JPH0311456B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention This invention relates to color photographic elements containing scavengers for oxidized developing agents. PRIOR ART It is known in the art to add scavengers for oxidized developer to photographic elements to allow the scavenger to interact with the oxidized developer and prevent the developer from reacting at undesired locations or at undesired times. ing. As a scavenger for oxidized developer known in the art, U.S. Pat.
Stabilization 2,5 described in specification 4205987
-disulfonamidophenols and
Research Disclosure, February, 1979, Item
Examples include 2- or 4-sulfonamidophenols shown in No. 17842. Research
Disclosure is Industrial Opportunities Ltd.
Homewell, Havant, Hampshire, P09 1EF,
Published by Uuited Kingdom. Certain phenols are dye-forming couplers;
and is known in the art to react with oxidized color developing agents to form cyan dyes. 4-Sulfonamidophenols are specifically disclosed as dye-forming couplers in US Pat. No. 3,737,316. In view of the knowledge of those skilled in the art regarding the coupling of phenols with oxidized color developing agents, the scavengers described in the aforementioned U.S. Pat. No. 4,205,987 and Research Disclosure are capable of coupling with oxidized color developing agents may be expected to have limited use in color photographic elements to be processed with oxidized color developing agents where such stains are undesirable. Therefore, U.S. Pat. No. 4,205,987 and Research
Disclosure's sulfonamide phenols are primarily used in image transfer materials that do not use color developing agents for processing or materials that are present in a layer that is not visible when a scavenger views the final image. SUMMARY OF THE INVENTION It is an object of the present invention to provide a color photographic element containing an oxidized developer scavenger that does not form undesirable stains. This object, according to the present invention, is a color photographic element comprising at least one silver halide photographic emulsion layer and a scavenger for oxidized developing agent, wherein the scavenger is 2,4-disulfonamidophenol. or an alkali-labile precursor of the phenol. 2,4-disulfonamidophenol and the like used as scavengers in the present invention do not react with oxidized developing agents to form dyes or release photographically useful groups. A preferred sulfonamidophenol scavenger for oxidized color developing agents used in the present invention can be represented by the following structural formula: [In the above formula, G is hydroxy or its alkali-labile precursor; each R ¹ is individually alkyl having 1 to 30 carbon atoms,
an aryl having 6 to 30 carbon atoms, or a heterocyclic group having 5 to 30 carbon atoms having one or more heteroatoms selected from nitrogen, oxygen, sulfur and selenium; R ² , R ³ and R ⁴ are each individually hydrogen, halogen, alkyl group having 1 to 30 carbon atoms, alkoxy having 1 to 30 carbon atoms, aryl having 6 to 30 carbon atoms, or aryloxy having 6 to 30 carbon atoms]. The scavenger has sufficient bulk to be non-diffusive in the layers of the element. A particularly preferred sulfonamidophenol scavenger has the following structural formula: [In the above formula, each R ¹ is individually an alkyl having 1 to 30 carbon atoms or an aryl having 6 to 30 carbon atoms; and R ² , R ³ and R ⁴ are each individually hydrogen, or an alkyl having 1 to 30 carbon atoms; 30 alkyl or alkoxy having 1 to 30 carbon atoms]. In particularly preferred scavengers, ^R3 is C1-4 alkyl or C1-4 alkoxy and ^R2 and ^R4 are hydrogen. As mentioned above, G is a hydroxy group or an alkali-labile precursor of a hydroxy group. In an alkali-labile precursor, the hydrogen atom of the hydroxy group is replaced with a blocking group that is removed upon contact with a base. Typical blocking groups can be removed by hydrolysis or intermolecular nucleophilic substitution. Typical groups that can be removed by hydrolysis are acyl groups such as aliphatic and aromatic carbonyl and sulfonyl groups. Typical groups that can be removed by intermolecular nucleophilic substitution are described in US Pat. No. 4,310,612. The aforementioned alkyl, alkoxy, aryl and aryloxy substituents can be further substituted. Representative such substituents include halogen, nitro, alkyl, aryl, alkenyl,
Alkoxy, aryloxy, alkenyloxy, heterocyclyl, alkylcarbonyl, arylcarbonyl, alkenylcarbonyl, alkylsulfonyl, arylsulfonyl, alkenylsulfonyl, amino, aminocarbonyl, aminosulfonyl, carboxy, alkoxycarbonyl, aryloxycarbonyl and alkenyloxycarbonyl can be mentioned. Thus, alkyl includes, for example, arylalkyl and aryloxyalkyl, aryl includes, for example, alkaryl and alkoxyaryl, and alkenyl includes, for example, aralkenyl. The amine moieties of these additional substituents include primary, secondary and tertiary amines and acylated amines. Representative scavengers of the present invention are shown below. The compound used in the present invention is a known compound or a compound similar to a known compound, and can be prepared by a known reaction. To prepare compounds in which the sulfonamide groups in the 2- and 4-positions are the same, 2,4-diaminophenol is reacted with a suitable sulfonyl halide. If a different sulfonamide group is desired, 2-amino-
