emulsion may be used singly or in combination with a bleach accelerator; the releasing coupler is a bleach accelerator-releasing compound that is added to the silver generator emulsion when the exposed photographic element is developed.
Condition in reactive combination with oxidized color developer

[
Photographic elements can be mixed in as shown. The coupler compound incorporated into the photographic processing solution should be of a processing size and structure. When incorporated into photographic elements, coupler compounds should generally be non-diffusive. That is, the compounds should have a molecular size and structure such that they do not significantly diffuse or migrate out of the layer being coated. Photographic elements incorporating couplers can be either unidirectional elements consisting of one silver halide emulsion layer or multilayer multicolor elements. The coupler compounds of the present invention can be used in silver halide emulsions 1 or 1, e.g., adjacent layers that come into reactive association with an oxidized color developing agent that regenerates the developed silver halide in the emulsion layer. It can be mixed inside and outside. The silver halide emulsion layer may contain or be combined with other photographically active compounds, such as development inhibitors, DIR couplers, color forming couplers and color masking couplers. These other photographic coupler compounds, also known as bleach accelerator-releasing compounds, are also known as bleach accelerator-releasing compounds. Furthermore, the iron halide emulsion 1 may contain magenta, which is normally included in such layers. Below 7. A typical multilayer, multicolor photographic element according to the present invention comprises a support and overlying K, a red-sensitive silver halide emulsion unit in combination with a cyan dye imaging material, a green-sensitive silver halide emulsion unit in combination with a magenta dye imaging material. a blue-sensitive silver halide emulsion unit in combination with a silver emulsion unit and a yellow dye image-forming material, at least one of the silver halide emulsion units being 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 with respect to each other. A typical arrangement is
U.S. Patent Nos. 3,227,554 and 3,620. No. 47 and No. 3,843,369 and British Patent No. 923,045. Coupler compounds may be incorporated into or combined with one or more layers or units of the element. The layers and units acted upon by bleach accelerator groups are:
Control can be achieved by providing at appropriate locations on the element a scavenger layer which confines the action of the bleach accelerator group to the desired layer or unit. Photosensitive silver halide emulsions are coarse, normal or fine.
containing silver chloride crystals or mixtures thereof, such as silver chloride, silver bromide, silver bromoiodide, silver chlorobromide, silver chlorobromide, silver bromoiodide and mixtures thereof; It may be included. The emulsions may be negative working or direct I diemulsions. These can form a latent image primarily on the surface of the halogenated steel grains, or they can form a latent image primarily within the halogenated scissor grains. These can be chemically and strategically sensitized. The emulsion is typically a gelatin emulsion, although other parent colloids can be used in a conventional manner. For example, Research Dis
closure, January 1983, Item 422
Particularly useful are the tabular grain silver halide photographic emulsions described in No. 534 and U.S. Pat. No. 4,434,226. If the coupler group is a dye-forming power coupler, it reacts with the oxidized developer in the same or an adjacent layer to produce a dye of the same or different color or hue than that obtained from the first coupler. can be formed. If the coupler group is a competitive sciller, it can react with oxidized color developer in the same or adjacent layer to reduce dye density. Typical concentrations of bleach accelerator releasing compounds in photographic elements range from about 50 m2 to about 5001197 m2. Particularly useful photographic elements according to the present invention are dye-forming photographic elements having layer structures known to be useful for forming multicolor images in subtractive processes. Any or all of the respective color records may be present in a two- or three-layer structure. Methods of forming dye images in photographic elements such as those described above involve conventional color processing including bleaching steps. Preferably, the bleaching step is carried out separately from fixing. Bleaching compositions include known bleaching agents. An example of a typical method is Research Disclosure, 1978
December, Item A17643 and “Modern
Photographic Processing
, by Grant Haist, vol. 2, 569-587.