4-nitrophenol or 4-amino-2-nitrophenol is reacted with a suitable sulfonyl halide, one of which is attached to the amino substituent, the nitro group is then reduced, and by reduction of the nitro group A second sulfonyl halide is bonded to the amino group. If blocked compounds are to be prepared, the blocking group can be attached to the hydroxyl before or after attachment of the sulfonamide group. Representative preparations are shown in the Examples. The scavengers used in this invention can be used in the manner and for the purposes for which oxidized developer scavengers are used in the art. Scavengers can be included in the silver halide emulsion layer of the photographic element or in another layer of the element. If included in a separate layer, that layer is preferably an intermediate layer between silver halide emulsion layers, but any undercoat layer or silver halide emulsion layer coated below all of the silver halide emulsion layers. It can be an overcoat layer applied over the. The amount of scavenger compound used depends on the particular purpose for which the scavenger is being used and the degree of scavenging desired. 5 to 2000 scavengers
Useful results are typically obtained when used in amounts of mg/m ² . Scavengers can be incorporated into photographic elements by techniques known in the art. In certain preferred embodiments, the scavenger is dissolved in a high boiling point solvent, such as a water-insoluble coupler solvent;
It is then dispersed in a silver halide emulsion layer or another vehicle such as gelatin. Typically useful coupler solvents are solvents of moderate polarity such as tritolyl phosphate, di-N-butyl phthalate, diethyl lauramide, 2,4-dipentylphenol, and the like. Typical vehicles are gelatin and other hydrophilic colloids commonly used in silver halide photographic elements. These vehicles are described in Research Disclosure , December 1978,
Listed in Item No. 17643, Section IX.
Scavengers can be incorporated into the polymer latex of the element. A suitable technique for dispersing scavengers in latex is described in U.S. Pat. No. 4,203,716.
and 4214047 specification and Research
Disclosure, July 1977, Item 15930 and
Described in July 1980, Item 19551. Photographic elements of this invention can be simple monochrome color elements or multicolor multilayer elements comprising a support carrying a silver halide emulsion layer. These photographic elements can be designed to be processed in a separate solution or in-camera. Multicolor multilayers have dye image-forming units sensitive to each of the three primary regions of the spectrum.
Each unit can be composed of a single emulsion layer or multiple emulsion layers sensitive to a certain region of the spectrum. The layers of the element, including the layers of imaging units, can be arranged in various orders as is known in the art. In another form, the emulsion may be, for example,
It can be arranged as one or more segmented layers by using microcontainers or microcells as described in Belgian Patent No. 881,513. Preferred photographic elements according to the invention include at least one blue-sensitive silver halide emulsion layer having an associated yellow image dye-forming material, at least one green-sensitive silver halide emulsion layer having an associated magenta image dye-forming material, and a cyan image. It comprises a support carrying at least a red-sensitive silver halide emulsion layer having an associated dye-forming substance and a scavenger of the present invention. The scavenger is preferably present in an interlayer between silver halide emulsion layers sensitive to different regions of the visible spectrum, but not in interlayers between silver halide emulsion layers or silver halide emulsion layers sensitive to the same region of the visible spectrum. can exist in The photographic elements of the present invention may contain additional layers that are conventional in photographic elements such as overcoat layers, spacer layers, filter layers, antihalation layers, PH reducing layers (sometimes referred to as acidic and neutralizing layers), timing layers, opaque layers, etc. It can have a reflective layer, an opaque light absorbing layer, etc. The support can be any suitable support used in photographic elements.
Typical supports include polymeric films, paper (polymer coated paper), glass, and the like. For more information regarding the supports and other layers of photographic elements of this invention, see Research Disclosure , supra.