Page (John Wiley and Sons1=:L
- Yo2r%C, published in 1979). Processing of dye-forming photographic elements according to the present invention typically includes color development steps, bleaching steps, and fixing steps. The bleaching and fixing steps can be combined into one step if desired. Other processing steps useful in this method include a precuring 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 at a temperature range of 18-60<0>C. Bleach accelerator releasing compounds are prepared by organic synthesis procedures known in the art of organic compound synthesis. For example, the coupler group can be reacted with a bleach accelerator in a suitable solvent. Two synthetic examples A describing representative methods of preparing bleach accelerator-releasing couplers: This example relates to the synthesis of bleach accelerator-releasing couplers: The following compound (coupler component) NiH 20g (33 mmol), -1=(2-carxyethyl)tetranoline-i-j on (bleach accelerator component) 51
9 (33 mmol) and potassium carbonate (K2Co, )
Heat the solution of 1411 at 80° C. for 2 hours. The resulting composition is then cooled and placed in water-cooled dilute hydrochloric acid. The resulting product is isolated and purified. This was done by extraction and then purification by silica chromatography and recrystallization from acetonitrile, yielding 11 t! j A colorless product is obtained. 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 cassola: cassol component: 6X; coct - (produced by the procedure described in U.S. Pat. )5.6jF (8 mmol・
), the formula in anhydrous pyridine 25d: i
2-dimethylamino-engineered tanthiol hydrochloride represented by iijζ-,-) 1. Add lII (8 mmol). τ the mixture
Stir at night? The resulting product is then poured into J water and extracted and made into a pulp. Each time the desired product is extracted with ethyl acetate, the isolated S-li geloin t1s-
The mixture is dried to give the desired bleach accelerator-releasing cup with a melting point of 130 °C and 111 °C, which is identified by spectroscopic and elemental analysis. ,,
,,---14 2l-・-mi, Ginma-sha completed example C knee 2-. L) :・-7,-Heh・:I・-′-Col. An example of -, -t is t for the synthesis of a bleach accelerator-releasing coupler.
-Is, ,,,1))][,. H r＼ Coupler component in tetrahydrofuran 75- stirred under nitrogen gas: 8H- r, -1,1--,,,,・'-''・--Pago'・-Drop# G q,,p Add 1.4 g (9,9 mmol) of St≧methykgufnidine and then add ethyl acetate t 1 yxl (−9,,9 mmol) to the solution, 3Q After a minute, the menu
50... and 1.25N sodium hydroxide solution 1G1
Add 17 and stir the resulting IjAIit product for 15 minutes. The mixture is then placed in urine cold dilute acid. 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 to 14
It is a colorless solid at 1°C. Further, the product is identified by elemental and spectroscopic analysis. Synthesis Example D = This example concerns the synthesis of a bleach accelerator-releasing coupler: 2ON (70 mmol) and 3-mercaptopropionic acid < H8CH2CH2COOH) 7.41 ()
dimethylformamide 251 to a stirred solution of 0 mmol)
3.85 ml of bromine in No. 17 is added dropwise. After stirring overnight, the mixture is placed in water. A single product (denoted P-2): Karibo N'rico is isolated by filtration. Next, P in ice vinegar #200y
11 J of zinc in a solution of -25-61 (13.7 mmol)
Add I and stir for 30 minutes before sifting. Next, 6.9 # (131 humimoles) of a compound designated as P-3 was added to the oral fluid, and 1
Stir for an hour and pour the mixture into water. The resulting product, isolated by extraction, is then dissolved in methanol/tetrahydrofuran (equal parts by volume), hydrolyzed with 50-sodium hydroxide solution and rendered hostile with an excess of cold dilute hydrochloric acid. The desired confession promoter-releasing coupler is then extracted and purified by silica chromatography. Ren's stimulant-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 hydration water. EXAMPLES Example q below further illustrates the invention '411'. Example 1 This example shows the bleach accelerator-releasing turnip according to the invention (・1
[,; A multilayer color photographic element designated as sample a was prepared by coating the following layers on a cellulose triacetate film support in the order listed: (shown as silver specularity): Layer l (bottom layer → low-sensitivity cyan layer - low-sensitivity vertical and horizontal sensitization^iodide #i semi-plate grain, +-v:, Latin emulsion (1615 啼-2 啓 gelatin (21153 m + 19/
m2). In this layer #i history, layer -4-e = 1 indicates shea y, -image dye-forming coupler (603 group t2): Below is a margin) The following coloring coupler (65If
/m2) and a development inhibitor-releasing type Kagura (43-4) designated as D-l. 0H. Layer 2: High Sensitivity Cyan Layer - As prescribed in U.S. Pat. No. 4,434,226
−,,,−fu,−. The 1ζ layer of the 1ζ layer of a red-sensitivity red-voice-smelling tabular-grain gelatin emulsion produced as shown in FIG.