Described in December 1978, Item 17643. The light-sensitive silver halide emulsions used in the photographic elements of this invention contain coarse, regular or fine grained silver halide crystals or mixtures thereof, including silver chloride, silver bromide, silver bromoiodide, It can be composed of silver chlorobromide, silver chloroiodide, silver chlorobromoiodide, and mixtures thereof. The emulsion can be a negative working emulsion or a direct positive emulsion. The emulsion is capable of forming latent images primarily on or in the surface of the silver halide grains. Emulsions can be chemically and spectrally sensitized by conventional means. The emulsion is typically a gelatin emulsion, but other hydrophilic colloids can be used by conventional means. For more information about silver halide emulsions, see Research Disclosure ,
Item 17643, December, 1978 and the references listed in the text. Photographic silver halide emulsions may contain other auxiliaries that are common in photographic technology. Useful auxiliaries include, for example, Research Disclosure ,
Described in December 1978, Item 17643.
Useful auxiliaries include spectral sensitizing dyes and desensitizers, antifoggants, masking couplers, DIR
(Development inhibitor releasing) couplers, DIR compounds, antistain agents, image dye stabilizers, absorbing materials such as filter dyes and UV absorbers, light scattering materials, coating aids, plasticizers and lubricants. Depending on the dye-imaging material used in the photographic element, the dye-imaging material can be incorporated into the silver halide emulsion layer or into a separate layer associated with the emulsion layer. The dye image-forming material can be any of a number of materials known in the art, such as dye-forming couplers, bleachable dyes, dye developers, and redox dye releasing agents, depending on the particular used. This will vary depending on the nature of the element and the type of image desired. Dye imaging materials used with regular color materials that are designed to be processed in separate solutions are
Preferred are dye-forming couplers, ie compounds that couple with oxidized developing agents to form dyes. Preferred couplers that form cyan dye images are phenols and naphthols. Preferred couplers that form magenta dye images are pyrazolones and pyrazolotriazoles. Preferred couplers that form yellow dye images are benzoylacetonilides and pivalylacetonilides. Dye imaging materials useful in diffusion transfer film units include dye groups and monitoring
Contains groups. The monitor group is responsible for changes in the mobility of the dye group in the presence of alkaline processing solutions and as a function of silver halide development. These dye image-forming materials can be initially mobile and made immobile as a function of silver halide development, as described in US Pat. No. 2,983,606. Alternatively, the dye image-forming material can be initially immobile and rendered mobile as a function of silver halide development in the presence of an alkaline processing solution. This latter type of material includes redox dye releasing compounds. In such compounds, the monitor group is a carrier that releases dye as a direct function of silver halide development or as an inverse function of silver halide development, and includes 3-pyrazolidones such as 1-phenyl-3-pyrazolidone and 1-phenyl-3-pyrazolidone. Phenyl-4,4-dimethyl-3-pyrazolidone is a preferred developer. Compounds that release dye as a direct function of silver halide development are
They are called negative-working release compounds, while compounds that release dye as an inverse function of silver halide development are called positive-release compounds. A preferred class of negative-acting release compounds are the ortho- or para-sulfonamidophenols and naphthols described in US Pat. Nos. 4,054,312, 4,055,428 and 4,076,529. In these compounds, the dye group is attached to a sulfonamide group that is ortho or para to the phenolic hydroxy group and is released by hydrolysis after oxidation of the sulfonamide compound during development. A preferred class of positive release compounds are the nitrobenzene and quinone compounds described in US Pat. No. 4,139,379. In these compounds, the dye group is attached to a nitro group or an electrophilic cleavable group, such as a carbamate group, which is ortho to the quinone oxygen and is released upon reduction of the compound by an electron donor compound contained in the element or treatment composition. be done. However, in this case, it is necessary that the electron donor is not oxidized during development. Developing agents that can be used to develop photographic elements of this invention that can be reduced to oxidized forms by the scavenger of this invention include aminohydroxypyrazoles, aminophenols, and phenylenediamines. Certain developing agents, when used in certain applications, are referred to in the art as electron transfer agents. The particular developing agent used will vary depending on the particular type of photographic element being processed. As a representative preferred color developing agent, 4-
Amino-N-ethyl-N-β-hydroxy-ethyl-3-toluidine, N,N-diethyl-p-phenylenediamine, 3-methyl-N,N-diethyl-p-phenylenediamine, 3-methoxy-
Mention may be made of N,N-diethyl-p-phenylenediamine and N,N,N',N'-tetramethyl-p-phenylenediamine. In this text, "non-diffusive" has the meaning normally applied to the term in photography, and for all practical purposes processed in alkaline media, in photographic elements and preferably in media with a pH of 10 or higher. In this case, it refers to a substance that does not move or migrate in an organic colloid layer, such as gelatin. "diffusion"
has the opposite meaning and refers to a material that has the property of effectively diffusing through the colloidal layer of a photographic element in an alkaline medium. In this text, "in association" means that the materials can be present in the same or different layers, as long as the materials can be accessed to each other during processing. Example A mixture of 4.5 g (0.03 mol) of 2-amino-4-nitrophenol and palladium on charcoal catalyst in 60 ml of dimethylformamide was reduced in a Parr bottle with 40 psi of hydrogen until the theoretical amount was absorbed. Immediately after removing the catalyst by filtration, 6.3
g (0.075 mol) of sodium bicarbonate and 21.7
g (0.06 mol) of 4-dodecyloxybenzenesulfonyl chloride was added with stirring and the mixture was heated to drive off the carbon dioxide. The product isolated by pouring the reaction mixture into ice water was successively recrystallized from methanol, ethanol/hexane and acetonitrile to obtain 7.5 g of almost colorless crystals. mp137−139℃. The crystals had the correct elemental analysis values for Compound 1. 46.2 g (0.3 mol) of 4-amino-2-nitrophenol with 500 ml of tetrahydrofuran and 240 ml
34.4 g in a -10°C solution in pyridine of
(0.3 mol) of methanesulfonyl chloride was added dropwise over 10 minutes with stirring. After stirring for 18 hours, the liquid reaction mixture was poured into a vigorously stirred solution of 240 ml of concentrated hydrochloric acid in 800 ml of water, and the resulting precipitate was collected, washed, dried, decolorized, and recrystallized from acetonitrile. (2b) yellow crystals (mp164-6℃) with correct infrared and NMR spectra and good elemental analysis values at 32.5
I got g. A solution of 15 g (0.065 mol) of (2b) in 80 ml of tetrahydrofuran and 80 ml of methanol was hydrogenated over palladium on charcoal in a Parr apparatus overnight. The catalyst was then removed by filtration and the solvent was evaporated off. The obtained gray solid (2c) was dissolved in 200 ml of tetrahydrofuran and 50 ml of pyridine, and a solution of 21 g (0.065 mol) of 1-hexadecanesulfonyl chloride in 100 ml of tetrahydrofuran was added dropwise with stirring. After 4 hours, the reaction mixture was poured into 600 ml of ice water containing 50 ml of concentrated hydrochloric acid and the precipitate was collected. Recrystallization from acetonitrile gave 15.7 g of white crystals (mp 147 - 9°C) with correct analysis and spectrum for compound 8. The invention is illustrated by the following examples. To evaluate the effectiveness of the scavenger compounds used in the photographic elements of this invention as interlayer scavengers for oxidized color developing agents, a color negative test photographic element represented by the following schematic structure was used: In the element, the curing agent is bis(vinylsulfonylmethyl)ether and the coupler has the following formula: Couplers and test compounds were coated as dispersions in dibutyl phthalate or comparable coupler solvents. In this photographic element, the oxidized color developing agent that forms in the emulsion layer as exposed silver halide is developed can react with the yellow coupler to form a yellow dye. The oxidized color developing agent can also pass through the interlayer to the cyan layer where it can react with the coupler to form a cyan dye. Reactive test compounds in the interlayer can also react with the oxidized color developing agent, thereby limiting cyan dye formation in the cyan layer. For color negative photographic elements, it is usually more preferable to reduce the scavenger compound to couple with the oxidized developing agent. This is because the latter coupling reaction can lead to undesirable dye staining. The scavenging effectiveness of each test compound was determined by measuring the developed density ratio of cyan dye (665 nm) to yellow dye (450 nm). The more active scavenger compounds used in the present invention reduce this red/blue density ratio from a control value of about 0.40 (no scavenger in the interlayer) to about 0.20. One sample of each photosensitive element containing a different desired test compound prepared as described above was
Exposure through the stepped density test subject and then
British Journal of Photography, July, 12,
Color negative C described in 1974, pp.597-8
-41 process. Cyan dye staining (red density) of the final yellow dye image (blue density) was then measured on the sample. Cyan dye formation due to scavenger coupling was determined by visual inspection of a cross section of the sample. If cyan dye concentration was observed in the interlayer, the scavenger was considered to have coupled with the oxidized color developing agent.
The results are shown in the table below. TABLE TABLE The above table shows that the control and comparative compounds have lower scavenging capacity at equimolar levels and a greater tendency to form pigments due to undesired coupling compared to the scavengers used in the present invention.

Claims (1)

[Claims] 1 A color photographic element comprising at least one silver halide photographic emulsion layer and a scavenger for oxidized developing agent, wherein said scavenger is 2,4-disulfonamidophenol or an alkali of said phenol. A color photographic element characterized by being an unstable precursor.