61 one wv7m")" Tomoaki C-2 and 1 ↓ An image pigment forming Kailer (194"ff/m2):,
)1r Rini...he layer-, knee~-rya bi-←knee"
, 4"l(:j, sa;\i' and color development shown as 6C-3 - Lubra ←?<18~-勺二-imie"; ---j,
+: ζ-1 Mi 1 U18-5-＼;j-ぢIlsan-Hei,-,Body/knee and below margin-,,,,! t, j sea (l, 1・-
10), Ba, -On-layer-t-2\! 0 ■ NHCOCH. +1...-. 80, including H 03H. Layer 1':'\-Oki-Ku = Gelatin (1292 condolences (-2) Layer 4: Hyposensitive wrinkles Manen Ren III-Q!, y,. j-
Detailed Description: U.S. Patent No. 4.4. ．． ,4.4. %, a green sensitized silver bromoiodide tabular grain dried cyan emulsion prepared as described in No. 26. This layer further includes a magenta image dye-forming coupler designated as coupler M-1: J υ and a color-forming coupler designated as M3: ct ct \. and development inhibitor-releasing coupler L:5H,,-t, designated as K DIR coupler D-2. Layer 5: High Heat Magenta Layer High heat green sensitized silver iodide tabular grain gelatin emulsion prepared as described in U.S. Pat. No. 4,434,226. This layer further includes a magenta image dye-forming coupler designated as M-2: ct ct ¥2 I ct and a coloring power 1 color designated as M-3: Below is a margin CR Layer 6: Intermediate layer gelatin layer Ani Low sensitivity yellow layer US patent No. 4,434,226, an evening sensitized silver bromoiodide tabular grain gelatin emulsion (3-6 moles of iodine, 96 moles). This layer further includes a yellow image dye-forming layer Y-1 and a development inhibitor releasing layer Y-1.
DIR coupler 2 or less full white 1□ Highly sensitive evening sensitized silver bromoiodide gelatin emulsion. This layer further includes Y
Yellow negative image dye-forming capro-ANHS02C, designated -l;
6■3゜Layer 9: Overcoat layer A mixture of ultraviolet absorber and gelatin Coupler C-2 in layer 2 was mixed with comparative coupler C-4 in the amount shown in Table 1, and a bleaching accelerator. Release type coupler BARC
Samples s, d, f, and h were produced in the same manner as sample a, except that -1, -2, and -3 were used. Additionally, samples c, e, g, and i were similarly prepared by replacing coupler C-1 in layer l of sample a with the amounts indicated in the table of comparison coupler C-4 and BAR coupler 1.2 or 3, respectively. did. Each of these samples was exposed to white light through a graduated density stepper and a horn tablet, and Br.
itish Journal of Photography
phy Annual. 1979, pages 204-206. For the number of exposures, the density for red light is calculated as follows:
in E units) and are shown in Table 'A. The silver remaining after the bleaching step was measured by X-ray fluorometry and the average for the two highest exposure steps is shown in Table A. Kawa-1111 Toto dumb eyes 〒l2...l big...! 1 From the data shown in Table A, BARC-1, -2 or -3
It has been found that the addition of silver to the cyan layer of a multilayer element improves the removal of silver that would otherwise be retained and cause color reproduction problems. When added to a high-sensitivity layer at a relatively high concentration, BARC-1 and -2 cause a significant decrease in sensitivity, but with BARC-3, such a decrease is slight, and when added to a low-sensitivity layer, , all except BARC-2 increase the minimum concentration. In the present specification, comparison c-4 is the following compound: In the present specification, BARC-1 is the following compound: 71 is the following compound H In the present specification, BARC-2 is the following compound :H In the present specification, BARC-3 is a compound multilayer coupler-incorporated photographic element prepared by the same method as Sample a of Example 1 (the amount of coverage at the end is indicated by ■h-), and Control Sample j. was coated onto a film support as follows. Layer 1 (bottom layer) Low speed cyan layer - red sensitized silver bromoiodide tabular grain emulsion blend (1615),
Gelatin (21g3), cyan image coupler C-1 (6
03), chromogenic coupler C-2 (32) and DIR layer 2
: Layer 3: Layer 4: Layer 5: High speed cyan layer - High speed red sensitized silver bromoiodide tabular grain emulsion (1076), gelatin (1615), cyan image coupler C-2 (51) and color forming coupler C-3(4
8). Intermediate layer - Contains gelatin (1292). Low speed magenta layer - green sensitized silver bromoiodide tabular grain emulsion blend (1292),
Gelatin (16) 5), magenta image coupler M-1
(646), chromogenic coupler M-3 (43) and DIR coupler D-2 (13). High speed magenta layer - High speed red sensitized silver bromoiodide tabular grain emulsion (969), gelatin 7 (1292), magenta image coupler M-2 (108) and magenta layer except for the following changes: Sample k was produced in the same manner as Sample j. Trial layer 4: Layer 5: Coupler M-1 (484), coupler D-2 (32) and added bleach accelerator releasing coupler BARC-4 (
10B) Coupler M-2 (54) and added BA
RC-4 (54) Sample 1 was produced in the same manner as j except that the cyan layer was changed as follows. Sample layer 1: Layer 2: Coupler C-1 (5] 7 BARC-3 (s 6 ) Coupler C-2 (75 BARC-3 (60) ) and added) and added to the sample and in the preparation of t Sample m was prepared similarly to sample j except that bleach accelerator releasing couplers were added to cyan and magenta layers 1, 2.4 and 5 modified as indicated. Table B shows the photographic results after exposure and processing in the same manner as in Example. In the table, R, G, and W indicate that the sample was exposed to red light, green light, or white light, respectively. Table B Residual Ag (IIIg/m2) (and 1% removed)
Sample BAR compound GRW (control) Magenta layer 7 60 2] (80) (22), (75) Cyan layer (91) (94) (9]) Magenta and cyan layer 8 F 6 (76) (9]) ( 93) In this example, BARC-4 is the following compound: Below in the margin C72) The example below is adapted from Example IK, except that the bleach accelerator releasing coupler is replaced by the bleach accelerator releasing coupler shown in the example below. It can be implemented. t-S\8CH2eH2COOH In this example, BARC-6 is the following compound: /72N In this example κ, BARC-7 is the following compound [Effect of the invention]

Claims (1)

Claims: 1. A silver halide photographic element comprising a silver halide photographic emulsion layer and a bleach accelerator releasing coupler, wherein said bleach accelerator releasing coupler has the formula: -(TIME)_n- S
-R_1-R_2 [In the formula, TIME represents a timing group, n represents 0 or 1, R_1 is an alkylene group having 1 to 8 carbon atoms, or ▲There are numerical formulas, chemical formulas, tables, etc.▼ (In the formula, L' is represents a bonding group consisting of an alkylene group or a phenylene group having 1 to 8 carbon atoms, and R_2
represents a water-solubilizing group or a precursor thereof.